Olefin polymer of very low polydispersity and process for preparing the same

The present invention relates to an olefin polymer and a method for producing the same, and more specifically, an olefin polymer having an extremely narrow molecular weight distribution, an olefin polymer containing two or more specific polymer blocks, and the above-mentioned olefin polymer having a functional group at the terminal. , Block copolymers and methods for producing olefin polymers used in the production of these olefin polymers.

Polymers with a narrow molecular weight distribution and a specific range of molecular weight, polymers with functional groups introduced at the ends, and block polymers with different segments bonded show various useful physical properties, so only from an academic point of view. Not only that, it is also very important from an industrial point of view.

It is generally well known that living polymerization, in which a termination reaction and a chain transfer reaction do not substantially occur during polymerization, is an effective method for producing a polymer having such a specific structure.

However, when a polymer having a specific structure as described above is produced, if polymerization is carried out under normal conditions using a general Zieglar catalyst or metallocene catalyst as an olefin polymerization catalyst, a chain transfer reaction of growing polymer chains will occur. It was very difficult to produce an olefin polymer by living polymerization because of the frequent occurrence of olefin polymers. For example, it has been clarified by analysis of molecular weight distribution, composition distribution, etc. that a mixture of homo and random copolymers is produced when an attempt is made to synthesize a block copolymer or the like using a known catalyst system (Non-Patent Document 1: Boor). , "Zieglar-Natta Catalyst and Polymerization", Academic Press, 1979).

Under these circumstances, some examples have been reported in which living polymerization of olefins was investigated. For example, Dohi et al. Have reported an example of performing living polymerization of propylene using a specific vanadium catalyst (Non-Patent Document 2: Macromolecules, Vol. 19, p. 2896, 1986). However, this method requires an extremely low polymerization temperature of -78 ° C to -40 ° C, and the polymerization activity is several tens of g-Polymer / mmol-M · h, which is not commercially sufficient. In addition, the polymer species that can be synthesized are also limited to polypropylene or propylene / ethylene copolymers having a low ethylene content (50 mol% or less), depending on the living polymerization of commercially useful polyethylene or ethylene-based copolymers. Manufacture is difficult. In addition, there is a problem that the obtained polypropylene has low stereoregularity (lasemidiad 0.8 or less), which is insufficient for industrial use.

Brookhart et al. And McConvill et al. Report methods for living polymerization of higher α-olefins such as propylene and 1-hexene with specific nickel complexes and titanium complexes, respectively (Non-Patent Document 3: Journal of American Chemical Society, Vol. 118). , 11664, 1996, Non-Patent Document 4: Journal of American Chemical Society, Vol. 118, p. 10008, 1996). In this case as well, it is often necessary to carry out low-temperature polymerization at 0 ° C. or lower, and the obtained polymer has an atactic structure having no stereoregularity. Further, with the above nickel complex and titanium complex, living polymerization of polyethylene or ethylene polymer is difficult.

Soga, Shiono et al. Are studying the living polymerization of propylene using a metallocene catalyst, but an extremely low polymerization temperature of -78 ° C to -60 ° C is required, and the polymerization activity and the molecular weight of the produced polymer are also low. Level (Non-Patent Document 5: Macromolecules, Vol. 31, p. 3184, 1998, Non-Patent Document 6: Macromolecular Rapid Communication, Vol. 20, p. 637, 1999).

Regarding the synthesis of polyethylene by living polymerization, which is generally considered difficult, Nakamura et al. Reported a method using niobium and tantalum complexes, and Yasuda et al. Reported a method using a samarium complex. However, even with these methods, the activity is low, the molecular weight of the produced polyethylene is limited to about 100,000, and there is a drawback that copolymerization of comonomer other than ethylene cannot be performed (Non-Patent Document 6: Journal of American Chemical Society, Vol. 115, 10990 pages, 1993).

Further, as a method for synthesizing a block polymer in which different segments are bonded, a method using a specific metallocene catalyst has been proposed (see Patent Document 1: International Publication WO91 / 12285, WO94 / 21700, etc.). It is stated that these methods also require low activity and low temperature polymerization (-10 ° C to 0 ° C), and that simply raising the polymerization temperature to 10 ° C reduces the blocking efficiency to less than 10%. ing. Therefore, it is impossible to produce a block polymer at a polymerization temperature (50 ° C to 75 ° C) that is usually used industrially. Furthermore, even in the case of low-temperature polymerization, the molecular weight distribution (Mw / Mn) of the block copolymer, which is an index of living polymerizability, cannot be said to be as narrow as 1.35 or more, and the living polymerization is not sufficiently controlled. Therefore, in most cases, the product has many industrial restrictions such as a large amount of unblocked polymer as a by-product and separation to remove unnecessary polymer in the post-treatment step is indispensable.

Therefore, if a method capable of living-polymerizing olefins at a high temperature that can be industrially produced and with high polymerization activity appears, its industrial value will be extremely large.

<p num="0011"><patcit num="1"><text>International release WO91 / 12285, WO94 / 21700</text></patcit></p>

<p num="0012"><nplcit num="1"><text>Boor, "Ziegler-Natta Catalyst and Polymerization", Academic Press, 1979</text></nplcit><nplcit num="2"><text>Macromolecules, Vol. 19, p. 2896, 1986</text></nplcit><nplcit num="3"><text>Journal of American Chemical Society, Vol. 118, p. 11664, 1996</text></nplcit><nplcit num="4"><text>Journal of American Chemical Society, Vol. 118, p. 10008, 1996</text></nplcit><nplcit num="5"><text>Macromolecules, Vol. 31, p. 3184, 1998</text></nplcit><nplcit num="6"><text>Macromolecular Rapid Communication, Vol. 20, p. 637, 1999</text></nplcit></p>

<p num="0013"> Under these circumstances, the applicant has found a transition metal compound having a salicylaldimine ligand as a new catalyst for olefin polymerization. Among the transition metal compounds having a salicylaldehyde ligand, those having a specific structure have a very high activity as compared with the conventionally known living polymerization at a high temperature that can be industrially produced. The present invention has been completed by discovering that living polymerization has progressed and it is possible to produce polyolefins having a high molecular weight and a narrow molecular weight distribution, polyolefins having quantitatively functionalized ends, and block copolymers. In addition, the present invention has been completed by inventing a method for efficiently producing such a polymer.</p><p num="0014"> That is, the present invention has an olefin weight showing various useful physical properties such as a polymer having a narrow molecular weight distribution and a specific range of molecular weight, a polymer having a functional group introduced at the terminal, and a block polymer in which different segments are bonded. The purpose is to provide coalescence. Another object of the present invention is to provide a method for producing these olefin polymers. Another object of the present invention is to provide a method for efficiently producing such a polymer.</p>

<p num="0015"> The olefin polymer according to the present invention is a polymer of at least one olefin selected from olefins having 2 to 20 carbon atoms, has a number average molecular weight of 500 or more, and has Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) is 1.5 or less. (Hereinafter, such a polymer may be referred to as "monodisperse polyolefin".) The monodisperse polyolefin according to the present invention includes polyethylene, high density polyethylene (hereinafter referred to as "HDPE"), linear low density polyethylene (hereinafter referred to as "LLDPE"), polybutene, ethylene and 4 to 20 carbon atoms. A copolymer with at least one olefin selected from olefins, dienes and cyclic olefins, and a copolymer with propylene and at least one olefin selected from olefins having 4 to 20 carbon atoms, dienes and cyclic olefins. Examples include olefin polymers.</p><p num="0016"> The monodisperse polyolefin according to the present invention is at least selected from ethylene polymers having a number average molecular weight of 110,000 or more and Mw / Mn of 1.5 or less, and olefins having 3 to 20 carbon atoms. Examples thereof include polymers of one type of olefin having a number average molecular weight of 500 or more, Mw / Mn of 1.5 or less, and a melting point of 70 ° C or more.</p><p num="0017"> Further, the monodisperse polyolefin according to the present invention is a polymer of propylene or butene.¹³Examples thereof include olefin polymers and ethylene / propylene copolymers having a racemic diad (r) of 0.85 or more measured by C-NMR and having an ethylene content of 60 mol% or more.</p><p num="0018"> The olefin polymer according to the present invention is at least two types of olefin copolymers selected from olefins having 2 to 20 carbon atoms, having a number average molecular weight of 500 or more, and two or more types of monomers in the polymer chain. Examples thereof include olefin polymers which are tapered polymers containing segments whose composition changes continuously, and examples thereof include tapered polymers having a Mw / Mn of 2.5 or less and tapered polymers having an ethylene content of 30 mol% or more.</p><p num="0019"> The olefin polymer according to the present invention includes a monomer unit M derived from an olefin having 2 to 20 carbon atoms.₁And the monomer unit M₁At least one monomer unit different from M₂It is an olefin copolymer consisting of¹³Measured by C-NMR [M₁ M₂], [M₁ M₁], [M₂ M₂], [M₁] And [M₂] Is also an olefin copolymer characterized by satisfying the following relationship.</p><p num="0020"> 1&gt; [M₁ M₂] / (2 × [M₁] × [M₂]) 1&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) (In the formula, [M₁] Is the monomer unit M₁Mole fraction, [M₂] Is Monomer M₂Mole fraction, [M₁ M₂] Is the monomer unit M₁And monomer unit M₂And the mole fraction of adjacent units, [M₁ M₁] Is the monomer unit M₁And monomer unit M₁And the mole fraction of adjacent units, [M₂ M₂] Is the monomer unit M₂And monomer unit M₂Indicates the mole fraction of adjacent units. )</p><p num="0021"> Further, as the olefin polymer according to the present invention, the monomer unit M isolated in the polymer and the polymer chain satisfying the above conditions and having Mw / Mn of 2.5 or less.¹And two or more consecutive monomer units M₁The chain of¹³Olefin copolymer detected by C-NMR, two consecutive monomer units M in the polymer chain₁Chain and 3 or more contiguous monomer units M₁Chain together¹³Also included are olefin copolymers detected by C-NMR.</p><p num="0022"> In this case, the monomer unit M₁Is preferably an ethylene unit, and there are two or more consecutive chains of methylene groups.¹³Also included are olefin copolymers that are detected by C-NMR and have both a chain of two consecutive methylene groups and a chain of three or more consecutive methylene groups.</p><p num="0023"> Further, the olefin polymer according to another aspect of the present invention includes (i) a polymer block obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms, and (ii) 2 to 2 carbon atoms. There are olefin block copolymers obtained from at least one olefin selected from 20 olefins and containing a polymer block different from the polymer block (i).</p><p num="0024"> Such an olefin-based block copolymer consists of two or more polymer blocks in which adjacent polymer blocks are different, the number average molecular weight of the entire polymer is 500 or more, and Mw / Mn is 2.5 or less. Some polymers are also mentioned.</p><p num="0025"> The olefin-based block copolymer is a diblock copolymer composed of two polymer blocks, an olefin polymer having Mw / Mn of less than 1.35, and a triblock composed of three polymer blocks. Examples of the polymer include an olefin polymer having a Mw / Mn of less than 1.80, and a multi-block copolymer composed of four or more polymer blocks having a Mw / Mn of less than 2.00.</p><p num="0026"> In addition, these olefin block copolymers are copolymers of polypropylene, HDPE, LLDPE, ethylene and at least one olefin selected from olefins having 3 to 20 carbon atoms, diene and cyclic olefins. Atactic polypropylene (hereinafter referred to as "ata-polypropylene"), isotactic polypropylene (hereinafter referred to as "iso-polypropylene"), syndiotactic polypropylene (hereinafter referred to as "syn-polypropylene"), propylene and 4 carbon atoms. Examples include copolymers with at least one olefin selected from ~ 20 olefins, dienes and cyclic olefins, or those selected from the tapered polymers described above.</p><p num="0027"> Furthermore, each polymer block is polyethylene, HDPE, LLDPE, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer, ata-, syn-polypropylene, propylene / Also included are diblock copolymers or triblock copolymers selected from butene copolymers, propylene / hexene copolymers.</p><p num="0028"> The polymer block (i) and the polymer block (ii) are selected from, for example, the following (a), (b) and (c); (a) Polymer block obtained from ethylene, (b) Polymer block obtained from one α-olefin selected from α-olefins having 3 to 20 carbon atoms, (c) Polymer block obtained from 2 to 20 carbon atoms A polymer block obtained from two or more α-olefins selected from α-olefins.</p><p num="0029"> Such an olefin block copolymer contains at least one polymer block (a), the number average molecular weight of the polymer block (a) is in the range of 110,000 to 10,000,000, and Mw / Mn is 1.5 or less. There is a polymer.</p><p num="0030"> Further, the olefin polymer according to another aspect of the present invention includes those having a functional group at the end of the main chain of the monodisperse polyolefin, tapered polymer, olefin copolymer, and olefin block copolymer as described above.</p><p num="0031"> The molded product according to the present invention is characterized by containing the above-mentioned monodisperse polyolefin, tapered polymer, olefin copolymer or olefin block copolymer. The method for producing an olefin polymer according to the present invention is a transition metal compound represented by the following general formula (I) in which one of X in the following general formula (I) is replaced with an n-propyl group. In the β-agotic structure obtained by the density general function method for the complex, the distance between the nearest hetero atom that does not have a direct bond with the central metal M and the hydrogen at the β position is 3.0 Å or less, and the electrostatic energy is -10 kJ /. In the presence of an olefin polymerization catalyst composed of a transition metal compound of mol or less, an olefin having 2 to 20 carbon atoms is polymerized to form a monodisperse polyolefin, an olefin copolymer, a tapered polymer or an olefin block copolymer as described above. It is characterized by manufacturing.</p><p num="0032"> L_mMX_n ... (I) (In the equation, M indicates the transition metal atom of groups 3 to 11 of the periodic table. m indicates an integer from 1 to 5 n is a number that satisfies the valence of M L is a ligand that coordinates with the central metal M and has a heteroatom that does not have a direct bond with the central metal. X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, Indicates a silicon-containing group, germanium-containing group or tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X are bonded to each other. May form a ring. ) Examples of the transition metal compound include a transition metal compound represented by the following general formula (II-a) or (II-b).</p><p num="0033"><chemistry num="1"><img id="000002" he="34" wi="84" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, M¹Shows the transition metal atoms of groups 3-11 of the periodic table. m indicates an integer from 1 to 5 Q is a nitrogen atom or substituent R²Indicates a carbon atom with A is an oxygen atom, a sulfur atom, a selenium atom or a substituent R⁵Indicates a nitrogen atom with R¹Indicates a hydrocarbon group having one or more heteroatoms or a hydrocarbon group having one or more heteroatom-containing groups. R²~ R⁵May be the same or different from each other, and are hydrocarbon groups, halogen atoms, hydrogen atoms, hydrocarbon-substituted silyl groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, It represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of these may be linked to each other to form a ring, and m is 2 or more. When is R¹R²R³R⁴R⁵They may be the same or different from each other, and R contained in any one of the ligands.²~ R⁵R contained in one of the groups and the other ligand²~ R⁵One of the groups may be connected, n is M¹Is a number that satisfies the valence of X is synonymous with X in the above general formula (I). )</p><p num="0034"><chemistry num="2"><img id="000003" he="41" wi="78" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, M¹Shows the transition metal atoms of groups 3-11 of the periodic table. m indicates an integer from 1 to 5 Y indicates a nitrogen atom or a phosphorus atom, U is a substituent R⁶Indicates a carbon atom, nitrogen atom or phosphorus atom having Q is the substituent R⁷Indicates a carbon atom, nitrogen atom or phosphorus atom having S is the substituent R⁸Indicates a carbon atom, nitrogen atom or phosphorus atom having T is the substituent R⁹Indicates a carbon atom, nitrogen atom or phosphorus atom having R¹And R⁶~ R⁹Are R in the above general formula (II-a), respectively.¹And R²~ R⁵Indicates the same atom or group as, and when m is 2 or more, R¹R⁶R⁷R⁸R⁹They may be the same or different from each other, and R contained in any one of the ligands.⁶~ R⁹R contained in one of the groups and the other ligand⁶~ R⁹One of the groups may be connected, n is M¹Is a number that satisfies the valence of X is synonymous with X in the above general formula (I). )</p><p num="0035"> In this case, the transition metal compound represented by the general formula (II-a) or (II-b) does not have a direct bond with the central metal M like the transition metal compound represented by the general formula (I). It is preferable that the distance between the closest heteroatom and the hydrogen at the β-position is 3.0 Å or less and the electrostatic energy is -10 kJ / mol or less.</p><p num="0036"> The transition metal compound represented by the above general formula (II-a) or (II-b) is R.¹Is an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and in the case of a phenyl group, the 2nd and 6th positions are taken when the position of the carbon atom bonded to nitrogen is 1st. Heteroatom at least one position has one or more substituents selected from heteroatoms or heteroatom-containing groups, or heteroatoms other than fluorine atoms at at least one position at the 3-position, 4-position and 5-position, 1 At least one substituent selected from a fluorine-containing group containing 1 carbon atom and 2 or less fluorine atoms, a fluorine-containing group containing 2 or more carbon atoms, and a heteroatom-containing group excluding a fluorine atom. In the case of an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, at least one substituent selected from a heteroatom and a heteroatom-containing group can be used. It is preferably a compound having.</p><p num="0037"> Further, the transition metal compound represented by the above general formula (II-a) or (II-b) is R.¹A phenyl group having one or more substituents selected from a halogen atom or a halogen-containing group at at least one position at the 2-position and the 6-position, or a 3-position, when the position of the carbon atom bonded to nitrogen is set to the 1-position. , A fluorine-containing group containing one carbon atom and two or less fluorine atoms at least at one of the 4- and 5-positions, a fluorine-containing group containing two or more carbon atoms, a chlorine atom, a bromine atom, and iodine. Fragrances other than phenyl group having at least one substituent selected from atomic, chlorine-containing group, bromine-containing group and iodine-containing group, halogen atom and aromatic group having at least one substituent selected from halogen-containing group An aliphatic hydrocarbon group having at least one substituent selected from a hydrocarbon group, a halogen atom and a halogen-containing group, and an alicyclic hydrocarbon group having at least one substituent selected from a halogen atom and a halogen-containing group. It is preferable that it is a halogen-containing hydrocarbon group having 1 to 30 carbon atoms selected from the above.</p><p num="0038"> Further, examples of the transition metal compound include a transition metal compound represented by the following general formula (III).</p><p num="0039"><chemistry num="3"><img id="000004" he="43" wi="81" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, M¹Indicates transition metal atoms selected from groups 4-5 of the periodic table. m indicates 1 or 2 R¹⁰Is an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and in the case of a phenyl group, the 2nd and 6th positions are taken when the position of the carbon atom bonded to nitrogen is the 1st position. Heteroatom at least one position has one or more substituents selected from heteroatoms or heteroatom-containing groups, or heteroatoms other than fluorine atoms at at least one position at the 3-position, 4-position and 5-position, 1 At least one substituent selected from a fluorine-containing group containing 1 carbon atom and 2 or less fluorine atoms, a fluorine-containing group containing 2 or more carbon atoms, and a heteroatom-containing group excluding the fluorine atom. In the case of an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, at least one substituent selected from a heteroatom and a heteroatom-containing group can be used. Have and R¹¹~ R¹⁴May be the same or different from each other, indicating a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. R¹⁵Indicates a halogen atom, halogen-containing group, hydrocarbon group or hydrocarbon-substituted silyl group, n is M¹Is a number that satisfies the valence of X is synonymous with X in the above general formula (I). ).</p><p num="0040"> In the present invention, in the transition metal compound represented by the above general formula (III), R¹⁰A phenyl group having one or more substituents selected from a halogen atom or a halogen-containing group at at least one position at the 2-position and the 6-position, or a 3-position, when the position of the carbon atom bonded to nitrogen is set to the 1-position. , A fluorine-containing group containing one carbon atom and two or less fluorine atoms at least at one of the 4- and 5-positions, a fluorine-containing group containing two or more carbon atoms, a chlorine atom, a bromine atom, and iodine. Fragrances other than phenyl group having at least one substituent selected from atomic, chlorine-containing group, bromine-containing group and iodine-containing group, halogen atom, aromatic group having at least one substituent selected from halogen-containing group An aliphatic hydrocarbon group having at least one substituent selected from a hydrocarbon group, a halogen atom and a halogen-containing group, and an alicyclic hydrocarbon group having at least one substituent selected from a halogen atom and a halogen-containing group. It is preferable that it is a halogen-containing hydrocarbon group having 1 to 30 carbon atoms selected from the above.</p><p num="0041"> By such a production method, for example, the monodisperse polyolefin, tapered polymer or olefin block copolymer as described above can be produced. In the method for producing an olefin polymer according to another aspect of the present invention, an olefin having 2 to 20 carbon atoms is polymerized in the presence of an olefin polymerization catalyst composed of the above transition metal compound to produce an olefin polymer. Next, the polymer is brought into contact with a functional group-containing compound to produce an olefin polymer having a functional group at the terminal.</p><p num="0042"> Further, the method for producing an olefin polymer according to another aspect of the present invention comprises at least two types of polymerization reactivity selected from olefins having 2 to 20 carbon atoms in the presence of an olefin polymerization catalyst composed of the above transition metal compound. It is characterized in that different olefins coexist to produce a tapered polymer containing segments in which two or more kinds of monomer compositions change continuously.</p><p num="0043"> Further, the method for producing an olefin polymer according to another aspect of the present invention is an olefin system composed of a plurality of polymer blocks by performing the following steps (1) and (2), and if necessary, an arbitrary number of steps (3). It is characterized by producing block copolymers; (1) A step of producing a polymer block by polymerizing at least one olefin selected from olefins having 2 to 20 carbon atoms in the presence of an olefin polymerization catalyst composed of the above transition metal compound. (2) The polymer block produced in (1) by polymerizing at least one olefin selected from olefins having 2 to 20 carbon atoms in the presence of the polymer block produced in the above step (1). The process of manufacturing a polymer block different from (3) At least selected from olefins having 2 to 20 carbon atoms in the presence of a block copolymer containing the polymer block obtained in the above step (1) and the polymer block obtained in (2). A step of polymerizing one type of olefin to produce a polymer block different from the polymer block produced in the previous step.</p><p num="0044"> Further, in the method for producing an olefin polymer according to another aspect of the present invention, a tapered polymer or an olefin-based block copolymer is produced by the above method, and then the copolymer is brought into contact with a functional group-containing compound. It is characterized by producing a tapered polymer or an olefin-based block polymer having a functional group at the terminal.</p><p num="0045"> Further, in the method for producing an olefin polymer according to another aspect of the present invention, the olefin is polymerized in the presence of a polymerization catalyst that promotes the living polymerization of the olefin, and the bond between the catalyst generated in the system and the produced polymer chain is chain-transferred. It is characterized in that olefins are further polymerized using a catalyst obtained by cleaving by a reaction.</p><p num="0046"> The chain transfer reaction can be carried out using at least one compound selected from, for example, hydrogen, organoaluminum compounds, organoboron compounds, organozinc compounds, organosilicon compounds, organocadadmium compounds and organolead compounds.</p><p num="0047"> Examples of the olefin polymerization catalyst used at this time include an olefin polymerization catalyst composed of the above-mentioned transition metal compound, and examples of the polymer to be produced include the above-mentioned monodisperse polyolefin, olefin copolymer, tapered polymer or olefin-based block polymer. Can be mentioned.</p><p num="0048"> Further, in the above method for producing an olefin polymer, at least one of the olefin polymer obtained before the chain transfer reaction and the olefin polymer obtained after the chain transfer reaction are monodisperse polyolefin, olefin copolymer, tapered polymer or It is preferably an olefin-based block polymer, and both the olefin polymer obtained before the chain transfer reaction and the olefin polymer obtained after the chain transfer reaction are the above-mentioned monodisperse polyolefin, olefin copolymer, tapered polymer or More preferably, it is an olefin-based block polymer. Further, the olefin polymer obtained before the chain transfer reaction and the olefin polymer obtained after the chain transfer reaction may be the same.</p>

<p num="0049"> The olefin polymer according to the present invention exhibits various useful physical characteristics. According to the method for producing an olefin polymer of the present invention, an olefin polymer having a high polymerization activity, a high molecular weight and a narrow molecular weight distribution, a tapered polymer having a precisely controlled structure, or various olefin block copolymers is highly polymerized. Can be obtained at temperature.</p>

<figref num="1">FIG. 1 is a schematic view showing an example of a step of preparing an olefin polymerization catalyst that may be used in the present invention.</figref>

Hereinafter, the olefin polymer according to the present invention and a method for producing the same will be specifically described. In the present specification, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" is used not only for homopolymers but also for copolymerization. It may be used in the sense of including coalescence.

The olefin polymer (monodisperse polyolefin) according to one aspect of the present invention is a polymer of at least one olefin selected from olefins having 2 to 20 carbon atoms (hereinafter, may be referred to as olefins). is there. This olefin polymer may be a polymer of one kind of olefin selected from olefins having 2 to 20 carbon atoms, and may be a random copolymer of two or more kinds of olefins selected from olefins having 2 to 20 carbon atoms. It may be a coalesced or block copolymer.

Here, examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-. Linear or branched α-olefins with 2 to 20 carbon atoms such as 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. ; Cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Examples thereof include cyclic olefins having 3 to 20 carbon atoms such as naphthalene.

Further, examples of the olefin having 2 to 20 carbon atoms include vinylcyclohexane, diene and polyene. Examples of the diene or polyene include cyclic or chain compounds having 4 to 20 carbon atoms and having two or more double bonds. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadien, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, ethiridene norbornene, vinyl norbornene, dicyclopentadiene; Examples thereof include 7-methyl-1,6-octadien, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatorien and the like.

Further, as olefins, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like can be used. Mono or polyalkyl styrene; And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. These olefins can be used alone or in combination of two or more.

Further, examples of the olefin used in the present invention include monomers having atoms other than carbon and hydrogen, and specific examples of such monomers include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, and itacone anhydride. Α, β-unsaturated carboxylic acids such as acids, cyclic olefin carboxylic acids such as bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acids and their anhydrides, and their sodium and potassium salts. , Lithium salt, zinc salt, magnesium salt, calcium salt and other metal salts; Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; Unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl ester of itaconic acid; Halogenated olefins such as vinyl fluoride, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide; Unsaturated cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amides such as acrylamide, methacryloamide, N, N-dimethylacrylamide Vinyl methyl ketone, unsaturated ketones such as vinyl ethyl ketone; Unsaturated ethers such as methyl vinyl ether and ethyl vinyl ether; Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; Examples thereof include vinyl group-containing heterocyclic compounds such as N-vinylpyrrolidone, N-vinylcarbazole, and vinylpyridine.

At least one of the olefins used in the present invention is an olefin consisting only of carbon and hydrogen. The amount ratio of the olefin consisting only of carbon and hydrogen to the total olefin is not particularly limited, and examples thereof include an amount of 5 mol% or more and 100 mol% or less of the total olefin. Further, at least one kind is sufficient if at least one kind of olefin consisting only of carbon and hydrogen is contained in the whole olefin polymer according to the present invention, for example, an olefin polymer composed of a plurality of polymer blocks. If so, any polymer block may contain an olefin consisting only of carbon and hydrogen.

The monodisperse polyolefin has a number average molecular weight of 500 or more, preferably 500 to 10,000,000, more preferably 1,000 to 5,000,000, and Mw / Mn of 1.5 or less, preferably 1.3 or less.

The weight average molecular weight, number average molecular weight and Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) were measured at 140 ° C using GPC (gel permeation chromatography) in an orthodichlorobenzene solvent. To. The obtained polymer molecular weight was converted into polystyrene-equivalent molecular weight by the universal method. When the produced polymer was monodisperse polyethylene and monodisperse ethylene / propylene copolymer, it was calculated in terms of polyethylene, and in other cases (tapered polymer, olefin block copolymer), it was calculated in terms of polypropylene. The parameter values used are as follows.

Polystyrene standard sample: K = 0.000137 α = 0.686 Polyethylene K = 0.000326 α = 0.77 Polypropylene K = 0.0001 q = 0.8 The melting point of the obtained polymer is measured using a differential thermal analyzer (DSC) under a nitrogen stream under a heating condition of 10 ° C / min.

¹³Measurement and analysis by C-NMR can be carried out by a conventionally known method.¹³The literature on measurement and analysis by C-NMR is illustrated below. 1) LPLindeman, JQ Adams, Anal. Chem., 43, 1245 (1971). 2) FABovey, MC Sacchi, A. Zambelli, Macromolecules, 7,752 (1974). 3) JC Landall, Macromolecules, 11,33 (1978). 4) A. Zambelli, P. Locatelli, G. Bajo, Locatelli, 12,154 (1979). 5) Y. Doi, Macromolecules, 12,248 (1979). 6) N.Kashiwa, A.Mizuno, S.Minami, Polymer.Bull., 12,105 (1984). 7) P.Ammendola, L.Oliva, G.Gianotti, A.Zambelli, Macromolecules, 18,1407 (1985). 8) T. Tsutsui, A. Mizuno, N. Kashiwa, Polymer, 30,428 (1989). 9) T.Tsutsui, N.Ishimaru, A.Mizuno, A.Toyota, N.Kashiwa, Polymer, 30,1350 (1989).

The monodisperse polyolefin according to the present invention includes polyethylene, HDPE, and LLDPE (polyethylene is an ethylene polymer having a comonomer content of less than 0.01 mol%, and HDPE is an olefin having 3 to 8 carbon atoms as a comonomer component. It is preferably an ethylene copolymer containing propylene, 1-butene or 1-hexene in a proportion of 0.01 mol% or more and less than 3 mol%, and LLDPE is an olefin having 3 to 8 carbon atoms as a comonomer component, preferably propylene. , 1-Butene or 1-Hexene in an proportion of less than 3-10 mol%), Polyethylene, Polyethylene, 1-Pentene, 1-Hexene, 1-octene, 1-decene, etc. Monopolymer, Ethylene and propylene copolymer, ethylene and olefin with 4 to 20 carbon atoms (1-butane, 1-pentene, 1-hexene, 1-octene as olefins with 4 to 20 carbon atoms Alpha-olefins such as 1-decene; butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, diene such as 1,7-octadiene; aromatic vinyl compounds such as styrene; tetracyclododecene, norbornene, Cyclic olefin compounds such as methylnorbornene can be mentioned. When the comonomer is an olefin having 3 to 8 carbon atoms, the comonomer content is 10 mol% or more, and in other cases, the comonomer content is 0.01 mol% or more. is there.).

A copolymer of propylene and an olefin having 4 to 20 carbon atoms (including the above-mentioned diene, aromatic vinyl compound, and cyclic olefin compound) is preferably used. Of the above examples, the copolymer may contain one or more comonomer.

Among these, polyethylene, HDPE, LLDPE, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / butene copolymer, and ethylene / hexene copolymer are preferable, and HDPE, LLDPE, polypropylene, polybutene, and ethylene / propylene are used together. Polymers, ethylene / butene copolymers and ethylene / hexene copolymers are particularly preferred.

The monodisperse polyolefin according to the present invention is a polymer of ethylene having a number average molecular weight of 110,000 or more, preferably 110,000 to 10,000,000, more preferably 150,000 to 5,000,000, and Mw / Mn of 1.5 or less. It is preferably a polymer having a number of 1.3 or less, preferably a polymer of at least one olefin selected from olefins having 3 to 20 carbon atoms, and having a number average molecular weight of 500 or more, preferably 500 to 10,000,000. More preferably, it is a polymer in the range of 1,000 to 5,000,000, Mw / Mn is 1.5 or less, preferably 1.3 or less, and a polymer having a melting point of 70 ° C. or more is also preferable.

In the case of a polymer of propylene or 1-butene, the number average molecular weight is in the range of 500 or more, preferably 500 to 10,000,000, more preferably 1,000 to 5,000,000, and Mw / Mn is 1.5 or less, preferably 1.3 or less. Yes,¹³The racemic diad (r) measured by C-NMR is 0.85 or more, preferably 0.90 or more.

In the case of an ethylene / propylene copolymer, the ethylene content is preferably 60 mol% or more, more preferably 70 mol% or more. The monodisperse polyolefin according to the present invention may be further bonded to other structural portions as long as the object of the present invention is not impaired. Further, the polymer of the present invention may be graft-modified or the like.

Further, the olefin polymer according to the present invention is a copolymer of at least two types of olefins selected from olefins having 2 to 20 carbon atoms, and has a number average molecular weight of 500 or more, preferably 500 to 10,000,000, more preferably. Is in the range of 1000 to 5,000,000 and includes so-called tapered polymers containing segments in which two or more monomer compositions change continuously.

Here, the tapered polymer is a polymer in which the comonomer composition gradually changes from one end of the polymer to the other end. This polymer can be synthesized by polymerizing two or more monomers (eg ethylene and propylene) in a complete living polymerization system where chain transfer reactions do not occur substantially. If the living property of the polymerization system is insufficient, a completely tapered polymer cannot be obtained, resulting in a mixture of copolymers having different compositions. The living property of the polymerization system is judged by the molecular weight distribution (Mw / Mn) of the polymer to be produced. When the livability of the polymerization system is high and a completely tapered polymer is produced, the value of Mw / Mn is preferably 2.5 or less, more preferably 1.8 or less, and further preferably 1.5 or less.

In this case, the two or more kinds of monomers are selected from the above-mentioned olefins having 2 to 20 carbon atoms, and are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, and 1 -Preferably selected from octene, more preferably ethylene, propylene, 1-butene. Further, one of the monomers is more preferably ethylene, and the ethylene content is particularly preferably 30 mol% or more.

Specific examples of the tapered polymer include ethylene / propylene tapered polymer, ethylene / butene tapered polymer, ethylene / hexene tapered polymer, propylene / butene tapered polymer, and propylene / hexene tapered polymer.

As long as the tapered polymer according to the present invention has the above-mentioned structure, it may be bonded to a portion having a structure other than the above-mentioned structure as long as the object of the present invention is not impaired. Further, the polymer of the present invention may be graft-modified or the like.

Further, examples of the olefin polymer according to the present invention include the following olefin copolymers. A polymer composed of two or more types of monomer units, which is a monomer unit (M) derived from an olefin having 2 to 20 carbon atoms.₁) And the monomer unit M₁At least one monomer unit different from (M₂)¹³Obtained by C-NMR [M₁ M₂], [M₁ M₁], [M₂ M₂], [M₁], [M₂] Is an olefin copolymer that satisfies the relationship of the following formula.

1&gt; [M₁ M₂] / (2 × [M₁] × [M₂]) ... (A) 1&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B) Here, [M₁] Is the monomer unit M₁Mole fraction, [M₂] Is the monomer unit M₂Mole fraction, [M₁ M₂] Is the olefin unit M₁And monomer unit M₂And the mole fraction of adjacent units, [M₁ M₁] Is M₁And M₁And the mole fraction of adjacent units, [M₂ M₂] Is the monomer unit M₂And monomer unit M₂Is the mole fraction of adjacent units. Here [M₁] + [M₂] = 1.0, and [M₁ M₂] + [M₁ M₁] + [M₂ M₂] = 1.0.

Monomer unit M in the polymer chain₁And monomer unit M₂If and is included statistically randomly, then [M₁ M₂] Generation probability is 2 × [M₁] × [M₂]become. Here, multiplying by 2 is [M₁ M₂] Is strictly M₁-M₂Unit and M₂-M₁This is because it is the mole fraction of the unit which is the sum of the units of. The above formula (A) is a monomer unit M.₁And monomer unit M₂Indicates that there are fewer adjacent units than if they were included statistically randomly. This is the monomer unit M in one polymer chain₁High content of and monomer unit M₂It is shown that the portion having a high content of is coexisting, which is a phenomenon observed in tapered polymers and block polymers.

Since the structure of the olefin copolymer according to the present invention is precisely controlled, Mw / Mn is usually 2.5 or less, preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.6 or less, still more preferably 1.5 or less. , Most preferably 1.3 or less.

When synthesizing a tapered polymer or a block polymer satisfying the above formula (A) by the conventional technique, the monomer unit M at the time of polymerization₁And monomer unit M₂There is a possibility that a polymer apparently satisfying the above formula (A) can be synthesized by changing the supply ratio with and over time. But the monomer unit M₁And monomer unit M₂Since the reactivity at the time of polymerization is different from that of the above, the reactivity of the supplied monomer changes with time, and Mw / Mn does not decrease as in the present invention.

On the other hand, when trying to produce a polymer having a small Mw / Mn by the conventional technique, the monomer unit M at the time of polymerization is prevented in order to prevent the reactivity of the supplied monomer from changing with time.₁And monomer unit M₂Since it is necessary to keep the supply ratio with and constant, [M₁ M₂] Generation probability is 2 × [M₁] × [M₂], And it becomes impossible to satisfy the above equation (A).

In the present invention, it is possible to precisely control the polymer structure even when the reactivity of the supplied monomer changes with time. The formula (A) is preferably the following formula (A-2). 0.95 [M₁ M₂] / (2 × [M₁] × [M₂]) ... (A-2) Further, it is more preferable that the following formula (A-3) is used. 0.90 [M₁ M₂] / (2 × [M₁] × [M₂]) ... (A-3) The formula (B) is a formula for verifying the contents described in the formula (A) with higher accuracy.

As mentioned above [M₁ M₂] Is strictly M₁-M₂Unit and M₂-M₁Since it is the mole fraction of the unit that is the sum of the units of₁Next to the monomer unit M₂Is inserted M₁-M₂Unit and monomer unit M₂Next to the monomer unit M₁Is inserted M₂-M₁The probability of generating all units is [M₁ M₂] / 2. The end of the polymer is the monomer unit M₁And then the monomer unit M₁Or monomer unit M₂Is inserted and M₁-M₁Unit or M₁-M₂If the polymerization proceeds statistically randomly, the production ratio of both is [M.₁] And [M₂] Matches the ratio. That is, the following equation (B-0-1) is satisfied.

([M₁ M₂] / 2) / [M₁ M₁] = [M₂] / [M₁] ... (B-0-1) On the other hand, the terminal indicator monomer unit M of the polymer₂And then the monomer unit M₁Or monomer unit M₂Is inserted and M₂-M₁Unit or M₂-M₂If the polymerization proceeds statistically randomly, the production ratio of both is [M.₁] And [M₂] Matches the ratio. That is, the following equation (B-0-2) is satisfied.

([M₁ M₂] / 2) / [M₂ M₂] = [M₁] / [M₂] ... (B-0-2) That is, when the polymerization proceeds statistically randomly, the following equation (B-0) is established by multiplying both sides of (B-0-1) and (B-0-2).

1 = [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-0) The above formula (B) is a monomer unit M.₁And monomer unit M₂Indicates that there are fewer adjacent units than if they were statistically randomly generated. This indicates that the probability of continuous insertion of homologous comonomer at the end of the polymer chain during formation is higher than the probability of insertion of comonomer different from the end of the polymer chain. It shows that it is possible to synthesize a block polymer.

Since the structure of the olefin copolymer according to the present invention is precisely controlled, Mw / Mn is 2.5 or less, preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.6 or less, still more preferably 1.5 or less. Most preferably, it is 1.4 or less. The formula (B) is preferably the following formula (B-2), more preferably the following formula (B-3), more preferably the following formula (B-4), and the following. The formula (B-5) is even more preferable, the formula (B-6) below is even more preferable, and the formula (B-7) below is most preferable.

0.95&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-2) 0.90&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-3) 0.85&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-4) 0.80&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-5) 0.75&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-6) 0.70&gt; [M₁ M₂]²/ (4 × [M₁ M₁] × [M₂ M₂]) ... (B-7) The reason why a polymer having a small Mw / Mn and satisfying the above formula (B) cannot be produced by the conventional technique like the tapered polymer manipulated in the present invention is that the above-mentioned Mw / Mn is small and the above formula (A) is used. This is similar to the reason why the polymer that meets the requirements cannot be produced.

Among the olefin copolymers according to the present invention, which satisfy the relationship of the formulas (A) and (B) and have Mw / Mn of 2.5 or less, the tapered polymer is an isolated monomer unit M in the polymer chain.₁And two or more consecutive monomer units M₁That both chains exist¹³Detected by C-NMR. Such a tapered polymer structure¹³There is no precedent analyzed by C-NMR, and it was revealed for the first time by the technique of the present invention capable of advancing highly precise polymerization.

On the other hand, in the block polymer, the isolated monomer unit M₁Is not detected and two or more consecutive monomer units M₁Only the chain of is detected. In the tapered polymer structure first revealed in the present invention, two consecutive monomer units M₁Chain and 3 or more contiguous monomer units M₁It is preferable that the chain of is detected. That is, the isolated monomer unit M₁, Monomer unit M₁Only two consecutive units, three or more monomer units M₁Are three consecutive units at the same time¹³It is preferably detected by C-NMR.

Monomer unit M₁And monomer unit M₂Is derived from the monomer exemplified as the above-mentioned olefin having 2 to 20 carbon atoms. Monomer unit M₁As, those derived from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene are preferable, and those derived from ethylene are more preferable. Monomer unit M₂As for the above, those derived from propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene are preferable, and those derived from propylene and 1-butene are more preferable.

Monomer unit M¹If is an ethylene unit, then the isolated monomer unit M¹, Monomer unit M¹Only two consecutive units, three or more monomer units M¹Are three consecutive units at the same time¹³It is preferably detected by C-NMR. In addition, the isolated monomer unit M²And two or more monomer units M²Is a continuous monomer unit M²Is also preferably detected at the same time. That is, a chain of two or more consecutive methylene groups¹³It is preferable that all chains of 1, 2, 3, 4, 5, and 6 or more methylene groups are detected by C-NMR. Further, it is more preferable that the mole fractions of chains of 1, 2, 3, 4, 5, and 6 or more methylene groups are detected as different values.

¹³As described above, the measurement and analysis by C-NMR can be carried out by a conventionally known method. Such olefin copolymers are suitably used for various molding materials such as films, sheets and blow molded products, various additives such as compatibilizers and modifiers, paints and adhesives. The application will be described later.

The method for producing the olefin copolymer according to the present invention as described above will be described later. The olefin copolymer according to the present invention may have a functional group at the end of the main chain. Further, as long as the olefin copolymer according to the present invention has the above-mentioned structure, it may be bonded to a portion having a structure other than the above-mentioned structure as long as the object of the present invention is not impaired. Further, the polymer of the present invention may be graft-modified or the like.

As the functional group, an aromatic hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a metal atom-containing group and the like are preferable. Specifically, examples of the aromatic hydrocarbon group include phenyl, naphthyl, trill, biphenylyl, anthryl and the like.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The oxygen-containing group is, for example, a group containing 1 to 5 oxygen atoms in the group, and does not contain a heterocyclic compound residue as described later. Further, a group containing a nitrogen atom, a sulfur atom, a phosphorus atom or a halogen atom and in which these atoms and an oxygen atom are directly bonded is not included in the oxygen-containing group. Specifically, the oxygen-containing group is a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy; an arylalkoxy group such as phenylmethoxy, phenylethoxy; acetoxy. Groups; carbonyl groups; carboxyl groups; ester groups; acetyl groups and the like. When the oxygen-containing group contains carbon atoms, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

The nitrogen-containing group is, for example, a group containing 1 to 5 nitrogen atoms in the group, and does not contain a heterocyclic compound residue as described later. Specific examples of the nitrogen-containing group include amino groups; alkylamino groups such as methylamino, dimethylamino, ethylamino, propylamino, butylamino and cyclohexylamino; arylamino groups such as phenylamino, trillamino and naphthylamino. Be done.

The sulfur-containing group is, for example, a group containing 1 to 5 sulfur atoms in the group, and does not contain a heterocyclic compound residue as described later. Specifically, as the sulfur-containing group, methyl sulphonate, trifluoromethane sulphonate, phenyl sulphonate, benzyl sulphonate, p-toluene sulphonate, trimethyl benzene sulphonate, triisobutyl benzene sulphonate, Sulfonate groups such as p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene Sulfinate groups such as sulfinate; alkylthio groups; arylthio groups and the like can be mentioned. When the sulfur-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

The phosphorus-containing group is, for example, a group containing 1 to 5 phosphorus atoms in the group, and specifically, a trialkylphosphine group such as trimethylphosphine, tributylphosphine, or tricyclohexylphosphine; triphenylphosphine, tritrylphosphine. Triarylphosphine groups such as; phosphite groups (phosphide groups) such as methylphosphite, ethylphosphite, phenylphosphite; phosphonic acid groups; phosphinic acid groups and the like.

Examples of the metal atom-containing group include a group containing atoms such as silicon, aluminum, boron, zinc, and magnesium, and a metal atom such as lithium. Specific examples thereof include a silicon-containing group, an aluminum-containing group, and a boron-containing group. , Zinc-containing group, magnesium-containing group, lithium atom and the like.

The silicon-containing group is, for example, a group containing 1 to 5 silicon atoms in the group. Specific examples of the silicon-containing group include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, tritrilsilyl, trinaphthylsilyl, and methyldiphenylsilyl. Alkyl-substituted silyl ether groups such as trimethylsilyl ether; Silicon-substituted alkyl groups such as trimethylsilylmethyl; Silicon-substituted aryl groups such as trimethylsilylphenyl; Hydrocarbon-substituted siloxy groups such as trimethylsiloxy. As the hydrocarbon-substituted silyl group, a trialkylsilyl group such as trimethylsilyl, triethylsilyl, tripropylsilyl, and tricyclohexylsilyl is preferable.

The aluminum-containing group is, for example, a group containing 1 to 5 aluminum atoms in the group. Specifically, as an aluminum-containing group, -AlR₂Examples thereof include a group (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

A boron-containing group is a group containing 1 to 5 boron atoms in the group. Specifically, as a boron-containing group, -BR₂Examples thereof include a group (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

A zinc-containing group is, for example, a group containing 1 to 3 zinc atoms in the group. Specific examples of the zinc-containing group include a -ZnR group (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

A magnesium-containing group is a group containing 1 to 3 magnesium atoms in the group. Specific examples of the magnesium-containing group include a -MgR group (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of such an olefin polymer having a functional group at the end of the main chain include a single weight of polyethylene, HDPE, LLDPE, polypropylene, polybutene and 1-pentene, 1-hexene, 1-octene, 1-decene and the like. Combined or copolymer of ethylene and propylene, copolymer of olefin with 4 to 20 carbon atoms, specifically ethylene and 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene Α-Olefin such as α-olefins; butadiene, isoprene, 1,4-pentadiene, 1,5-hexadien, 1,7-octadien and other diene; aromatic vinyl compounds such as styrene; tetracyclododecene, norbornene, methylnorbornene and the like. A copolymer with a cyclic olefin compound, or a copolymer of propylene and the above-mentioned olefin having 4 to 20 carbon atoms, or a halogen atom, a phenyl group, a hydroxy group, an alkoxy group, or a carbonyl group at the end of the above-mentioned tapered polymer. , Carboxyl group, ester group, acetyl group, alkylamino group, trialkylsilyl group, trimethylsiloxy group, dialkylaluminum group, dialkylboron group, alkylzinc group, lithium and the like.

Among these, polyethylene, HDPE, LLDPE, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer have chlorine atom, bromine atom, iodine atom, and hydroxy group at the end. Alternatively, a polymer having an alkyl zinc group is particularly preferable.

Such an olefin polymer having a functional group at the end of the main chain is suitably used for various additives such as compatibilizers and modifiers, paints and adhesives. The uses of these polymers will be described later.

The method for producing an olefin polymer having a functional group at the end of the main chain according to the present invention as described above will be described later. Further, the olefin polymer according to another aspect of the present invention is (i) With a polymer block obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms. (ii) An olefin block copolymer containing a polymer block different from the polymer block (i) obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms.

Here, different polymer blocks refer to those in which at least one of the primary structures of the polymer is different, such as monomer species, comonomer species, comonomer composition, comonomer content, comonomer arrangement, and stereoregularity.

The polymer blocks (i) and (ii) may be a polymer of one type of olefin selected from olefins having 2 to 20 carbon atoms, and two types selected from olefins having 2 to 20 carbon atoms. It may be a random copolymer of the above olefins.

The olefin block copolymer may further have one or more polymer blocks (iii) in addition to the polymer block (i) and the polymer block (ii). In this case, the block copolymer takes the form of (i)-(ii)-(iii) n. Here, n is an integer of 1 or more, preferably 1 to 8, and more preferably 1 to 3, and adjacent polymer blocks are different polymer blocks.

The polymer block (iii) may be a polymer of one kind of olefin selected from olefins having 2 to 20 carbon atoms, and may be a polymer of two or more kinds of olefins selected from carbon and olefins having 2 to 20 atoms. It may be a random copolymer.

In such an olefin block copolymer, it is preferable that the polymer block (i) and the polymer block (ii) are block copolymers selected from the following (a), (b) and (c). .. (a) Polymer block obtained from ethylene, (b) Polymer block obtained from one α-olefin selected from α-olefins having 3 to 20 carbon atoms, (c) A polymer block obtained from two or more types of α-olefins selected from α-olefins having 2 to 20 carbon atoms.

As the polymer block (b), a block composed of homopolymers of propylene, 1-butene, 1-hexene and 1-octene is preferable. As the polymer block (c), a block composed of an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, or the like is preferable.

In the present invention, at least one polymer block (a) obtained from ethylene is contained, and the number average molecular weight of the polymer block (a) is in the range of 110,000 or more, preferably 110,000 to 10,000,000, and more preferably 150,000 to 5,000,000. It is preferable that Mw / Mn is 1.5 or less and 1.3 or less.

Further, in the above-mentioned olefin polymer, an arbitrary number of polymer blocks obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms are bonded, and the number average molecular weight (Mn) of all the polymers is 500 or more. , Preferably in the range of 500 to 10,000,000, more preferably 1000 to 5,000,000, each adjacent polymer block is a different polymer block, and the number average molecular weight of each polymer block is 100 or more, preferably 100 to 100 to. Those in the range of 9,999,900, more preferably in the range of 500 to 4,999,500, and having a Mw / Mn of 2.5 or less can be mentioned.

In the present invention, the number of polymer blocks is an integer of 2 or more, usually in the range of 2 to 10, preferably 2 to 6, and particularly preferably 2 to 4. Further, in the case of a diblock polymer having 2 polymer blocks, the olefin block copolymer preferably has Mw / Mn of less than 1.35, more preferably less than 1.30.

In the case of a triblock polymer having 3 polymer blocks, Mw / Mn is preferably less than 1.80, more preferably less than 1.50. In the case of a multi-block polymer having 4 or more polymer blocks, Mw / Mn is preferably less than 2.00, more preferably less than 1.80.

In addition, these olefin block copolymers include polyethylene, HDPE, LLDPE, ethylene and olefins having 3 to 20 carbon atoms (including diene and cyclic olefins), ata-polypropylene, and iso-. It is preferably selected from polypropylene, syn-polypropylene, a copolymer of propylene and a monomer selected from olefins having 4 to 20 carbon atoms (including diene and cyclic olefins), or the tapered polymer described above.

Furthermore, each polymer block is polyethylene, HDPE, LLDPE, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer, ata-polypropylene, syn-polypropylene, propylene. Diblock polymers or triblock polymers characterized by being selected from butene copolymers, propylene / hexene copolymers or the tapered polymers described above are particularly preferred.

Specific examples of these block polymers include the following. (Here, polyethylene-HDPE refers to an olefin-based block copolymer in which a polyethylene block and an HDPE block are bonded. In addition, this polymer block is a copolymer composed of two or more kinds of monomers such as an ethylene / propylene copolymer. In the case of polymers, the monomer sequence may be either a random copolymer or a tapered polymer.)

Polyethylene-HDPE, polyethylene-LLDPE, polyethylene-ethylene / propylene copolymer, polyethylene-ethylene / butene copolymer, polyethylene-ethylene / hexene copolymer, polyethylene-ethylene / octene copolymer, polyethylene-ata-polypropylene, Polyethylene-syn-polypropylene, polyethylene-propylene / butene copolymer, polyethylene-propylene / hexene copolymer, HDPE-LLDPE, HDPE-ethylene / propylene copolymer, HDPE-ethylene / butene copolymer, HDPE-ethylene / Hexen copolymer, HDPE-ethylene / octene copolymer, HDPE-ata-polypropylene, HDPE-syn-polypropylene, HDPE-propylene / butene copolymer, HDPE-propylene / hexene copolymer, LLDPE-ethylene / propylene copolymer, LLDPE-ethylene / butene copolymer, LLDPE-ethylene / hexene copolymer, LLDPE-ethylene / octene copolymer, LLDPE-ata-polypropylene, LLDPE-syn-polypropylene, LLDPE- Propylene-butene copolymer, LLDPE-propylene-hexene copolymer, Ethylene / propylene copolymer-ethylene / butene copolymer, ethylene / propylene copolymer-ethylene / hexene copolymer, ethylene / propylene copolymer-ethylene / octene copolymer, ethylene / propylene copolymer-ata -Polypropylene, ethylene / propylene copolymer-syn-polypropylene, ethylene / propylene copolymer-propylene / butene copolymer, ethylene / propylene copolymer-propylene / hexene copolymer, Ethylene-butene copolymer-ethylene-hexene copolymer, ethylene-butene copolymer-ethylene-octene copolymer, ethylene-butene copolymer-ata-polypropylene, ethylene-butene copolymer-syn-polypropylene, Ethylene-butene copolymer-propylene-butene copolymer, ethylene-butene copolymer-propylene-hexene copolymer, Ethylene / hexene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-ata-polypropylene, ethylene / hexene copolymer-syn-polypropylene, ethylene / hexene copolymer-propylene / butene copolymer, Ethylene / hexene copolymer-propylene / hexene copolymer, Ethylene / octene copolymer-ata-polypropylene, ethylene / octene copolymer-syn-polypropylene, ethylene / octene copolymer-propylene / butene copolymer, ethylene / octene copolymer-propylene / hexene copolymer, ata-polypropylene-syn-polypropylene, ata-polypropylene-propylene-butene copolymer, ata-polypropylene-propylene-hexene copolymer, syn-polypropylene-propylon-butene copolymer, syn-polypropylene-propylene-hexene copolymer, Propene / Butene Copolymer-Propene / Hexene Copolymer, Polyethylene-HDPE-polyethylene, polyethylene-LLDPE-polyethylene, polyethylene-ethylene / propylene copolymer-polyethylene, polyethylene-ethylene / butene copolymer-polyethylene, polyethylene-ethylene / hexene copolymer-polyethylene, polyethylene-ethylene / octene Copolymer-Polyethylene, Polyethylene-ata-Polyethylene-Polyethylene, Polyethylene-syn-Polyethylene-Polyethylene, Polyethylene-propylene / butene copolymer-Polyethylene, Polyethylene-propylene / hexene copolymer-Polyethylene, HDPE-Polyethylene-HDPE, HDPE-LLDPE-HDPE, HDPE-ethylene / propylene copolymer-HDPE, HDPE-ethylene / butene copolymer-HDPE, HDPE-ethylene / hexene copolymer-HDPE, HDPE-ethylene / octene Copolymer-HDPE, HDPE-ata-Polypropylene-HDPE, HDPE-syn-Polypropylene-HDPE, HDPE-propylene / butene copolymer-HDPE, HDPE-propylene / hexene copolymer-HDPE, LLDPE-Polyethylene-LLDPE, LLDPE-HDPE-LLDPE, LLDPE-ethylene / propylene copolymer-LLDPE, LLDPE-ethylene / butene copolymer-LLDPE, LLDPE-ethylene / hexene copolymer-LLDPE, LLDPE-ethylene / octene Copolymer-LLDPE, LLDPE-ata-Polypropylene-LLDPE, LLDPE-syn-Polypropylene-LLDPE, LLDPE-propylene / butene copolymer-LLDPE, LLDPE-propylene / hexene copolymer-LLDPE, Ethylene / propylene copolymer-polyethylene-ethylene / propylene copolymer, ethylene / propylene copolymer-HDPE-ethylene / propylene copolymer, ethylene / propylene copolymer-LLDPE-ethylene / propylene copolymer, ethylene / Propylene copolymer-ethylene / butene copolymer-ethylene / propylene copolymer, ethylene / propylene copolymer-ethylene / hexene copolymer-ethylene / propylene copolymer, ethylene / propylene copolymer-ethylene / octene Copolymer-ethylene / propylene copolymer, ethylene / propylene copolymer-ata-polypropylene-ethylene / propylene copolymer, ethylene / propylene copolymer-syn-polypropylene-ethylene / propylene copolymer, ethylene / propylene Copolymer-propylene / butene copolymer-ethylene / propylene copolymer, ethylene / propylene copolymer-propylene / hexene copolymer-ethylene / propylene copolymer, Ethylene-butene copolymer-polyethylene-ethylene-butene copolymer, ethylene-butene copolymer-HDPE-ethylene-butene copolymer, ethylene-butene copolymer-LLDPE-ethylene-butene copolymer, ethylene-butene copolymer Butene copolymer-ethylene-propylene copolymer-ethylene-butene copolymer, ethylene-butene copolymer-ethylene-hexene copolymer-ethylene-butene copolymer, ethylene-butene copolymer-ethylene-octene Copolymer-ethylene-butene copolymer, ethylene-butene copolymer-ata-polypropylene-ethylene-butene copolymer, ethylene-butene copolymer-syn-polypropylene-ethylene-butene copolymer, ethylene-butene Copolymers-propylene / butene copolymers-ethylene / butene copolymers, ethylene / butene copolymers-propylene / hexene copolymers-ethylene / butene copolymers,

Ethylene / hexene copolymer-polyethylene-ethylene / hexene copolymer, ethylene / hexene copolymer-HDPE-ethylene / hexene copolymer, ethylene / hexene copolymer-LLDPE-ethylene / hexene copolymer, ethylene / Hexen copolymer-ethylene / propylene copolymer-ethylene / hexene copolymer, ethylene / hexene copolymer-ethylene / butene copolymer-ethylene / hexene copolymer, ethylene / hexene copolymer-ethylene / octene Copolymer-ethylene-hexene copolymer, ethylene-hexene copolymer-ata-polypropylene-ethylene / hexene copolymer, ethylene / hexene copolymer-syn-polypropylene-ethylene / hexene copolymer, ethylene / hexene Copolymer-propylene / butene copolymer-ethylene / hexene copolymer, ethylene / hexene copolymer-propylene / hexene copolymer-ethylene / hexene copolymer, Ethylene-octene copolymer-polyethylene-ethylene-octene copolymer, ethylene-octene copolymer-HDPE-ethylene-octene copolymer, ethylene-octene copolymer-LLDPE-ethylene-octene copolymer, ethylene-octene copolymer Octene copolymer-ethylene / propylene copolymer-ethylene / octene copolymer, ethylene / octene copolymer-ethylene / butene copolymer-ethylene / octene copolymer, ethylene / octene copolymer-ethylene / hexene Copolymer-ethylene-octene copolymer, ethylene-octene copolymer-ata-polypropylene-ethylene-octene copolymer, ethylene-octene copolymer-syn-polypropylene-ethylene-octene copolymer, ethylene-octene Copolymer-propylene / butene copolymer-ethylene / octene copolymer, ethylene / octene copolymer-propylene / hexene copolymer-ethylene / octene copolymer, ata-polypropylene-polypropylene-ata-polypropylene, ata-polypropylene-HDPE-ata-polypropylene, ata-polypropylene-LLDPE-ata-polypropylene, ata-polypropylene-ethylene-propylene copolymer-ata-polypropylene, ata-polypropylene-ethylene Butene copolymer-ata-polypropylene, ata-polypropylene-ethylene-hexene copolymer-ata-polypropylene, ata-polypropylene-ethylene-octene copolymer-ata-polypropylene, ata-polypropylene-syn-polypropylene-ata- Polypropylene, ata-polypropylene-propylene / butene copolymer-ata-polypropylene, ata-polypropylene-propylene / hexene copolymer-ata-polypropylene, syn-polypropylene-polypropylene-syn-polypropylene, syn-polypropylene-HDPE-syn-polypropylene, syn-polypropylene-LLDPE-syn-polypropylene, syn-polypropylene-ethylene / propylene copolymer-syn-polypropylene, syn-polypropylene-ethylene -Buten copolymer-syn-polypropylene, syn-polypropylene-ethylene-hexene copolymer-syn-polypropylene, syn-polypropylene-ethylene-octene copolymer-syn-polypropylene, syn-polypropylene-ata-polypropylene-syn- Polypropylene, syn-polypropylene-propylene / butene copolymer-syn-polypropylene, syn-polypropylene-propylene / hexene copolymer-syn-polypropylene, Propylene-butene copolymer-polyethylene-propylene-butene copolymer, propylene-butene copolymer-HDPE-propylene-butene copolymer, propylene-butene copolymer-LLDPE-propylene-butene copolymer, propylene- Butene copolymer-ethylene / propylene copolymer-propylene / butene copolymer, propylene / butene copolymer-ethylene / butene copolymer-propylene / butene copolymer, propylene / butene copolymer-ethylene / hexene Copolymers-propylene / butene copolymers, propylene / butene copolymers-ethylene / octene copolymers-propylene / butene copolymers, propylene / butene copolymers-ata-polypropylene-propylene / butene copolymers, Protin-butene copolymer-syn-polypropylene-propylene-butene copolymer, propylene-butene copolymer-propylene-hexene copolymer-propylene-butene copolymer,

Propylene-Hexene Copolymer-Polyethylene-Propene-Hexene Copolymer, Propene-Hexene Copolymer-HDPE-Propene-Hexene Copolymer, Propene-Hexene Copolymer-LLDPE-Propene-Hexene Copolymer, Propene Hexene copolymer-ethylene / propylene copolymer-propylene / hexene copolymer, propylene / hexene copolymer-ethylene / butene copolymer-propylene / hexene copolymer, propylene / hexene copolymer-ethylene / hexene Copolymer-propylene / hexene copolymer, propylene / hexene copolymer-ethylene / octene copolymer-propylene / hexene copolymer, propylene / hexene copolymer-ata-polypropylene-propylene / hexene copolymer, Propene / Hexene Copolymer-syn-Polypropylene-Propene / Hexene Copolymer, Propene / Hexene Copolymer-Propene / Butene Copolymer-Propene / Hexene Copolymer Polyethylene-HDPE-LLDPE, Polyethylene-HDPE-ethylene / propylene copolymer, polyethylene-HDPE-ethylene / butene copolymer, polyethylene-HDPE-ethylene / hexene copolymer, polyethylene-HDPE-ethylene / octene copolymer, polyethylene-HDPE-ata- Polyethylene, polyethylene-HDPE-syn-polypropylene, polyethylene-HDPE-propylene / butene copolymer, polyethylene-HDPE-propylene / hexene copolymer, polyethylene-LLDPE-HDPE, polyethylene-LLDPE-ethylene-propylene copolymer, polyethylene -LLDPE-ethylene-butene copolymer, polyethylene-LLDPE-ethylene-hexene copolymer, polyethylene-LLDPE-ethylene-octene copolymer, polyethylene-LLDPE-ata-polyethylene, polyethylene-LLDPE-syn-polyethylene, polyethylene- LLDPE-propylene / butene copolymer, polyethylene-LLDPE-propylene / hexene copolymer, polyethylene-ethylene / propylene copolymer-HDPE, polyethylene-ethylene / propylene copolymer-LLDPE, polyethylene-ethylene / propylene copolymer -Ethethylene / butene copolymer, polyethylene-ethylene / propylene copolymer-ethylene / hexene copolymer, polyethylene-ethylene / propylene copolymer-ethylene / octene copolymer, polyethylene-ethylene / propylene copolymer-ata -Polyethylene, polyethylene-ethylene / propylene copolymer-syn-polyethylene, polyethylene-ethylene / propylene copolymer-propylene / butene copolymer, polyethylene-ethylene / propylene copolymer-propylene / hexene copolymer, polyethylene- Ethylene / butene copolymer-HDPE, polyethylene-ethylene / butene copolymer-LLDPE, polyethylene-ethylene / butene copolymer-ethylene / propylene copolymer, polyethylene-ethylene / butene copolymer-ethylene / hexene copolymer Coalescence,Polyethylene-ethylene-butene copolymer-ethylene-octene copolymer, polyethylene-ethylene-butene copolymer-ata-polypropylene, polyethylene-ethylene-butene copolymer-syn-polypropylene, polyethylene-ethylene-butene copolymer -Polyethylene / butene copolymer, polyethylene-ethylene / butene copolymer-propylene / hexene copolymer, polyethylene-ethylene / hexene copolymer-HDPE, polyethylene-ethylene / hexene copolymer-LLDPE, polyethylene-ethylene Hexen copolymer-ethylene / propylene copolymer, polyethylene-ethylene / hexene copolymer-ethylene / butene copolymer, polyethylene-ethylene / hexene copolymer-ethylene / octene copolymer, polyethylene-ethylene / hexene Polymer-ata-polypropylene, polyethylene-ethylene / hexene copolymer-syn-polypropylene, polyethylene-ethylene / hexene copolymer-propylene / butene copolymer, polyethylene-ethylene / hexene copolymer-propylene / hexene copolymer Combined, polyethylene-ethylene / octene copolymer-HDPE, polyethylene-ethylene / octene copolymer-LLDPE, polyethylene-ethylene / octene copolymer-ethylene / propylene copolymer, polyethylene-ethylene / octene copolymer-ethylene -Butene copolymer, polyethylene-ethylene-octene copolymer-ethylene-hexene copolymer, polyethylene-ethylene-octene copolymer-ata-polyethylene, polyethylene-ethylene-octene copolymer-syn-polyethylene, polyethylene- Ethylene / octene copolymer-propylene / butene copolymer, polyethylene-ethylene / octene copolymer-propylene / hexene copolymer, polyethylene-ata-polypropylene-HDPE, polyethylene-ata-polypropylene-LLDPE, polyethylene-ata- Polyethylene-ethylene-propylene copolymer, polyethylene-ata-polyethylene-dTylene-butene copolymer, polyethylene-ata-polyethylene-ethylene-hexene copolymer, polyethylene-ata-polypropylene-ethylene-octene copolymer, polyethylene-ata-polypropylene-syn-polypropylene, polyethylene-ata-polypropylene-propylene Butene copolymer, polyethylene-ata-polypropylene-propylene / hexene copolymer, polyethylene-syn-polypropylene-HDPE, polyethylene-syn-polypropylene-LLDPE, polyethylene-syn-polypropylene-ethylene / propylene copolymer, polyethylene- syn-polypropylene-ethylene-butene copolymer, polyethylene-syn-polyethylene-ethylene-hexene copolymer, polyethylene-syn-polypropylene-ethylene-octene copolymer, polyethylene-syn-polypropylene-ata-polyethylene, polyethylene-syn -Polyethylene-propylene / butene copolymer, polyethylene-syn-polyethylene-propylene / hexene copolymer, polyethylene-propylene / butene copolymer-HDPE, polyethylene-propylene / butene copolymer-LLDPE, polyethylene-propylene / butene Copolymer-ethylene / propylene copolymer, polyethylene-propylene / butene copolymer-ethylene / butene copolymer, polyethylene-propylene / butene copolymer-ethylene / hexene copolymer, polyethylene-propylene / butene copolymer Combined-ethylene-octene copolymer, polyethylene-propylene / butene copolymer-ata-polypropylene, polyethylene-propylene / butene copolymer-syn-polypropylene, polyethylene-propylene / butene copolymer-propylene / hexene copolymer , Polyethylene-propylene / hexene copolymer-HDPE, polyethylene-propylene / hexene copolymer-LLDPE, polyethylene-propylene / hexene copolymer-ethylene / propylene copolymer, polyethylene-propylene / hexenePolymer-ethylene butene copolymer, polyethylene-propylene / hexene copolymer-ethylene / hexene copolymer, polyethylene-propylene / hexene copolymer-ethylene / octene copolymer, polyethylene-propylene / hexene copolymer -ata-polyethylene, polyethylene-propylene / hexene copolymer-syn-polyethylene, polyethylene-propylene / hexene copolymer-propylene / butene copolymer HDPE-polyethylene-LLDPE, HDPE-polyethylene-ethylene / propylene copolymer,

HDPE-polyethylene-ethylene-butene copolymer, HDPE-polyethylene-ethylene-hexene copolymer, HDPE-polyethylene-ethylene-octene copolymer, HDPE-polyethylene-ata-polypropylene, HDPE-polyethylene-syn-polypropylene, HDPE -Polyethylene-propylene / butene copolymer, HDPE-polyethylene-propylene / hexene copolymer, HDPE-LLDPE-ethylene / propylene copolymer, HDPE-LLDPE-ethylene / butene copolymer, HDPE-LLDPE-ethylene / hexene Copolymer, HDPE-LLDPE-ethylene / octene copolymer, HDPE-LLDPE-ata-polypropylene, HDPE-LLDPE-syn-polypropylene, HDPE-LLDPE-propylene / butene copolymer, HDPE-LLDPE-propylene / hexene Polymer, HDPE-ethylene / propylene copolymer-LLDPE, HDPE-ethylene / propylene copolymer-ethylene / butene copolymer, HDPE-ethylene / propylene copolymer-ethylene / hexene copolymer, HDPE-ethylene / Propylene copolymer-ethylene / octene copolymer, HDPE-ethylene / propylene copolymer-ata-polypropylene, HDPE-ethylene / propylene copolymer-syn-polypropylene, HDPE-ethylene / propylene copolymer-propylene / butene Copolymer, HDPE-ethylene / propylene copolymer-propylene / hexene copolymer, HDPE-ethylene / butene copolymer-LLDPE, HDPE-ethylene / butene copolymer-ethylene / propylene copolymer, HDPE-ethylene -Buten copolymer-ethylene / hexene copolymer, HDPE-ethylene / butene copolymer-ethylene / octene copolymer, HDPE-ethylene / butene copolymer-ata-polypropylene, HDPE-ethylene / butene copolymer -syn-polypropylene, HDPE-ethylene / butene copolymer-propylene / butene copolymer, HDPE-ethylene / buteneTen copolymer-propylene / hexene copolymer, HDPE-ethylene / hexene copolymer-LLDPE, HDPE-ethylene / hexene copolymer-ethylene / propylene copolymer, HDPE-ethylene / hexene copolymer-ethylene / Butene copolymer, HDPE-ethylene / hexene copolymer-ethylene / octene copolymer, HDPE-ethylene / hexene copolymer-ata-polypropylene, HDPE-ethylene / hexene copolymer-syn-polypropylene, HDPE-ethylene -Hexene copolymer-propylene / butene copolymer, HDPE-ethylene / hexene copolymer-propylene / hexene copolymer, HDPE-ethylene / octene copolymer-LLDPE, HDPE-ethylene / octene copolymer-ethylene -Propylene copolymer, HDPE-ethylene / octene copolymer-ethylene / butene copolymer, HDPE-ethylene / octene copolymer-ethylene / hexene copolymer, HDPE-ethylene / octene copolymer-ata-polypropylene , HDPE-ethylene / octene copolymer-syn-polypropylene, HDPE-ethylene / octene copolymer-propylene / butene copolymer, HDPE-ethylene / octene copolymer-propylene / hexene copolymer, HDPE-ata- Polypropylene-LLDPE, HDPE-ata-Polypropylene-ethylene / propylene copolymer, HDPE-ata-polypropylene-ethylene / butene copolymer, HDPE-ata-polypropylene-ethylene / hexene copolymer, HDPE-ata-polypropylene-ethylene -Octen copolymer, HDPE-ata-polypropylene-syn-polypropylene, HDPE-ata-polypropylene-propylene / butene copolymer, HDPE-ata-polypropylene-propylene / hexene copolymer, HDPE-syn-polypropylene-LLDPE, HDPE-syn-polypropylene-ethylene / propylene copolymer, HDPE-syn-polypropylene-ethylene / butene copolymer, HDPE-syn-Polypropylene-ethylene-hexene copolymer, HDPE-syn-polypropylene-ethylene-octene copolymer, HDPE-syn-polypropylene-ata-polypropylene, HDPE-syn-polypropylene-propylene-butene copolymer, HDPE-syn- Polypropylene-propylene / hexene copolymer, HDPE-propylene / butene copolymer-LLDPE, HDPE-propylene / butene copolymer-ethylene / propylene copolymer, HDPE-propylene / butene copolymer-ethylene / butene copolymer Combined, HDPE-propylene / butene copolymer-ethylene / hexene copolymer, HDPE-propylene / butene copolymer-ethylene / octene copolymer, HDPE-propylene / butene copolymer-ata-polypropylene, HDPE-propylene -Buten copolymer-syn-polypropylene, HDPE-propylene / butene copolymer-propylene / hexene copolymer, HDPE-propylene / hexene copolymer-LLDPE, HDPE-propylene / hexene copolymer-ethylene / propylene Polymer, HDPE-propylene / hexene copolymer-ethylene / butene copolymer, HDPE-propylene / hexene copolymer-ethylene / hexene copolymer, HDPE-propylene / hexene copolymer-ethylene / octene copolymer , HDPE-propylene / hexene copolymer-ata-polypropylene, HDPE-propylene / hexene copolymer-syn-polypropylene, HDPE-propylene / hexene copolymer-propylene / butene copolymer,Polymer, HDPE-propylene / butene copolymer-ethylene / butene copolymer, HDPE-propylene / butene copolymer-ethylene / hexene copolymer, HDPE-propylene / butene copolymer-ethylene / octene copolymer , HDPE-propylene / butene copolymer-ata-polypropylene, HDPE-propylene / butene copolymer-syn-polypropylene, HDPE-propylene / butene copolymer-propylene / hexene copolymer, HDPE-propylene / hexene copolymer Combined-LLDPE, HDPE-propylene / hexene copolymer-ethylene / propylene copolymer, HDPE-propylene / hexene copolymer-ethylene / butene copolymer, HDPE-propylene / hexene copolymer-ethylene / hexene copolymer Combined, HDPE-propylene / hexene copolymer-ethylene / octene copolymer, HDPE-propylene / hexene copolymer-ata-polypropylene, HDPE-propylene / hexene copolymer-syn-polypropylene, HDPE-propylene / hexene Polymer-propylene / butene copolymer,Polymer, HDPE-propylene / butene copolymer-ethylene / butene copolymer, HDPE-propylene / butene copolymer-ethylene / hexene copolymer, HDPE-propylene / butene copolymer-ethylene / octene copolymer , HDPE-propylene / butene copolymer-ata-polypropylene, HDPE-propylene / butene copolymer-syn-polypropylene, HDPE-propylene / butene copolymer-propylene / hexene copolymer, HDPE-propylene / hexene copolymer Combined-LLDPE, HDPE-propylene / hexene copolymer-ethylene / propylene copolymer, HDPE-propylene / hexene copolymer-ethylene / butene copolymer, HDPE-propylene / hexene copolymer-ethylene / hexene copolymer Combined, HDPE-propylene / hexene copolymer-ethylene / octene copolymer, HDPE-propylene / hexene copolymer-ata-polypropylene, HDPE-propylene / hexene copolymer-syn-polypropylene, HDPE-propylene / hexene Polymer-propylene / butene copolymer,-Hexene copolymer-syn-polypropylene, HDPE-propylene-hexene copolymer-propylene-butene copolymer,-Hexene copolymer-syn-polypropylene, HDPE-propylene-hexene copolymer-propylene-butene copolymer,

LLDPE-polyethylene-ethylene-propylene copolymer, LLDPE-polyethylene-ethylene-butene copolymer, LLDPE-polyethylene-ethylene-hexene copolymer, LLDPE-polyethylene-ethylene-octene copolymer, LLDPE-polyethylene-ata- Polypropylene, LLDPE-polyethylene-syn-polypropylene, LLDPE-polyethylene-propylene / butene copolymer, LLDPE-polyethylene-propylene / hexene copolymer, LLDPE-HDPE-ethylene / propylene copolymer, LLDPE-HDPE-ethylene / butene Copolymer, LLDPE-HDPE-ethylene / hexene copolymer, LLDPE-HDPE-ethylene / octene copolymer, LLDPE-HDPE-ata-polypropylene, LLDPE-HDPE-syn-polypropylene, LLDPE-HDPE-propylene / butene Polymer, LLDPE-HDPE-propylene / hexene copolymer, LLDPE-ethylene / propylene copolymer-ethylene / butene copolymer, LLDPE-ethylene / propylene copolymer-ethylene / hexene copolymer, LLDPE-ethylene Propylene copolymer-ethylene / octene copolymer, LLDPE-ethylene / propylene copolymer-ata-polypropylene, LLDPE-ethylene / propylene copolymer-syn-polypropylene, LLDPE-ethylene / propylene copolymer-propylene / butene Copolymer, LLDPE-ethylene / propylene copolymer-propylene / hexene copolymer, LLDPE-ethylene / butene copolymer-ethylene / propylene copolymer, LLDPE-ethylene / butene copolymer-ethylene / hexene copolymer Combined, LLDPE-ethylene / butene copolymer-ethylene / octene copolymer, LLDPE-ethylene / butene copolymer-ata-polypropylene, LLDPE-ethylene / butene copolymer-syn-polypropylene, LLDPE-ethylene / butene Polymer-propylene butene copolymer, LLDPE-ethylene butteCopolymer-propylene / hexene copolymer, LLDPE-ethylene / hexene copolymer-ethylene / propylene copolymer, LLDPE-ethylene / hexene copolymer-ethylene / butene copolymer, LLDPE-ethylene / hexene Polymer-ethylene / octene copolymer, LLDPE-ethylene / hexene copolymer-ata-polypropylene, LLDPE-ethylene / hexene copolymer-syn-polypropylene, LLDPE-ethylene / hexene copolymer-propylene / butene copolymer Combined, LLDPE-ethylene / hexene copolymer-propylene / hexene copolymer, LLDPE-ethylene / octene copolymer-ethylene / propylene copolymer, LLDPE-ethylene / octene copolymer-ethylene / butene copolymer, LLDPE-ethylene / octene copolymer-ethylene / hexene copolymer, LLDPE-ethylene / octene copolymer-ata-polypropylene, LLDPE-ethylene / octene copolymer-syn-polypropylene, LLDPE-ethylene / octene copolymer -Propylene / butene copolymer, LLDPE-ethylene / octene copolymer-propylene / hexene copolymer, LLDPE-ata-polypropylene-ethylene / propylene copolymer, LLDPE-ata-polypropylene-ethylene / butene copolymer, LLDPE-ata-polypropylene-ethylene / hexene copolymer, LLDPE-ata-polypropylene-ethylene / octene copolymer, LLDPE-ata-polypropylene-syn-polypropylene, LLDPE-ata-polypropylene-propylene / butene copolymer, LLDPE -ata-polypropylene-propylene / hexene copolymer, LLDPE-syn-polypropylene-ethylene / propylene copolymer, LLDPE-syn-polypropylene-ethylene / butene copolymer, LLDPE-syn-polypropylene-ethylene / hexene copolymer , LLDPE-syn-Polypropylene-ethylene-octene copolymer, LLDPE-syn-Polypropylene-ata-polypropylene, LLDPE-syn-polypropylene-propylene / butene copolymer, LLDPE-syn-polypropylene-propylene / hexene copolymer, LLDPE-propylene / butene copolymer-ethylene / propylene copolymer, LLDPE-propylene / Butene copolymer-ethylene / butene copolymer, LLDPE-propylene / butene copolymer-ethylene / hexene copolymer, LLDPE-propylene / butene copolymer-ethylene / octene copolymer, LLDPE-propylene / butene Polymer-ata-polypropylene, LLDPE-propylene / butene copolymer-syn-polypropylene, LLDPE-propylene / butene copolymer-propylene / hexene copolymer, LLDPE-propylene / hexene copolymer-ethylene / propylene copolymer Combined, LLDPE-propylene / hexene copolymer-ethylene / butene copolymer, LLDPE-propylene / hexene copolymer-ethylene / hexene copolymer, LLDPE-propylene / hexene copolymer-ethylene / octene copolymer, LLDPE-propylene / hexene copolymer-ata-polypropylene, LLDPE-propylene / hexene copolymer-syn-polypropylene, LLDPE-propylene / hexene copolymer-propylene / butene copolymer,Copolymer, LLDPE-propylene / hexene copolymer-ethylene / propylene copolymer, LLDPE-propylene / hexene copolymer-ethylene / butene copolymer, LLDPE-propylene / hexene copolymer-ethylene / hexene copolymer Combined, LLDPE-propylene / hexene copolymer-ethylene / octene copolymer, LLDPE-propylene / hexene copolymer-ata-polypropylene, LLDPE-propylene / hexene copolymer-syn-polypropylene, LLDPE-propylene / hexene Polymer-propylene / butene copolymer,Copolymer, LLDPE-propylene / hexene copolymer-ethylene / propylene copolymer, LLDPE-propylene / hexene copolymer-ethylene / butene copolymer, LLDPE-propylene / hexene copolymer-ethylene / hexene copolymer Combined, LLDPE-propylene / hexene copolymer-ethylene / octene copolymer, LLDPE-propylene / hexene copolymer-ata-polypropylene, LLDPE-propylene / hexene copolymer-syn-polypropylene, LLDPE-propylene / hexene Polymer-propylene / butene copolymer,

Ethylene-butene copolymer-polyethylene-ethylene-hexene copolymer, ethylene-butene copolymer-polyethylene-ethylene-octene copolymer, ethylene-butene copolymer-polyethylene-ata-polypropylene, ethylene-butene copolymer Combined-polyethylene-syn-polypropylene, ethylene / butene copolymer-polyethylene-propylene / butene copolymer, ethylene / butene copolymer-polyethylene-propylene / hexene copolymer, ethylene / butene copolymer-HDPE-ethylene Hexen copolymer, ethylene / butene copolymer-HDPE-ethiresi / octene copolymer, ethylene / butene copolymer-HDPE-ata-polypropylene, ethylene / butene copolymer-HDPE-syn-polypropylene, ethylene Butene copolymer-HDPE-propylene / butene copolymer, ethylene / butene copolymer-HDPE-propylene / hexene copolymer, ethylene / butene copolymer-LLDPE-ethylene / hexene copolymer, ethylene / butene Polymer-LLDPE-ethylene / octene copolymer, ethylene / butene copolymer-LLDPE-ata-polypropylene, ethylene / butene copolymer-LLDPE-syn-polypropylene, ethylene / butene copolymer-LLDPE-propylene / butene Copolymers, ethylene / butene copolymers-LLDPE-propylene / hexene copolymers, ethylene / butene copolymers-ethylene / propylene copolymers-ethylene / hexene copolymers, ethylene / butene copolymers-ethylene / Propropylene copolymer-ethylene / octene copolymer, ethylene / butene copolymer-ethylene / propylene copolymer-ata-polypropylene, ethylene / butene copolymer-ethylene / propylene copolymer-syn-polypropylene, ethylene / Butene copolymer-ethylene / propylene copolymer-propylene / butene copolymer, ethylene / butene copolymer-ethylene-propylene copolymer-propylene / hexene copolymer, ethylene / butene copolymer-ethylene / hexene CopolymerizationBody-ethylene-octene copolymer, ethylene-butene copolymer-ethylene-hexene copolymer-ata-polypropylene, ethylene-butene copolymer-ethylene-hexene copolymer-syn-polypropylene, ethylene-butene copolymer Combined-ethylene / hexene copolymer-propylene / butene copolymer, ethylene / butene copolymer-ethylene / hexene copolymer-propylene / hexene copolymer, ethylene / butene copolymer-ethylene / octene copolymer -Ethethylene / hexene copolymer, ethylene / butene copolymer-ethylene / octene copolymer-ata-polypropylene, ethylene / butene copolymer-ethylene / octene copolymer-syn-polypropylene, ethylene / butene copolymer -Ethethylene / octene copolymer-propylene / butene copolymer, ethylene / butene copolymer-ethylene / octene copolymer-propylene / hexene copolymer, ethylene / butene copolymer-ata-polypropylene-ethylene / hexene Copolymer, ethylene / butene copolymer-ata-polypropylene-ethylene / octene copolymer, ethylene / butene copolymer-ata-polypropylene-syn-polypropylene, ethylene / butene copolymer-ata-polypropylene-propylene Butene copolymer, ethylene / butene copolymer-ata-polypropylene-propylene / hexene copolymer, ethylene / butene copolymer-syn-polypropylene-ethylene / hexene copolymer, ethylene / butene copolymer-syn- Polypropylene-ethylene-octene copolymer, ethylene-butene copolymer-syn-polypropylene-ata-polypropylene, ethylene-butene copolymer-syn-polypropylene-propylene-butene copolymer, ethylene-butene copolymer-syn -Polypropylene-propylene / hexene copolymer, ethylene / butene copolymer-propylene / butene copolymer-ethylene / hexene copolymer, ethylene / butene copolymer-propylene / butene copolymer-ethylene / octene copolymer Combined, ethylene / butene copolymerBody-propylene / butene copolymer-ata-polypropylene, ethylene / butene copolymer-propylene / butene copolymer-syn-polypropylene, ethylene / butene copolymer-propylene / butene copolymer-propylene / hexene copolymer weight Combined, ethylene / butene copolymer-propylene / hexene copolymer-ethylene / hexene copolymer, ethylene / butene copolymer-propylene / hexene copolymer-ethylene / octene copolymer, ethylene / butene copolymer -Propylene / hexene copolymer-ata-polypropylene, ethylene / butene copolymer-propylene / hexene copolymer-syn-polypropylene, ethylene / butene copolymer-propylene / hexene copolymer-propylene / butene copolymer ,

Ethylene / hexene copolymer-polyethylene-ethylene / octene copolymer, ethylene / hexene copolymer-polyethylene-ata-polyethylene, ethylene / hexene copolymer-polyethylene-syn-polyethylene, ethylene / hexene copolymer-polyethylene -Protein-butene copolymer, ethylene-hexene copolymer-Polyethylene-propylene-hexeCopolymer, ethylene / hexene copolymer-HDPE-ethylene / octene copolymer, ethylene / hexene copolymer-HDPE-ata-polypropylene, ethylene / hexene copolymer-HDPE-syn-polypropylene, ethylene / hexene Copolymer-HDPE-propylene / butene copolymer, ethylene-hexene copolymer-HDPE-propylene / hexene copolymer, ethylene / hexene copolymer-LLDPE-ethylene / octene copolymer, ethylene / hexene copolymer Combined-LLDPE-ata-Polypropylene, ethylene / hexene copolymer-LLDPE-syn-polypropylene, ethylene / hexene copolymer-LLDPE-propylene / butene copolymer, ethylene / hexene copolymer-LLDPE-propylene / hexene Polymer, ethylene / hexene copolymer-ethylene / propylene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-ethylene / propylene copolymer-ata-polypropylene, ethylene / hexene copolymer-ethylene -Propylene copolymer-syn-polypropylene, ethylene-hexene copolymer-ethylene-propylene copolymer-propylene-butene copolymer, ethylene-hexene copolymer-ethylene-propylene copolymer-propylene-hexene copolymer Combined, ethylene / hexene copolymer-ethylene / butene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-ethylene / butene copolymer-ata-polypropylene, ethylene / hexene copolymer-ethylene Butene copolymer-syn-polypropylene, ethylene / hexene copolymer-ethylene / butene copolymer-propylene / butene copolymer, ethylene / hexene copolymer-ethylene / butene copolymer-propylene / hexene copolymer , Ethylene / hexene copolymer-ethylene / octene copolymer-ata-polypropylene, ethylene / hexene copolymer-ethylene / octene copolymer-syn-polypropylene, ethylene / hexene copolymer-ethylene / octene copolymer -PropiRen-butene copolymer, ethylene-hexene copolymer-ethylene / octene copolymer-propylene / hexene copolymer, ethylene / hexene copolymer-ata-polypropylene-ethylene / octene copolymer, ethylene / hexene Polymer-ata-polypropylene-syn-polypropylene, ethylene / hexene copolymer-ata-polypropylene-propylene / butene copolymer, ethylene / hexene copolymer-ata-polypropylene-propylene / hexene copolymer, ethylene / hexene Copolymer-syn-polypropylene-ethylene / octene copolymer, ethylene / hexene copolymer-syn-polypropylene-ata-polypropylene, ethylene / hexene copolymer-syn-polypropylene-propylene / butene copolymer, ethylene / Hexen copolymer-syn-polypropylene-propylene / hexene copolymer, ethylene / hexene copolymer-propylene / butene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-propylene / butene copolymer -ata-Polypropylene, ethylene / hexene copolymer-propylene / butene copolymer-syn-polypropylene, ethylene / hexene copolymer-propylene / butene copolymer-propylene / hexene copolymer, ethylene / hexene copolymer -Propropylene / hexene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-propylene / hexene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-syn-polypropylene , Ethylene / hexene copolymer-propylene / hexene copolymer-propylene / butene copolymer,Ren-propylene / butene copolymer, ethylene / hexene copolymer-ata-polypropylene-propylene / hexene copolymer, ethylene / hexene copolymer-syn-polypropylene-ethylene / octene copolymer, ethylene / hexene copolymer Combined-syn-polypropylene-ata-polypropylene, ethylene / hexene copolymer-syn-polypropylene-propylene / butene copolymer, ethylene / hexene copolymer-syn-polypropylene-propylene / hexene copolymer, ethylene / hexene Polymer-propylene / butene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-propylene / butene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / butene copolymer-syn -Polypropylene, ethylene / hexene copolymer-propylene / butene copolymer-propylene / hexene copolymer, ethylene / hexene copolymer-propylene / hexene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer Combined-propylene / hexene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-syn-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-propylene / butene copolymer Coalescence,Ren-propylene / butene copolymer, ethylene / hexene copolymer-ata-polypropylene-propylene / hexene copolymer, ethylene / hexene copolymer-syn-polypropylene-ethylene / octene copolymer, ethylene / hexene copolymer Combined-syn-polypropylene-ata-polypropylene, ethylene / hexene copolymer-syn-polypropylene-propylene / butene copolymer, ethylene / hexene copolymer-syn-polypropylene-propylene / hexene copolymer, ethylene / hexene Polymer-propylene / butene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer-propylene / butene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / butene copolymer-syn -Polypropylene, ethylene / hexene copolymer-propylene / butene copolymer-propylene / hexene copolymer, ethylene / hexene copolymer-propylene / hexene copolymer-ethylene / octene copolymer, ethylene / hexene copolymer Combined-propylene / hexene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-syn-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-propylene / butene copolymer Coalescence,Combined-Propene / Butene Copolymer-syn-Polypropylene, Ethylene / Hexene Copolymer-Propene / Butene Copolymer-Propene / Hexene Copolymer, Ethylene / Hexene Copolymer-Propene / Hexene Copolymer-Ethylene Octene copolymer, ethylene / hexene copolymer-propylene / hexene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-syn-polypropylene, ethylene / hexene copolymer-propylene / Hexene copolymer-propylene / butene copolymer,Combined-Propene / Butene Copolymer-syn-Polypropylene, Ethylene / Hexene Copolymer-Propene / Butene Copolymer-Propene / Hexene Copolymer, Ethylene / Hexene Copolymer-Propene / Hexene Copolymer-Ethylene / Octene copolymer, ethylene / hexene copolymer-propylene / hexene copolymer-ata-polypropylene, ethylene / hexene copolymer-propylene / hexene copolymer-syn-polypropylene, ethylene / hexene copolymer-propylene / Hexene copolymer-propylene / butene copolymer,

Ethylene-octene copolymer-polyethylene-ata-polypropylene, ethylene-octene copolymer-polyethylene-syn-polypropylene, ethylene-octene copolymer-polyethylene-propylene-butene copolymer, ethylene-octene copolymer-polyethylene -Propropylene / hexene copolymer, ethylene / octene copolymer-HDPE-ata-polypropylene, ethylene / octene copolymer-HDPE-syn-polypropylene, ethylene / octene copolymer-HDPE-propylene / butene copolymer, Ethylene / octene copolymer-HDPE-propylene / hexene copolymer, ethylene / octene copolymer-LLDPE-ata-polypropylene, ethylene / octene copolymer-LLDPE-syn-polypropylene, ethylene / octene copolymer-LLDPE -Propylene / butene copolymer, ethylene / octene copolymer-LLDPE-propylene / hexene copolymer, ethylene / octene copolymer-ethylene / propylene copolymer-ata-polypropylene, ethylene / octene copolymer-ethylene -Propine copolymer-syn-polypropylene, ethylene-octene copolymer-ethylene-propylene copolymer-propylene-butene copolymer, ethylene-octene copolymer-ethylene-propylene copolymer-propylene-hexene copolymer Combined, ethylene / octene copolymer-ethylene / butene copolymer-ata-polypropylene, ethylene / octene copolymer-ethylene / butene copolymer-syn-polypropylene, ethylene / octene copolymer-ethylene / butene copolymer Combined-propylene / octene copolymer, ethylene / octene copolymer-ethylene / butene copolymer-propylene / hexene copolymer, ethylene / octene copolymer-ethylene / hexene copolymer-ata-polypropylene, ethylene / Octene copolymer-ethylene / hexene copolymer-syn-polypropylene, ethylene / octene copolymer-ethylene / hexene copolymer-propylene / butene copolymer, ethylene / octeneCopolymer-ethylene / hexene copolymer-propylene / hexene copolymer, ethylene / octene copolymer-ata-polypropylene-syn-polypropylene, ethylene / octene copolymer-ata-polypropylene-propylene / butene copolymer Combined, ethylene / octene copolymer-ata-polypropylene-propylene / hexene copolymer, ethylene / octene copolymer-syn-polypropylene-ata-polypropylene, ethylene / octene copolymer-syn-polypropylene-propylene / butene Polymer, ethylene / octene copolymer-syn-polypropylene-propylene / hexene copolymer, ethylene / octene copolymer-propylene / butene copolymer-ata-polypropylene, ethylene / octene copolymer-propylene / butene Polymer-syn-polypropylene, ethylene / octene copolymer-propylene / butene copolymer-propylene / hexene copolymer, ethylene / octene copolymer-propylene / hexene copolymer-ata-polypropylene, ethylene / octene Polymer-propylene / hexene copolymer-syn-polypropylene, ethylene / octene copolymer-propylene / hexene copolymer-propylene / butene copolymer,Body-syn-polypropylene, ethylene / octene copolymer-propylene / butene copolymer-propylene / hexene copolymer, ethylene / octene copolymer-propylene / hexene copolymer-ata-polypropylene, ethylene / octene copolymer Combined-Propene / Hexene Copolymer-syn-Polypropylene, Ethylene / Octen Copolymer-Propene / Hexene Copolymer-Propene / Butene Copolymer,Body-syn-polypropylene, ethylene / octene copolymer-propylene / butene copolymer-propylene / hexene copolymer, ethylene / octene copolymer-propylene / hexene copolymer-ata-polypropylene, ethylene / octene copolymer Combined-Propene / Hexene Copolymer-syn-Polypropylene, Ethylene / Octen Copolymer-Propene / Hexene Copolymer-Propene / Butene Copolymer,

ata-polypropylene-polypropylene-syn-polypropylene, ata-polypropylene-polypropylene-propylene-butene copolymer, ata-polypropylene-polypropylene-propylene-hexene copolymer, ata-polypropylene-HDPE-syn-polypropylene, ata-polypropylene- HDPE-propylene / butene copolymer, ata-polypropylene-HDPE-propylene / hexene copolymer, ata-polypropylene-ethylene / octene copolymer-syn-polypropylene, ata-polypropylene-ethylene / octene copolymer-propylene / Butene copolymer, ata-polypropylene-ethylene / octene copolymer-propylene / hexene copolymer, ata-polypropylene-ethylene / propylene copolymer-syn-polypropylene, ata-polypropylene-ethylene / propylene copolymer-propylene -Buten copolymer, ata-polypropylene-ethylene-propylene copolymer-propylene-hexene copolymer, ata-polypropylene-ethylene-butene copolymer-syn-polypropylene, ata-polypropylene-ethylene-butene copolymer- Propropylene / butene copolymer, ata-polypropylene-ethylene / butene copolymer-propylene / hexene copolymer, ata-polypropylene-ethylene / hexene copolymer-syn-polypropylene, ata-polypropylene-ethylene / hexene copolymer -Propropylene / butene copolymer, ata-polypropylene-ethylene / hexene copolymer-propylene / hexene copolymer, ata-polypropylene-ethylene / octene copolymer-syn-polypropylene, ata-polypropylene-ethylene / octene copolymer Combined-propylene / butene copolymer, ata-polypropylene-ethylene / octene copolymer-propylene / hexene copolymer, ata-polypropylene-syn-polypropylene-propylene / butene copolymer, ata-polypropylene-syn-polypropylene- Polypropylene and hexene co-weightCombined, ata-polypropylene-propylene / butene copolymer-syn-polypropylene, ata-polypropylene-propylene / butene copolymer-propylene / hexene copolymer, ata-polypropylene-propylene / hexene copolymer-syn-polypropylene, ata-Polypropylene-Propene / Hexen copolymer-Propene / Butene copolymer, syn-polypropylene-polyethylene-propylene-butene copolymer, syn-polypropylene-polyethylene-propylene / hexene copolymer, syn-polypropylene-HDPE-propylene / butene copolymer, syn-polypropylene-HDPE-propylene / hexene copolymer Combined, syn-polypropylene-LLDPE-propylene / butene copolymer, syn-polypropylene-LLDPE-propylene / hexene copolymer, syn-polypropylene-ethylene / propylene copolymer-propylene / butene copolymer, syn-polypropylene- Ethylene / propylene copolymer-propylene / hexene copolymer, syn-polypropylene-ethylene / butene copolymer-propylene / butene copolymer, syn-polypropylene-ethylene / butene copolymer-propylene / hexene copolymer, syn-polypropylene-ethylene / hexene copolymer-propylene / butene copolymer, syn-polypropylene-ethylene / hexene copolymer-propylene / hexene copolymer, syn-polypropylene-ethylene / octene copolymer-propylene / butene Copolymer, syn-polypropylene-ethylene / octene copolymer-propylene / hexene copolymer, syn-polypropylene-ata-polypropylene-propylene / butene copolymer, syn-polypropylene-ata-polypropylene-propylene-hexene copolymer Combined, syn-polypropylene-propylene / butene copolymer-propylene / hexene copolymer, syn-polypropylene-propylene / hexene copolymer-propylene / butene copolymer, Propylene / Butene Copolymer-Polyethylene-Propene / Hexene Copolymer, Propene / Butene Copolymer-HDPE-Propene / Hexene Copolymer, Propene / Butene Copolymer-LLDPE-Propene / Hexene Copolymer, Propene Butene copolymer-ethylene / propylene copolymer-propylene / hexene copolymer, propylene / butene copolymer-ethylene / butene copolymer-propylene / hexene copolymer, propylene / butene copolymer-ethylene / hexene Copolymer-propylene / hexene copolymer, propylene / butene copolymer-ethylene / octene copolymer-propylene / hexene copolymer, propylene / butene copolymer-ata-propylene-propylene / hexene copolymer, Propene-butene copolymer-syn-polypropylene-propylene-hexene copolymer.

Among such block copolymers, polyethylene-polyethylene, polyethylene-ethylene / propylene copolymer, polyethylene-ethylene / propylene copolymer-polypropylene, polyethylene-ethylene / propylene copolymer-LLDPE, polyethylene-ethylene / butene. Copolymers, polyethylene-ethylene / butene copolymer-LLDPE, polypropylene-ethylene / propylene copolymer, polyethylene-LLDPE-HDPE, polyethylene-LLDPE are particularly preferred.

As long as the olefin block copolymer of the present invention has the above structure, it may be bonded to a portion having a structure other than the above structure as long as the object of the present invention is not impaired. Good. Further, the polymer of the present invention may be graft-modified or the like.

Such olefin block copolymers are suitably used for various molding materials such as films, sheets and blow molded products, various additives such as compatibilizers and modifiers, paints and adhesives. The uses of these polymers will be described later.

The method for producing an olefin block copolymer as described above will be described later. The olefin block copolymer according to the present invention may have a functional group at the end of the main chain. Examples of this functional group include those mentioned above.

Such an olefin block copolymer having a functional group at the end of the main chain is suitably used for various additives such as compatibilizers and modifiers, paints and adhesives. The details of the application will be described later.

The method for producing an olefin block copolymer having a functional group at the end of the main chain according to the present invention as described above will be described later. Next, a method for producing an olefin polymer according to the present invention will be described.

In the method for producing an olefin polymer according to the present invention, a catalyst for olefin polymerization composed of the following transition metal compound (A), Preferably, (A) With the following transition metal compounds (B) (B-1) Organometallic compounds, (B-2) Organoaluminium oxy compounds, and (B-3) A compound that reacts with a transition metal compound (A) to form an ion pair. A catalyst for olefin polymerization consisting of at least one compound selected from the above is used. First, each component forming the olefin polymerization catalyst used in the present invention will be described.

<u style="single">(A) Transition metal compound</u> The transition metal compound (A) used in the present invention is represented by the following general formula (I), and is a central metal in a β-agostic structure obtained by a density general function method for a cation complex in which X is substituted with an n-propyl group. It is a compound characterized in that the distance (r value) between the closest heteroatom (Z) having no direct bond with and hydrogen at the β-position is 3.0 Å or less and the electrostatic energy is -10 kJ / mol or less. ..

Here, the density functional theory is the program ADF2000.01 (Developer: SCM (Netherlands) Obtaining method: After concluding a license agreement with SCM, SCM homepage (html: //www.scm.com) Refers to the calculation using the BLYP method using (download from). The basis function is a Slater type orbit, and regarding the structure, the triple zeta type is used for the central metal and the double zeta type is used for other atoms. However, when evaluating electrostatic energy, other atoms with a polarization function added to the Double zeta type are used. This basis function is also used for one-point calculation with the optimum structure obtained by structural calculation. In addition to structural calculation, Pauli's relativistic potential is corrected. Electrostatic energy refers to the electrostatic energy between hydrogen at the β-position and the closest heteroatom. More specifically, it is an interatomic electrostatic interaction based on an electronic state obtained by assigning a charge obtained by complex calculation to these two atoms. The electric charge here is the electron population of the s, p, and d orbitals of these two atoms obtained by complex calculation (one-point calculation with the β-agostic optimum structure obtained after structural calculation). ..

L_mMX_n ... (I) In the general formula (I), M represents a transition metal atom selected from groups 3 to 11 of the periodic table, preferably a transition metal atom selected from groups 4 to 5, and more preferably a transition metal atom of group 4. Specifically, titanium, zirconium, and hafnium, and particularly preferably titanium. m indicates an integer from 1 to 6. L is a ligand coordinated to the central metal M and is an organic or inorganic ligand having at least one heteroatom (Z) having no bond with the central metal M.

Specific ligand skeletons include cyclopentadienyl skeleton, acetylacetonate skeleton, phenoxy skeleton, amide skeleton, imide skeleton and the general formulas (II-a), (II-b) or (III) described later. Examples thereof include a ligand skeleton that forms a transition metal compound to be formed.

Here, the ligand skeleton represented by the general formula (II-a) is R in the general formula (II-a) described later.¹Is a hydrocarbon group, R³And R⁴A ligand skeleton having a heteroatom or a heteroatom-containing group described below in any of the above, that is, R.¹, R³And R⁴It also includes the case where at least one of them has a heteroatom or a heteroatom-containing group described later.

The ligand skeleton represented by the general formula (II-b) is R in the general formula (II-b) described later.¹Is a hydrocarbon group, R⁶, R⁷, R⁸And R⁹A ligand skeleton having a heteroatom or a heteroatom-containing group described below in any of the above, that is, R.¹, R⁶, R⁷, R⁸And R⁹It also includes the case where at least one of them has a heteroatom or a heteroatom-containing group described later.

The ligand skeleton represented by the general formula (III) is R in the general formula (III) described later.¹⁰Is a hydrocarbon group, R¹¹, R¹², R¹³, R¹⁴And R¹⁵A ligand skeleton having a heteroatom or a heteroatom-containing group described below in any of the above, that is, R.¹¹, R¹², R¹³, R¹⁴And R¹⁵It also includes the case where at least one of them has a heteroatom or a heteroatom-containing group described later.

Here, the hetero atom is a non-metal atom other than a carbon atom and a hydrogen atom, and specific examples thereof include halogen, nitrogen, oxygen, phosphorus, sulfur and selenium atoms. n is a number that satisfies the valence of M.

X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, Indicates a silicon-containing group, a germanium-containing group or a tin-containing group. The plurality of groups represented by X may be bonded to each other to form a ring.

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and aicosyl; cycloalkyls having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl. Groups; Alkyl groups such as vinyl, propenyl, cyclohexenyl; Alkyl alkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, trill, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl , Aryl groups such as phenyl drill, and the like. In addition, these hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one of the hydrocarbon groups having 1 to 20 carbon atoms is replaced with halogen.

The oxygen-containing group is, for example, a group containing 1 to 5 oxygen atoms in the group, and does not contain a heterocyclic compound residue as described later. Further, the oxygen-containing group does not include a group containing a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom or a silicon atom, and in which these atoms and an oxygen atom are directly bonded. Specifically, the oxygen-containing group is a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy; an arylalkoxy group such as phenylmethoxy, phenylethoxy; acetoxy. Group; carbonyl group and the like. When the oxygen-containing group contains carbon atoms, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

The sulfur-containing group is, for example, a group containing 1 to 5 sulfur atoms in the group, and does not contain a heterocyclic compound residue as described later. Specific examples of the sulfur-containing group include methyl sulphonate, trifluoromethane sulphonate, phenyl sulphonate, benzyl sulphonate, p-toluene sulphonate, trimethyl benzene sulphonate, and triisobutyl benzene sulphonate. Sulfonate groups such as nate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, penta Sulfinate groups such as fluorobenzenesulfinate; alkylthio groups; arylthio groups and the like can be mentioned. When the sulfur-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

A nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group, and does not contain a heterocyclic compound residue as described later. Specifically, as a nitrogen-containing group, specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditrilamino, dinaphthyl. Examples thereof include an arylamino group such as amino and methylphenylamino, or an alkylarylamino group.

The boron-containing group is, for example, a group containing 1 to 5 boron atoms in the group, and does not contain the above heterocyclic compound residue. Specifically, as a boron-containing group, BR₄(R indicates hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

An aluminum-containing group is a group containing 1 to 5 aluminum atoms in the group. Specifically, as an aluminum-containing group, AlR₄(R indicates hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

The phosphorus-containing group is, for example, a group containing 1 to 5 phosphorus atoms in the group, and does not contain the above heterocyclic compound residue. Specifically, the phosphorus-containing group includes a trialkylphosphine group such as trimethylphosphine, triftylphosphine and tricyclohexylphosphine; a triarylphosphine group such as triphenylphosphine and tritrylphosphine; methylphosphine, ethylphosphine and phenylphos. Phosphite groups (phosphide groups) such as phyto; phosphonic acid groups; phosphinic acid groups and the like can be mentioned.

Specifically, as a halogen-containing group, PF₆, BF₄Fluorine-containing groups such as ClO₄, SbCl₆Chlorine-containing groups such as IO₄Iodine-containing groups such as. Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples of the compound residue include an alkyl group having 1 to 30, preferably 1 to 20 carbon atoms, and a group further substituted with a substituent such as an alkoxy group.

The silicon-containing group is, for example, a group containing 1 to 5 silicon atoms in the group. Specific examples of the silicon-containing group include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritrilsilyl, and trinaphthylsilyl. Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl and the like. When the silicon-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

Specific examples of the germanium-containing group include a group in which the silicon of the silicon-containing group is replaced with germanium. Specific examples of the tin-containing group include a group in which silicon in the silicon-containing group is replaced with tin. Further, examples of the transition metal catalyst (A) used in the present invention include those represented by the following formulas (II-a) or (II-b).

<chemistry num="4"><img id="000005" he="34" wi="80" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In addition, N ...... M¹Generally indicates that they are coordinated, but in the present invention, they may or may not be coordinated. )

In general formula (II-a), M¹Indicates a transition metal atom selected from groups 3 to 11 of the periodic table, preferably a transition metal atom of groups 4 to 5, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. It is preferably a Group 4 transition metal atom, specifically titanium, zirconium, or hafnium, and more preferably titanium.

Q is a nitrogen atom or substituent R²Carbon atom with (-C (R)²) =) Is shown. A is an oxygen atom, a sulfur atom, a selenium atom or a substituent R⁵Nitrogen atom with (-N (R)⁵)-) Is shown.

R¹Is a hydrocarbon group having at least one heteroatom or a hydrocarbon group having at least one heteroatom-containing group. Examples of the hetero atom include halogen, nitrogen, oxygen, phosphorus, sulfur, and selenium atoms. The hetero atom-containing group is a group containing a non-metal atom other than a carbon atom and a hydrogen atom, and specifically, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a halogen atom-containing group, and a heterocyclic compound. Residues and the like can be mentioned. Examples of the oxygen-containing group, nitrogen-containing group, sulfur-containing group, phosphorus-containing group and heterocyclic compound residue include those similar to X in the general formula (I). Halogen-containing groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and icosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl. , Alkenyl groups such as propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, trill, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, etc. Examples thereof include a group in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms is substituted with halogen, such as an aryl group of the above, and specific examples thereof include trifluoromethyl and perfluoro. Examples thereof include ethyl, pentafluorophenyl, perfluorohexyl, trichloromethyl, perchloroethyl, pentachlorophenyl and perchlorohexyl.

R¹A halogen atom-containing hydrocarbon group having 1 to 30 carbon atoms is preferable, and a fluorine atom-containing hydrocarbon group having 1 to 30 carbon atoms is particularly preferable. R¹Specifically, Trifluoromethyl, Perfluoroethyl, Perfluoropropyl, Perfluorobutyl, Perfluoropentyl, Perfluorohexyl, Perfluoroheptyl, Perfluorooctyl, Perfluorodecyl, 1H, 1H-Perfluoropropyl, 1H, 1H-Perfluoro Butyl, 1H, 1H-perfluoropentyl, 1H, 1H-perfluorohexyl, 1H, 1H-perfluoroheptyl, 1H, 1H-perfluorooctyl, 1H, 1H-perfluorodecyl, perfluorocyclohexyl, trifluoromethylcyclohexyl , Bis (trifluoromethyl) diclohexyl trifluoromethylfluorocyclohexyl, monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluorophenyl, (trifluoromethyl) fluorophenyl , Trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) phenyl, perfluoroethyl phenyl, bis (perfluoroethyl) phenyl , Perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthril, perfluoroanthril, (trifluoromethyl) tetra Fluorophenyl and the like can be mentioned.

R²~ R⁵Can be the same or different from each other, and may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, or a phosphorus-containing group. , Halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group. R²~ R⁵May form a ring in which two or more of these are connected to each other.

R²~ R⁵Examples of the boron-containing group, aluminum-containing group, phosphorus-containing group, halogen atom, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group represented by X in the above general formula (I) are exemplified. Something similar to the one.

Also R²~ R⁵As the halogen-containing group represented by, the R of the above general formula (II-a)¹The same as the one illustrated in the above can be mentioned. R²~ R⁵Examples of the hydrocarbon group indicated by are those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Linear or branched alkyl groups; linear or branched alkenyl groups such as vinyl, allyl, isopropenyl, etc. with 2 to 30, preferably 2 to 20 carbon atoms; ethynyl, propargyl, etc., having 2 to 20 carbon atoms. 30, preferably 2 to 20 linear or branched alkynyl groups; 3 to 30, preferably 3 to 20 cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; cyclo Cyclic unsaturated hydrocarbon groups with 5 to 30 carbon atoms such as pentadienyl, indenyl, and fluorenyl; 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, and anthryl. Alkyl groups of: Tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl and other alkyl-substituted aryl groups and the like.

Further, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl. R²~ R⁵Examples of the hydrocarbon-substituted silyl group of the above include groups having a total number of carbon atoms of 1 to 30. Specific examples thereof include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl (pentafluorophenyl) silyl. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable.

R²~ R⁵Examples of the oxygen-containing group represented by are the same as those exemplified by X in the above general formula (I). R²~ R⁵Examples of the nitrogen-containing group represented by the above include the same groups as those exemplified by X in the general formula (I).

R²~ R⁵Examples of the sulfur-containing group represented by the above include the same groups as those exemplified by X in the general formula (I). R²~ R⁵The group is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a halogen-containing group, and is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon. It is more preferably a hydrogen-substituted silyl group or a halogen-containing group.

R²~ R⁵As the halogen atom and halogen-containing group represented by, R in the above general formula (II-a)¹The same can be mentioned. n is M¹It is a number satisfying the valence of, specifically, an integer of 2 to 4, preferably 2.

X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group, and specific examples thereof include an atom or group similar to X in the above general formula (I).

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.

<chemistry num="5"><img id="000006" he="40" wi="77" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In addition, N ...... M¹Generally indicates that they are coordinated, but in the present invention, they may or may not be coordinated. )

In general formula (II-b), M¹Indicates a transition metal atom selected from groups 3 to 11 of the periodic table, preferably a transition metal atom of groups 4 to 5, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. It is preferably a Group 4 transition metal atom, specifically titanium, zirconium, or hafnium, and more preferably titanium.

m represents an integer of 1 to 5, preferably 2 to 4, and more preferably 2. A indicates a nitrogen atom or a phosphorus atom, U is a substituent R⁶Carbon atom with (-C (R)⁶) =), Indicates a nitrogen or phosphorus atom, Q is the substituent R⁷Carbon atom with (-C (R)⁷) =), Indicates a nitrogen or phosphorus atom, S is the substituent R⁸Carbon atom with (-C (R)⁸) =), Indicates a nitrogen or phosphorus atom, T is the substituent R⁹Carbon atom with (= C (R)⁹)-), Indicates a nitrogen or phosphorus atom, R¹Indicates a hydrocarbon group having one or more heteroatoms or a hydrocarbon group having one or more heteroatom-containing groups, and specifically, R in the above general formula (II-b).¹Is synonymous with.

R⁶~ R⁹Can be the same or different from each other, and may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, or a phosphorus-containing group. , Halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group. R²~ R⁵Oxygen-containing group, nitrogen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group. Examples of the germanium-containing group and the tin-containing group include groups similar to X in the above general formula (I).

R⁶~ R⁹The group is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a halogen-containing group, and is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon. It is more preferably a hydrogen-substituted silyl group or a halogen-containing group.

R⁶~ R⁹May form a ring by connecting two or more of these to each other, and when m is 2 or more, R¹R⁶R⁷R⁸R⁹They may be the same or different from each other, and R contained in any one of the ligands.⁶~ R⁹R contained in one of the groups and the other ligand⁶~ R⁹One of the groups may be linked.

n is a number that satisfies the valence of M. X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group, and specific examples thereof include an atom or group similar to X in the above general formula (I).

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. The transition metal compound (A) represented by the general formula (II-a) or (II-b) has a direct bond with the central metal M in the same manner as the transition metal compound represented by the general formula (I). It is preferable that the distance between the closest heteroatom that does not have and the hydrogen at the β-position is 3.0 Å or less and the electrostatic energy is -10 kJ / mol or less.

Further, as the transition metal catalyst (A) used in the present invention, among the transition metal compounds represented by the above general formulas (II-a) or (II-b), the following formula (II-a') or ( Represented by II-b'), R¹However, the one with the following structure can also be mentioned.

<chemistry num="6"><img id="000007" he="35" wi="86" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In addition, N ...... M¹Generally indicates that they are coordinated, but in the present invention, they may or may not be coordinated. )

In the general formula (II-a'), M¹Indicates a transition metal atom selected from groups 3 to 11 of the periodic table, preferably a transition metal atom of groups 4 to 5, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. It is preferably a Group 4 transition metal atom, specifically titanium, zirconium, or hafnium, and more preferably titanium.

Q is a nitrogen atom or substituent R²Carbon atom with (-C (R)²) =) Is shown. A is an oxygen atom, a sulfur atom, a selenium atom or a substituent R⁵Nitrogen atom with (-N (R)⁵)-) Is shown.

R¹Indicates a phenyl group having at least one substituent selected from a heteroatom and a heteroatom-containing group and other aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups.¹Is a phenyl group, it has one or more substituents selected from heteroatoms and heteroatom-containing groups at least at one of the 2nd and 6th positions, where the carbon atom bonded to the nitrogen atom is at the 1st position. Or, a heteroatom excluding a fluorine atom at the 3-position, 4-position, and 5-position, a fluorine-containing group containing 1 carbon atom and 2 or less fluorine atoms, and a fluorine-containing group containing 2 or more carbon atoms. It has at least one substituent selected from heteroatom-containing groups having a heteroatom other than a fluorine atom, and has an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group, and an alicyclic hydrocarbon group. In the case of, it is preferable to have one or more substituents selected from a heteroatom and a heteroatom-containing group.

R¹As the heteroatom and the heteroatom-containing group represented by, R in the above general formula (II-a)¹The same can be mentioned. Further, the transition metal compound represented by the above general formula (II-a') is R.¹A phenyl group having one or more substituents selected from a fluorine atom or a fluorine atom-containing group at at least one position at the 2nd and 6th positions, or 3 when the position of the carbon atom bonded to nitrogen is set to the 1st position. It has at least one substituent selected from a fluorine-containing group containing one carbon atom and two or less fluorine atoms at the 4-position, 4-position and 5-position, and a fluorine-containing group containing two or more carbon atoms. A fat having at least one substituent selected from a phenyl group, a fluorine atom, and an aromatic hydrocarbon group other than a phenyl group having at least one substituent selected from a fluorine atom and a fluorine atom-containing group. It is preferably a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms selected from alicyclic group hydrocarbon groups having at least one substituent selected from a group hydrocarbon group, a fluorine atom, and a fluorine atom-containing group. Such transition metal compounds are preferred in terms of activity and molecular weight of the resulting polymer.

R¹Specifically, Trifluoromethyl, Perfluoroethyl, Perfluoropropyl, Perfluorobutyl, Perfluoropentyl, Perfluorohexyl, Perfluoroheptyl, Perfluorooctyl, Perfluorodecyl, 1H, 1H-Perfluoropropyl, 1H, 1H-Perfluoro Butyl, 1H, 1H-perfluoropentyl, 1H, 1H-perfluorohexyl, 1H, 1H-perfluoroheptyl, 1H, 1H-perfluorooctyl, 1H, 1H-perfluorodecyl, perfluorocyclohexyl, trifluoromethylcyclohexyl , Bis (trifluoromethyl) cyclohexyltrifluoromethylfluorocyclohexyl, monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluorophenyl, (trifluoromethyl) fluorophenyl, Trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) phenyl, perfluoroethyl phenyl, bis (perfluoroethyl) phenyl, Perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthril, perfluoroanthril, (trifluoromethyl) tetrafluoro Examples include phenyl.

Preferably R¹Is a fluorine-containing aliphatic hydrocarbon group having 3 to 30 carbon atoms, specifically 1H, 1H-perfluoropropyl, 1H, 1H-perfluorobutyl, 1H, 1H-perfluoropentyl, 1H, 1H- Perfluorohexyl, 1H, 1H-perfluoroheptyl, 1H, 1H-perfluorooctyl, 1H, 1H-perfluorodecyl and the like can be mentioned. Or monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluorophenyl, (trifluoromethyl) fluorophenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, Tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) phenyl, perfluoroethyl phenyl, bis (perfluoroethyl) phenyl, perfluoropropyl phenyl, perfluorobutyl phenyl, perfluoropentyl Substituted with fluorine and / or fluorine-containing hydrocarbons such as phenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthryl, perfluoroanthryl, (trifluoromethyl) tetrafluorophenyl Examples thereof include aromatic hydrocarbon groups having 6 to 30 carbon atoms.

Of the above examples, R¹Particularly preferred are monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluorophenyl, 1H, 1H-perfluorooctyl. R²~ R⁵Can be the same or different from each other, and may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, or a phosphorus-containing group. , Halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group. R²~ R⁵May form a ring in which two or more of these are connected to each other.

R²~ R⁵Examples of the boron-containing group, aluminum-containing group, phosphorus-containing group, halogen atom, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group represented by X in the above general formula (I) are exemplified. Something similar to the one.

Also R²~ R⁵As the halogen-containing group represented by, the R of the above general formula (II-a)¹The same as the one illustrated in the above can be mentioned. R²~ R⁵Examples of the hydrocarbon group indicated by are those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Linear or branched alkyl groups; linear or branched alkenyl groups such as vinyl, allyl, isopropenyl, etc. with 2 to 30, preferably 2 to 20 carbon atoms; ethynyl, propargyl, etc., having 2 to 20 carbon atoms. 30, preferably 2 to 20 linear or branched alkynyl groups; 3 to 30, preferably 3 to 20 cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; cyclo Cyclic unsaturated hydrocarbon groups with 5 to 30 carbon atoms such as pentadienyl, indenyl, and fluorenyl; 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, and anthryl. Alkyl groups of: Tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl and other alkyl-substituted aryl groups and the like.

Further, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl. R²~ R⁵Examples of the hydrocarbon-substituted silyl group of the above include groups having a total number of carbon atoms of 1 to 30. Specific examples thereof include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl (pentafluorophenyl) silyl. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable.

R²~ R⁵Examples of the oxygen-containing group represented by are the same as those exemplified by X in the above general formula (I). R²~ R⁵Examples of the nitrogen-containing group represented by are the same as those exemplified by X in the above general formula (I). R²~ R⁵Examples of the sulfur-containing group represented by the above include the same groups as those exemplified by X in the general formula (I). R²~ R⁵As the halogen atom and halogen-containing group represented by, R in the above general formula (II-a)¹The same can be mentioned. R²~ R⁵The group is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a halogen-containing group, and is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon. It is more preferably a hydrogen-substituted silyl group or a halogen-containing group.

n is M¹It is a number satisfying the valence of, specifically, an integer of 2 to 4, preferably 2. X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group, and specific examples thereof include an atom or group similar to X in the above general formula (I).

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.

<chemistry num="7"><img id="000008" he="39" wi="82" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In addition, N ...... M¹Generally indicates that they are coordinated, but in the present invention, they may or may not be coordinated. )

In the general formula (II-b'), M¹Indicates a transition metal atom selected from Group 3 to 11 of the Periodic Table, preferably Group 4 to 5 of the Periodic Table. Specifically, is titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., preferably Group 4. It is a transition metal atom of, specifically titanium, zirconium, hafnium, and more preferably titanium.

m represents an integer of 1 to 5, preferably 2 to 4, and more preferably 2. A indicates a nitrogen atom or a phosphorus atom, U is a substituent R⁶Carbon atom with (-C (R)⁶) =), Indicates a nitrogen or phosphorus atom, Q is the substituent R⁷Carbon atom with (-C (R)⁷) =), Indicates a nitrogen or phosphorus atom, S is the substituent R⁸Carbon atom with (-C (R)⁸) =), Indicates a nitrogen or phosphorus atom, T is the substituent R⁹Carbon atom with (= C (R)⁹)-), Indicates a nitrogen or phosphorus atom, R¹Indicates a hydrocarbon group having one or more heteroatoms or a hydrocarbon group having one or more heteroatom-containing groups, and specifically, R in the above general formula (II-a').¹Is synonymous with.

R⁶~ R⁹Can be the same or different from each other, and may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, or a phosphorus-containing group. , Halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group. R²~ R⁵Oxygen-containing group, nitrogen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group. Examples of the germanium-containing group and the tin-containing group include groups similar to X in the above general formula (I).

R⁶~ R⁹The group is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a halogen-containing group, and is preferably a hydrogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl. More preferably, it is a group, a halogen atom, or a halogen-containing group.

R⁶~ R⁹May form a ring by connecting two or more of these to each other, and when m is 2 or more, R¹R⁶R⁷R⁸R⁹They may be the same or different from each other, and R contained in any one of the ligands.⁶~ R⁹R contained in one of the groups and the other ligand⁶~ R⁹One of the groups may be linked.

n is a number that satisfies the valence of M. X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group, and specific examples thereof include an atom or group similar to X in the above general formula (I).

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. Further, the transition metal catalyst (A) used in the present invention is a central metal in the β-agostic structure obtained by the density general function method for a cationic complex in which one of X in the formula is substituted with an n-propyl group. The distance between the closest heteroatom having no direct bond and the hydrogen at the β-position is 3.0 Å or less and the electrostatic energy is -10 kJ / mol or less, and the one represented by the following formula (III) can also be mentioned.

<chemistry num="8"><img id="000009" he="44" wi="81" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In addition, N ...... M¹Generally indicates that they are coordinated, but in the present invention, they may or may not be coordinated. )

In general formula (III), M¹Indicates a transition metal atom selected from groups 4 to 5 of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., preferably a transition metal atom of group 4, specifically. Is titanium, zirconium, hafnium, more preferably titanium.

m represents 1 or 2, preferably 2. R¹⁰Is a hydrocarbon group having at least one heteroatom or a hydrocarbon group having at least one heteroatom-containing group. Examples of the hetero atom include halogen, nitrogen, oxygen, phosphorus, sulfur, and selenium atoms. The hetero atom-containing group is a group containing a non-metal atom other than a carbon atom and a hydrogen atom, and specifically, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a halogen atom-containing group, and a heterocyclic compound. Residues and the like can be mentioned. Examples of the oxygen-containing group, nitrogen-containing group, sulfur-containing group, phosphorus-containing group and heterocyclic compound residue include those similar to X in the general formula (I).

Halogen-containing groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and icosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl. , Alkenyl groups such as propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, trill, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, etc. Examples thereof include a group in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms is substituted with halogen, such as an aryl group of the above, and specific examples thereof include trifluoromethyl and perfluoro. Examples thereof include ethyl, pentafluorophenyl, perfluorohexyl, trichloromethyl, perchloroethyl, pentachlorophenyl and perchlorohexyl.

R¹⁰A halogen atom-containing hydrocarbon group having 1 to 30 carbon atoms is preferable, and a fluorine atom-containing hydrocarbon group having 1 to 30 carbon atoms is particularly preferable. R¹⁰Specifically, as trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorodecyl, 1H, 1H-perfluoropropyl, 1H, 1H-perfluorobutyl, 1H, 1H-perfluoropentyl, 1H, 1H-perfluorohexyl, 1H, 1H-perfluoroheptyl, 1H, 1H-perfluorooctyl, 1H, 1H-perfluorodecyl, perfluoro Cyclohexyl, trifluoromethylcyclohexyl, bis (trifluoromethyl) cyclohexyltrifluoromethylfluorocyclohexyl, monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluorophenyl, (trifluoromethyl) Fluoromethyl) fluorophenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) phenyl, perfluoroethylphenyl, bis ( Perfluoroethyl) phenyl, perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthryl, perfluoroanthril, ( Examples thereof include trifluoromethyl) tetrafluorophenyl. R¹¹~ R¹⁴Indicates a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. R in general formula (II-a)²~ R⁵Indicates an atom or group similar to.

R¹⁵Indicates a halogen atom, a halogen-containing group, a hydrocarbon group or a hydrocarbon-substituted silyl group, and specifically, R in the above general formula (II-a).²~ R⁵Shows a group similar to. R¹⁵Examples of the hydrocarbon group indicated by are those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms. 1 to 20 linear or branched alkyl groups; hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. having an alicyclic skeleton with 3 to 30, preferably 3 to 20 carbon atoms. An aryl group having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthryl, and phenanthryl; and these groups having 1 to 30 carbon atoms, preferably. Is preferably an alkyl group having 1 to 20, a group further substituted with a substituent such as an aryl group having 6 to 30 carbon atoms, preferably 6 to 20, and more preferably a tert-butyl group.

R¹⁵The hydrocarbon-substituted silyl group represented by is R in the above general formula (II-a).²~ R⁵The same thing can be mentioned. R¹⁵As the heteroatom and the heteroatom-containing group represented by, R in the above general formula (II-a)¹The same can be mentioned.

Also, R¹⁰And R¹¹~ R¹⁵May be the same or different from each other, and two or more of them may be connected to each other to form a ring. n is M¹It is a number satisfying the valence of, specifically, an integer of 2 to 4, preferably 2.

X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group, and specific examples thereof include an atom or group similar to X in the above general formula (I).

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. Further, the transition metal catalyst (A) used in the present invention is represented by the following formula (III'), and is represented by R.¹⁰However, the one with the following structure can also be mentioned.

<chemistry num="9"><img id="000010" he="42" wi="84" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In addition, N ...... M¹Generally indicates that they are coordinated, but in the present invention, they may or may not be coordinated. ) In the formula, M¹, M, R¹¹~ R¹⁴, R¹⁵, N and X are M in the above general formula (III), respectively.¹, M, R¹¹~ R¹⁴, R¹⁵, N and X are synonymous.

R¹⁰Indicates a phenyl group having at least one substituent selected from a heteroatom and a heteroatom-containing group and other aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups.¹⁰Is a phenyl group, it has one or more substituents selected from heteroatoms and heteroatom-containing groups at at least one of the 2nd and 6th positions, where the carbon atom bonded to the nitrogen atom is at the 1st position. Or, a heteroatom excluding a fluorine atom at the 3-position, 4-position, and 5-position, a fluorine-containing group containing 1 carbon atom and 2 or less fluorine atoms, and a fluorine-containing group containing 2 or more carbon atoms. It has at least one substituent selected from heteroatom-containing groups having a heteroatom other than a fluorine atom, and has an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. In the case of, it has at least one substituent selected from a heteroatom and a heteroatom-containing group.

As the heteroatom and the heteroatom-containing group, R in the above general formula (II-a)¹The same can be mentioned. Further, the transition metal compound represented by the above general formula (III') is R.¹⁰A phenyl group having one or more substituents selected from a fluorine atom or a fluorine atom-containing group at at least one position at the 2nd and 6th positions, or 3 when the position of the carbon atom bonded to nitrogen is set to the 1st position. It has at least one substituent selected from a fluorine-containing group containing one carbon atom and two or less fluorine atoms at the 4-position, 4-position and 5-position, and a fluorine-containing group containing two or more carbon atoms. A fat having at least one substituent selected from a phenyl group, a fluorine atom, and an aromatic hydrocarbon group other than a phenyl group having at least one substituent selected from a fluorine atom and a fluorine atom-containing group. It is preferably a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms selected from alicyclic group hydrocarbon groups having at least one substituent selected from a group hydrocarbon group, a fluorine atom, and a fluorine atom-containing group. Such transition metal compounds are preferred in terms of activity and molecular weight of the resulting polymer.

Regarding the substitution position of the heteroatom or the substituent having a heteroatom-containing group, R¹⁰If is aromatic, R bound to a nitrogen atom¹⁰It is preferably located at the carbon atom (beta-position carbon atom) adjacent to the carbon atom inside, and R¹⁰When is an aliphatic, it is preferably in the adjacent position or further adjacent position (beta position or gamma position).

Heteroatoms and heteroatom-containing groups include those mentioned above. In particular, fluorine is preferable as the heteroatom, and fluorine-containing group is preferable as the heteroatom-containing group. R¹⁰Specifically, as trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorodecyl, 1H, 1H-perfluoropropyl, 1H, 1H-perfluorobutyl, 1H, 1H-perfluoropentyl, 1H, 1H-perfluorohexyl, 1H, 1H-perfluoroheptyl, 1H, 1H-perfluorooctyl, 1H, 1H-perfluorodecyl, perfluoro Cyclohexyl, trifluoromethylcyclohexyl, bis (trifluoromethyl) cyclohexyltrifluoromethylfluorocyclohexyl, monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluorophenyl, (trifluoromethyl) Fluoromethyl) fluorophenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) phenyl, perfluoroethylphenyl, bis ( Perfluoroethyl) phenyl, perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthryl, perfluoroanthril, ( Examples thereof include trifluoromethyl) tetrafluorophenyl.

Preferably R¹⁰Is a fluorine-containing aliphatic hydrocarbon group having 3 to 30 carbon atoms. Specifically, 1H, 1H-perfluoropropyl, 1H, 1H-perfluorobutyl, 1H, 1H-perfluoropentyl, 1H, 1H- Perfluorohexyl, 1H, 1H-perfluoroheptyl, 1H, 1H-perfluorooctyl, 1H, 1H-perfluorodecyl, or monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (tri Fluoromethyl) pentafluorophenyl, (trifluoromethyl) fluorophenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) Phenyl, perfluoroethyl phenyl, bis (perfluoroethyl) phenyl, perfluoropropyl phenyl, perfluorobutyl phenyl, perfluoropentyl phenyl, perfluorohexyl phenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorofe Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms substituted with fluorine and / or fluorine-containing hydrocarbons such as nantril, perfluoroanthryl, (trifluoromethyl) tetrafluorophenyl.

More preferably, R¹⁰Is an aromatic hydrocarbon group having 6 to 30 carbon atoms substituted with fluorine, an aromatic hydrocarbon group having 8 to 30 carbon atoms substituted with a fluorine-containing hydrocarbon having 2 or more carbon atoms, or a fluorine and fluorine-containing hydrocarbon. It is an aromatic hydrocarbon group having 7 to 30 carbon atoms substituted with a group, specifically monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) pentafluoro. Phenyl, (trifluoromethyl) fluorophenyl, trifluoromethylphenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentax (trifluoromethyl) phenyl, perfluoroethylphenyl, bis (perfluoroethyl) Phenyl, perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthryl, perfluoroanthril, (trifluoromethyl) Examples include tetrafluorophenyl.

Of the above examples, R¹⁰Especially preferably, 2-fluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group, pentafluorophenyl group, 4-trifluoromethyl 2,3,5,6-tetrafluoro. It is a phenyl group, a 2-trifluoromethylphenyl group, and a 1H, 1H-perfluorooctyl group.

Regarding the substitution position of fluorine, R¹⁰If is aromatic, R bound to a nitrogen atom¹⁰It is preferably located at the carbon atom (beta-position carbon atom) adjacent to the carbon atom inside, and R¹⁰When is an aliphatic, it is preferably in the adjacent position or further adjacent position (beta position or gamma position).

R¹¹~ R¹⁴Indicates a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. R in general formula (II-a)²~ R⁵Indicates an atom or group similar to.

R¹⁵Indicates a halogen atom, a halogen-containing group, a hydrocarbon group or a hydrocarbon-substituted silyl group, and specifically, R in the above general formula (II-a).²~ R⁵Shows a group similar to. R¹⁵Examples of the hydrocarbon group indicated by are those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms. 1 to 20 linear or branched alkyl groups; hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. having an alicyclic skeleton with 3 to 30, preferably 3 to 20 carbon atoms. An aryl group having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthryl, and phenanthryl; and these groups having 1 to 30 carbon atoms, preferably. Is preferably an alkyl group having 1 to 20, a group further substituted with a substituent such as an aryl group having 6 to 30 carbon atoms, preferably 6 to 20, and more preferably a tert-butyl group.

R¹⁵The hydrocarbon-substituted silyl group represented by is R in the above general formula (II-a).²~ R⁵The same thing can be mentioned. R¹⁵As the halogen atom and halogen-containing group represented by, R in the above general formula (II-a)¹The same can be mentioned.

Also, R¹⁰And R¹¹~ R¹⁵May be the same or different from each other, and two or more of them may be connected to each other to form a ring. n is M¹It is a number satisfying the valence of, specifically, an integer of 2 to 4, preferably 2.

X is an oxygen atom, a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group, and specific examples thereof include an atom or group similar to X in the above general formula (I).

When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. The transition metal compounds represented by the above general formulas (II-a'), (II-b') or (III') have a general density of cation complexes in which one of X in the formula is replaced with an n-propyl group. In the β-agostic structure obtained by the functional method, the distance between the closest heteroatom that does not have a direct bond with the central metal M and the hydrogen at the β position is 3.0 Å or less, and the electrostatic energy is -10 kJ / mol or less. Is preferable.

The transition metals represented by the above general formulas (I), (II-a), (II-b), (II-a'), (II-b'), (III) or (III') are described below. Specific examples of the compound are shown, but the present invention is not limited thereto.

<chemistry num="10"><img id="000011" he="223" wi="146" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

<chemistry num="11"><img id="000012" he="225" wi="148" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

<chemistry num="12"><img id="000013" he="132" wi="142" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

<chemistry num="13"><img id="000014" he="120" wi="147" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

<chemistry num="14"><img id="000015" he="231" wi="148" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

<chemistry num="15"><img id="000016" he="223" wi="148" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

<chemistry num="16"><img id="000017" he="145" wi="149" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the above example, Bu represents a butyl group.

In the present invention, in the above-mentioned compounds, a transition metal compound in which the titanium metal is replaced with a metal other than titanium such as zirconium and hafnium can also be used. The method for producing such a transition metal compound (A) is not particularly limited, and for example, the transition metal compound represented by the above general formula (III) can be used as a ligand when the transition metal compound is synthesized. Compound (ligand precursor) and M¹X_k(M and X are M in the above general formula (III).¹And X, where k is M¹It is a number that satisfies the valence of. Transition metal M represented by)¹It can be synthesized by reacting with the contained compound.

Ligand precursors are salicylaldehyde compounds and formula R¹⁰-NH₂(R¹⁰Is synonymous with the above. ) Is reacted with a primary amine compound, for example, an aniline compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those usually used for such a reaction are used, and among them, an alcohol solvent such as methanol and ethanol, or a hydrocarbon solvent such as toluene is preferable. The resulting solution is then stirred from room temperature under reflux conditions for about 1-100 hours to give the corresponding ligand precursor. When synthesizing the ligand precursor, an acid catalyst such as formic acid, acetic acid, or toluenesulfonic acid may be used as the catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as the dehydrating agent, or dehydration is performed by Dean Stark, it is effective for the reaction progress.

Next, the ligand precursor thus obtained and the transition metal M¹By reacting with the contained compound, the corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand precursor is dissolved in a solvent, and if necessary, it is contacted with a base to prepare a phenoxide salt, and then it is mixed with a metal compound such as a metal halide or a metal alkylated product at a low temperature. Mix and stir at -78 ° C to room temperature or under reflux conditions for about 1-48 hours. As the solvent, those usually used for such a reaction are used, and among them, ether, a polar solvent such as tetrahydrofuran (THF), a hydrocarbon solvent such as toluene, and the like are preferably used. Further, as the base used when preparing the phenoxide salt, a metal salt such as a lithium salt such as n-butyllithium and a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable.

In addition, depending on the nature of the compound, the ligand precursor and the transition metal M do not go through the phenoxide salt preparation.¹The corresponding transition metal compound can also be synthesized by directly reacting with the contained compound.

In addition, the metal M in the synthesized transition metal compounds¹Can be replaced with another transition metal by a conventional method. Also, for example, R¹⁰, R¹¹~ R¹⁵If any of the above is H, a substituent other than H can be introduced at any stage of the synthesis.

Further, the reaction solution of the ligand precursor and the transition metal M-containing compound can be used as it is for polymerization without isolating the transition metal compound. The general method for producing these complexes is also described in EP1008595A2. The transition metal compound (A) as described above is used alone or in combination of two or more.

<u style="single">(B-1) Organometallic compound</u> As the (B-1) organometallic compound used as necessary in the present invention, the following organometallic compounds of Groups 1, 2 and 13 of the periodic table are specifically used.

(B-1a): General formula R^a_mAl (OR^{b b})_nH_pX_q(In the formula, R^aAnd R^{b b}May be the same or different from each other, indicating hydrocarbon groups having 1 to 15, preferably 1 to 4 carbon atoms, X indicating a halogen atom, m 0 &lt;m3, n 0 n &lt;3 and p are 0 p &lt;3, q is a number of 0 q &lt;3, and m + n + p + q = 3. ) Organoaluminium compound represented by.

(B-1b): General formula M²AlR^a₄(In the formula, M²Indicates Li, Na or K, R^aIndicates a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms. ) Periodic table represented by a complex alkylated product of Group 1 metal and aluminum.

(B-1c): General formula R^aR^{b b}M³(In the formula, R^aAnd R^{b b}May be the same or different from each other and represent hydrocarbon groups with 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, M.³Is Mg. ) The compound represented by.

Examples of the organoaluminum compound belonging to (B-1a) include the following compounds. General formula R^a_mAl (OR^{b b})_3-m(In the formula, R^aAnd R^{b b}May be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably a number of 1.5 m 3. ) Organoaluminium compound, represented by General formula R^a_mAlX_3-m(In the formula, R^aRepresents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 &lt;m &lt;3. ) Organoaluminium compound, represented by General formula R^a_mAlH_3-m(In the formula, R^aIndicates a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably 2 m &lt;3. ) Organoaluminium compound, represented by General formula R^a_mAl (OR^{b b})_nX_q(In the formula, R^aAnd R^{b b}May be the same or different from each other, indicating hydrocarbon groups having 1 to 15, preferably 1 to 4 carbon atoms, X indicating a halogen atom, m 0 &lt;m3, n 0 n &lt;3 and q are numbers 0 q &lt;3, and m + n + q = 3. ) Organoaluminium compound represented by.

More specifically, as the organoaluminum compound belonging to (B-1a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like Tri-n-alkylaluminum; Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Tri-branched alkylaluminum such as methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum; Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; Triarylaluminum such as triphenylaluminum, tritrylaluminum; (I c₄H₉)_xAl_y(C₅H₁₀)_z(In the equation, x, y, z are positive numbers and z 2x.) Trialkenyl aluminum such as triisoprenyl aluminum; Alkoxides such as isobutylaluminum methoxydo, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxyde, diethylaluminum ethoxide, dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide; R^a_2.5Al (OR^{b b})_0.5Partially alkoxylated alkylaluminum with an average composition represented by, etc.; Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-) Di-t-butyl-4-methylphenoxide), dialkylaluminum allyloxides such as isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide; Partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride, alkylaluminum dihalide such as butylaluminum dibromid; Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride; Other partially hydrogenated alkylaluminum such as ethylaluminum dihydride, alkylaluminum dihydride such as propylaluminum dihydride; Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromid and the like.

A compound similar to (B-1a) can also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound, (C₂H₅)₂AlN (C₂H₅) Al (C₂H₅)₂And so on.

The compound belonging to (B-1b) is LiAl (C).₂H₅)₄, LiAl (C₇H₁₅)₄And so on. In addition, as (B-1) organic metal compounds, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound such that the above-mentioned organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, a combination of aluminum halide and alkylmagnesium, and the like can also be used.

Among the organometallic compounds (B-1), organoaluminum compounds are preferable. The above-mentioned (B-1) organometallic compound is used alone or in combination of two or more.

<u style="single">(B-2) Organoaluminium oxy compound</u> The (B-2) organoaluminum oxy compound used as necessary in the present invention may be a conventionally known aluminoxane, or benzene-insoluble organoaluminum as exemplified in JP-A-2-78687. It may be an oxy compound.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.

(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, the solvent or unreacted organoaluminum compound may be distilled and removed from the recovered solution of aluminoxane, and then redissolved in the solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used when preparing alminoxane include organoaluminum compounds similar to those exemplified as the organoaluminum compounds belonging to (B-1a) above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymen; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane; petroleum distillates such as gasoline, kerosene, light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, especially chlorine Examples thereof include hydrocarbon solvents such as isomers and bromines. Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

The benzene-insoluble organic aluminum oxy compound has an Al component dissolved in benzene at 60 ° C of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, that is, benzene. It is preferably insoluble or sparingly soluble.

Examples of the organoaluminum oxy compound include an organoaluminum oxy compound containing boron represented by the following general formula (IV).

<chemistry num="17"><img id="000018" he="25" wi="92" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R²¹Indicates a hydrocarbon group having 1 to 10 carbon atoms. R²²May be the same or different from each other, and indicate a hydrocarbon group having a hydrogen atom, a halogen atom, and a carbon atom number of 1 to 10. )

The organoaluminum oxy compound containing boron represented by the general formula (II) is the alkylboronic acid represented by the following general formula (V). R²¹-B- (OH)₂ ... (V) (In the formula, R²¹Indicates the same group as above. ) It can be produced by reacting the organoaluminum compound in an inert solvent under an atmosphere of an inert gas at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (V) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-hexylboronic acid. Acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like can be mentioned. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These are used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include organoaluminum compounds similar to those exemplified as the organoaluminum compounds belonging to (B-1a) above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more. The above-mentioned (B-2) organoaluminum oxy compound is used alone or in combination of two or more.

<u style="single">(B-3) A compound that reacts with a transition metal compound (A) to form an ion pair.</u> Examples of the compound (B-3) (hereinafter referred to as ionized ionic compound) that reacts with the transition metal compound (A) used in the present invention to form an ion pair include JP-A 1-501950. Published in JP-A No. 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A 3-207703, JP-A 3-207704, USP-5321106, etc. Examples thereof include Lewis acid, an ionic compound, a borane compound and a carborane compound. Further, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as Lewis acid, BR₃(R is a phenyl group or fluorine which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group.) Examples thereof include trifluoroboron, triphenylboron and tris. (4-Fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) ) Boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (VI).

<chemistry num="18"><img id="000019" he="26" wi="77" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the formula, R²³As H⁺, Carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptiltyrienyl cation, ferrosenium cation having a transition metal and the like.

R²⁴~ R²⁷May be the same or different from each other and are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specifically, the ammonium cations include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-dialkylanilinium cations such as N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as di (isopropyl) ammonium cations, dicyclohexylammonium cations And so on.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R²³As, carbonium cations, ammonium cations and the like are preferable, and triphenylcarbonium cations, N, N-dimethylanilinium cations and N, N-diethylanilinium cations are particularly preferable.

Further, as the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n) -Butyl) Ammonium Tetra (o-trill) Boron and the like.

Specifically, as N, N-dialkylanilinium salt, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Furthermore, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Cyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compound represented by the following formula (VII) or (VIII) and the like can also be mentioned.

<chemistry num="19"><img id="000020" he="38" wi="96" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, Et represents an ethyl group.)

<chemistry num="20"><img id="000021" he="34" wi="88" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> Specific examples of the borane compound include tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III) and tri (n-butyl) ammonium bis (undecahydride-). 7,8-Dicarbaundecaborate) Tetrate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarbaundecaborate) Cobalate (III), Tri (n-butyl) ) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Nickate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7,8-Dicarba Undecaborate) Copper Acidate ( III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-dicarbaundecaborate) Hydrochloride (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl- 7,8-Dicarbaundecaborate) Tetrate (III), Tri (n-butyl) Ammonium Bis (Nonahydrate-7,8-Dimethyl-7,8-Dicarbaundecaborate) Chromate (III), Tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydrate-7-carbaun) Decaborate) Chromate (III), Bis [Tri (n-butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaun Decaborate) Manganate (IV), Bis [Tri (n-Butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Cobalate (III), Bis [Tri (n-Butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Nickate (IV), etc. Examples include salts of the metal carborane anion of.

Heteropoly compounds consist of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, limvanadate acid, germanovanadate acid, arsenic vanadate acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdenum acid, germanomolydic acid, arsenic molybdenum acid, tin molybdenum acid, phosphorus. Tungsonic acid, germanotungstate, tin-tungstate, phosphoribdovanadate, lintangustovanadate, germanotangstovanadate, phosphoribdotangstovanadate, germanomoribdotangstovanadate, phosphoribbed Tungsic acid, phosphoribdoniobic acid, and salts of these acids, such as Group 1 or Group 2 metals of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, berylium, magnesium, calcium, strontium. , Salts with barium and the like, organic salts with triphenylethyl salt and the like can be used, but this is not the case.

The above-mentioned (B-3) ionized ionic compounds are used alone or in combination of two or more. When the above-mentioned transition metal compound (A) is used as a catalyst for olefin polymerization, when it is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component, very high polymerization activity for olefins is obtained. Shown.

In the present invention, the transition metal compound (A) represented by any of the general formulas (I), (II-a), (II-b) or (III) may be used alone as an olefin polymerization catalyst. Then, it reacts with (A) transition metal compound, (B) (B-1) organometallic compound (B-2) organoaluminum oxy compound, and (B-3) transition metal compound (A) to form an ion pair. At least one compound selected from the compounds to be formed may be used as an olefin polymerization catalyst.

When the transition metal compound (A) and the component (B) are used in combination, when the transition metal compound (A) is represented by the general formula (III), the following general formula (III-a) is used in the polymerization system. Form the compound represented.

<chemistry num="21"><img id="000022" he="45" wi="100" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the formula, R¹⁰~ R¹⁵, M¹, M, n and X are R in the above general formula (III), respectively.¹⁰~ R¹⁵, M¹, M, n and X, where Y represents the so-called weakly coordinated anion.

In the above general formula (III-a), the bond between the metals M and Y may be a covalent bond or an ionic bond. Specific examples of Y include the weakly coordinated anions described in Chemical Review, Vol. 88, p. 1405 (1988), Chemical Review, Vol. 93, p. 927 (1993), WO98 / 30612, p. 6 To AlR^4-(Rs may be the same or different from each other Oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom or substituent containing these, Alternatively, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, Alternatively, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group substituted with an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom, Alternatively, it indicates a group in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group is substituted with an oxygen atom, a nitrogen atom, a substituent having a phosphorus atom or a halogen atom. ) BR^4-(Rs may be the same or different from each other Oxygen atom, nitrogen atom, phosphorus atom, halogen atom or substituent containing these, Alternatively, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, Alternatively, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group substituted with an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom, Alternatively, it indicates a group in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group is substituted with a substituent having an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom. ) Or PF^6-, SbF^5-, Trifluoromethanesulfonate, p-toluenesulfonate and the like.

The olefin polymerization catalyst used in the present invention includes the above-mentioned transition metal compound (A), an organometallic compound (B-1), an organoaluminum oxy compound (B-2) and an ionized ionic compound (B-3). In addition to at least one compound (B) selected from the above (hereinafter, may be referred to as "component (B)"), the following carrier (C) and / or an organic compound (D) as described later may be added as necessary. Can include.

<u style="single">(C) Carrier</u> The carrier (C) used as needed in the present invention is an inorganic or organic compound, which is a solid in the form of granules or fine particles.

Of these, as the inorganic compound, a porous oxide, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable. As a porous oxide, specifically SiO₂, Al₂O₃, MgO, ZrO, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂Etc., or use composites or mixtures containing these, eg natural or synthetic zeolites, SiO₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO etc. can be used. Of these, SiO₂And / or Al₂O₃Is preferable.

The above-mentioned inorganic oxide contains a small amount of Na.₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg (NO)₃)₂, Al (NO)₃)₃, Na₂OK₂O, Li₂It does not matter if it contains a carbonate such as O, a sulfate, a nitrate, or an oxide component.

The properties of such porous oxides differ depending on the type and manufacturing method, but the preferably used carrier has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m.²/ g, preferably 100-700m²It is in the range of / g and has a pore volume of 0.3 to 3.0 cm.³It is desirable to be in the range of / g. Such a carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

As an inorganic halide, MgCl₂, MgBr₂, MnCl₂, MnBr₂Etc. are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a solvent in which inorganic chlorides are dissolved in a solvent such as alcohol, and then these are precipitated in the form of fine particles with a precipitant.

Clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Also, as clay, clay mineral or ion-exchange layered compound, clay, clay mineral, hexagonal fine packing type, antimony type, CdCl₂Type, CdI₂An ionic crystalline compound having a layered crystal structure such as a mold can be exemplified.

Such clays and clay minerals include kaolin, bentonite, knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dicite. , Halloysite, etc., and examples of ion-exchangeable layered compounds include α-Zr (HAsO).₄)₂ H₂O, α-Zr (HPO₄)₂, Α-Zr (KPO)₄)₂ 3H₂O, α-Ti (HPO₄)₂, Α-Ti (HAsO)₄)₂ H₂O, α-Sn (HPO₄)₂ H₂O, γ-Zr (HPO₄)₂, Γ-Ti (HPO₄)₂, Γ-Ti (NH₄PO₄)₂ H₂Examples include crystalline acid salts of multivalent metals such as O.

Such clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by a mercury intrusion method, and particularly preferably 0.3 to 5 cc / g. Here, the pore volume is determined by the mercury intrusion method using a mercury porosimeter, and the pore radius is 20 to 3 × 10.⁴Measured over the range of Å.

When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity. It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion-exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. TiCl is a guest compound that can be intercalated.₄, ZrCl₄Cationic inorganic compounds such as Ti (OR)₄, Zr (OR)₄, PO (OR)₃, B (OR)₃Metal alkoxides such as (R is a hydrocarbon group, etc.), [Al₁₃O₄(OH)₂₄]⁷⁺, [Zr₄(OH)₁₄]²⁺, [Fe₃O (OCOCH₃)₆]⁺Metal hydroxide ions and the like can be mentioned. These compounds are used alone or in combination of two or more. Also, when intercalating these compounds, Si (OR)₄, Al (OR)₃, Ge (OR)₄Polymerized product obtained by hydrolyzing metal alkoxides such as (R is a hydrocarbon group, etc.), SiO₂Colloidal inorganic compounds such as, etc. can coexist. In addition, examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

Clays, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after treatments such as ball milling and sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

Of these, preferred are clays or clay minerals, with particular preference being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica. Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer or vinylcyclohexane or styrene produced mainly of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Examples of (co) polymers produced with the above as a main component and variants thereof.

<u style="single">(D) Organic compound component</u> In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical characteristics of the produced polymer, if necessary. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

Alcohols and phenolic compounds are usually R²⁸The one represented by -OH is used, where R²⁸Indicates a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As alcohols, R²⁸Is preferably a halogenated hydrocarbon. Further, as the phenolic compound, those in which the α and α'-positions of the hydroxyl groups are substituted with hydrocarbons having 1 to 20 carbon atoms are preferable.

As a carboxylic acid, usually R²⁹-The one represented by COOH is used. R²⁹Indicates a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acids having a POH bond, P-OR, phosphate having a P = O bond, and a phosphine oxide compound are preferably used. As the sulfonate, those represented by the following general formula (IX) are used.

<chemistry num="22"><img id="000023" he="26" wi="101" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the formula, M is an element of groups 1 to 14 of the periodic table.

R³⁰Is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

m is an integer from 1 to 7, and n is 1 n 7. FIG. 1 shows an example of a step of preparing an olefin polymerization catalyst that may be used in the present invention. At the time of polymerization, the usage and the order of addition of each component are arbitrarily selected, and the following methods are exemplified. (1) A method of adding the transition metal compound (A) alone to the polymerizer. (2) A method of adding the transition metal compound (A) and the component (B) to the polymerizer in an arbitrary order. (3) A method of adding a catalyst component in which a transition metal compound (A) is supported on a carrier (C) and a component (B) to a polymerizer in an arbitrary order. (4) A method of adding a catalyst component in which a component (B) is supported on a carrier (C) and a transition metal compound (A) to a polymerizer in an arbitrary order. (5) A method of adding a catalyst component in which a transition metal compound (A) and a component (B) are supported on a carrier (C) to a polymerizer.

In each of the above methods (2) to (5), at least two or more of each catalyst component may be contacted in advance. In each of the above methods (4) and (5) in which the component (B) is supported, the component (B) in which the component (B) is not supported may be added in any order, if necessary. In this case, the component (B) may be the same or different.

Further, the solid catalyst component in which the transition metal compound (A) is supported on the above component (C) and the solid catalyst component in which the transition metal compound (A) and the component (B) are supported on the component (C) are olefins. It may be prepolymerized, and the catalyst component may be further supported on the prepolymerized solid catalyst component.

In the olefin polymerization method according to the present invention, a polymer is obtained by polymerizing or copolymerizing an olefin having 2 to 20 carbon atoms in the presence of the above-mentioned olefin polymerization catalyst. Examples of the olefin having 2 to 20 carbon atoms include the same as above. In the present invention, the polymerization can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method.

Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, etc., and the olefin itself is used as a solvent. You can also do it.

When polymerizing an olefin having 2 to 20 carbon atoms using the above catalyst for olefin polymerization, the transition metal compound (A) is usually 10 per liter of reaction volume.^-12~ 1 mol, preferably 10^-10~10^-2It is used in an amount that makes it a mole.

When component (B-1) is used, the molar ratio of component (B-1) to the transition metal atom (M) in the transition metal compound (A) is usually [(B-1) / M]. It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. When the component (B-2) is used, the molar ratio of the aluminum atom in the component (B-2) to the transition metal atom (M) in the transition metal compound (A) [(B-2) / M ] Is usually used in an amount such that it is usually 10 to 500,000, preferably 20 to 100,000. When the component (B-3) is used, the molar ratio [(B-3) / M] of the component (B-3) to the transition metal atom (M) in the transition metal compound (A) is usually It is used in an amount of 1 to 10, preferably 1 to 5.

When the component (D) is used, when the component (B) is the component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. When the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. When the component (B) is the component (B-3), the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. Used.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of -40 to + 200 ° C, preferably 0 to + 100 ° C. Polymerization pressure is usually normal pressure ~ 100kg / cm², Preferably normal pressure ~ 50kg / cm²The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by controlling the monomer / catalyst ratio and the polymerization time. According to the production method of the present invention, the olefin polymer, for example, the number average molecular weight as described above is in the range of 500 or more, preferably 500 to 10,000,000, more preferably 1,000 to 5,000,000, and Mw / Mn is 1.5 or less, preferably 1.3. The following olefin polymer is obtained.

According to the production method of the present invention, it is possible to obtain an olefin polymer having a high molecular weight and a narrow molecular weight distribution, an olefin-based tapered polymer having a precisely controlled structure, or an olefin-based block copolymer having high polymerization activity at a high polymerization temperature. it can.

In the method for producing an olefin polymer according to another aspect of the present invention, the polymer obtained as described above is brought into contact with a functional group-containing compound to obtain an olefin polymer having a functional group at the terminal as described above. To manufacture. The functional group-containing compound also includes a compound that can be converted into a functional group.

Here, examples of the functional group-containing compound or the compound that can be converted into a functional group include compounds having a functional group such as an aromatic hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a phosphorus-containing group, and a metal atom-containing group. Specific examples include aromatic vinyl compounds, iodine, chlorine, bromine, carbon dioxide, ester compounds, aldehyde compounds, carboxylic acid compounds, oxygen, alkylamine compounds, silicon halides, alkylaluminum compounds, and alkylboron compounds. , Alkyl zinc compounds, alkyl lithium compounds and the like.

Further, after contacting with a functional group-containing compound, it is also possible to convert to another functional group by a known method. The temperature at which the olefin polymer is brought into contact with the functional group-containing compound is -78 to + 300 ° C, preferably -78 to + 200 ° C, and the pressure is normal pressure to 100 kg / cm.², Preferably normal pressure ~ 50kg / cm²Is the range of. The contact time is in the range of 1 minute to 100 hours, preferably 10 minutes to 24 hours.

The contact between the olefin polymer and the functional group-containing compound can be carried out in a solvent or in the absence of a solvent, and the solvents used include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and the like. Aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, diethyl ether, Oxygen-containing compounds such as tetrahydrofuran or mixtures thereof and the like can be mentioned.

Further, in the method for producing an olefin polymer according to another aspect of the present invention, at least two kinds selected from olefins having 2 to 20 carbon atoms in the presence of the above-mentioned transition metal compound (A) -containing catalyst for olefin polymerization. It is characterized in that the above-mentioned olefins having different polymerization reactivity coexist to produce a tapered polymer containing segments in which two or more kinds of monomer compositions change continuously.

Here, as described above, the tapered polymer is a polymer in which the comonomer composition gradually changes from one end of the polymer to the other end. This polymer can be synthesized by polymerizing two or more kinds of monomers having different reactivity (for example, ethylene and propylene) in a living polymerization system in which a chain transfer reaction does not substantially occur.

In this case, as a method of supplying the monomers, a method of supplying the monomers while continuously changing the composition of the plurality of monomers, or a method of charging the plurality of monomers at the initial stage of polymerization and utilizing the difference in polymerization reactivity to provide a tapered polymer. The method of obtaining it can be mentioned. The same as above can be mentioned with respect to the temperature and pressure at which this polymerization is carried out, the method of adding the catalyst, the method of supporting the polymer, and the like.

The two or more types of monomers used are selected from the above-mentioned olefins having 2 to 20 carbon atoms, and are selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, and 1-octene. It is preferably selected, more preferably ethylene, propylene, 1-butene.

Further, in the method for producing an olefin polymer according to another aspect of the present invention, the following steps (1) and (2) and, if necessary, an arbitrary number of steps (3) are performed to form an olefin composed of a plurality of polymer blocks. Produce a block polymer.

In step (1), a polymer block is produced by polymerizing at least one olefin selected from olefins having 2 to 20 carbon atoms in the presence of the olefin polymerization catalyst. Examples of the olefin having 2 to 20 carbon atoms include the same as above, and these can be used individually by 1 type or in combination of 2 or more types. Moreover, as the polymer block, the same thing as above can be mentioned.

In step (1), the polymerization temperature is usually in the range of -40 to + 200 ° C, preferably 0 to + 150 ° C. Polymerization pressure is usually normal pressure ~ 100kg / cm², Preferably normal pressure ~ 50kg / cm²Under the conditions of.

In the step (2), at least one olefin selected from olefins having 2 to 20 carbon atoms is polymerized in the presence of the polymer block produced in the above step (1), and the polymer block is defined as the above polymer block. Produce different polymer blocks.

Here, different polymer blocks refer to those in which at least one of the primary structures of the polymer is different, such as monomer species, comonomer species, comonomer composition, comonomer content, comonomer arrangement, and stereoregularity.

Examples of the olefin having 2 to 20 carbon atoms include the same as above, and these can be used individually by 1 type or in combination of 2 or more types. Moreover, as the polymer block obtained in this step (2), the same thing as above can be mentioned.

In step (2), the polymerization temperature is usually in the range of -40 to + 200 ° C, preferably 0 to + 150 ° C. Polymerization pressure is usually normal pressure ~ 100kg / cm², Preferably normal pressure ~ 50kg / cm²Under the conditions of.

Step (3) Selected from olefins having 2 to 20 carbon atoms in the presence of a block polymer containing the polymer block obtained in the above step (1) and the polymer block obtained in the step (2). At least one kind of olefin is polymerized to produce a polymer block different from the polymer block produced in the previous step. Examples of the olefin having 2 to 20 carbon atoms include the same as above, and these can be used individually by 1 type or in combination of 2 or more types. Moreover, as the polymer block obtained in the step (3), the same thing as above can be mentioned.

In step (3), the polymerization temperature is usually in the range of -40 to + 200 ° C, preferably 0 to + 150 ° C. Polymerization pressure is usually normal pressure ~ 100kg / cm², Preferably normal pressure ~ 50kg / cm²Under the conditions of.

This step (3) can be performed any number of times by changing the type, combination or polymerization conditions of the olefin. By the production method of the present invention, for example, the above-mentioned olefin block copolymer can be obtained.

According to the production method of the present invention, an olefin-based block copolymer having high polymerization activity, high molecular weight, and narrow molecular weight distribution can be obtained at a high polymerization temperature. In the present invention, the block copolymer obtained as described above and a functional group-containing compound can be brought into contact with each other to obtain an olefin block copolymer having a functional group at the terminal.

The contact between the olefin-based block copolymer and the functional group-containing compound is carried out in the same manner as described above. Further, in the method for producing an olefin polymer according to another aspect of the present invention, the olefin is polymerized in the presence of a catalyst that promotes the living polymerization of the olefin, and the bond between the catalyst produced in the system and the produced polymer chain is chain-transferred. Polymerization is carried out using a catalyst obtained by cutting with.

It can be confirmed that the living polymerization proceeds by narrowing the molecular weight distribution of the obtained polymer and increasing the molecular weight of the produced polymer with the polymerization time. According to this, for example, the above-mentioned monodisperse polyolefin and olefin It is possible to produce copolymers, tapered polymers or olefin block copolymers.

Whether or not the above-mentioned living polymerization is proceeding is best confirmed by polymerizing the olefin under the conditions excluding the chain transfer agent, for example. Whether or not the above monodisperse polyolefin, olefin copolymer, tapered polymer or olefin block copolymer can be provided is exactly the same condition except that the operation of cutting by a chain transfer reaction is not performed (simply removing the chain transfer agent). (Conditions), it is best to confirm whether or not the olefin can be polymerized to give the olefin-based polymer described in the above-mentioned olefin polymer, tapered polymer or olefin block copolymer.

In this case, examples of the olefin polymerization catalyst used include those (1) to (5) below. (1) Olefin polymerization catalyst composed of Group 4 metallocene compound and soluble non-coordinating anion compound Specifically, the following structure can be mentioned. [YCpM²X¹] [(C₂B₉H₁₁)₂Co] [(YCp)₂M²X²(L)] [X³ B (C₆F₅)₃] [(Y-CpM²X⁴)₂X⁵] [B'] In the formula M²Is titanium, zirconium or hafnium, Y is a hydrocarbon group with one or more carbon atoms 1 to 20 Cp is a ligand with a cyclopentadienyl skeleton. When multiple Cp are included, one type or two or more types may be used.

X¹~ X⁵Is the same as X described above, L is a neutral Lewis acid, and B'is a non-coordinating anion described above. (2) (YCp)₂SmX⁶, Y-CpTaX⁷, Y-CpNbX⁸(In the formula, Y and Cp are the same as above, X⁶~ X⁸Is the same as X above. ) And methylaluminoxane combined with an olefin polymerization catalyst (3) Compound represented by the following formula

<chemistry num="23"><img id="000024" he="35" wi="50" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the formula, R³¹~ R³³Indicates an alkyl group or an aryl group having a hydrogen atom or 1 to 8 carbon atoms. However, R³¹~ R³³At least one of the must be a hydrogen atom, but R³¹~ R³³Not all of them are hydrogen atoms.

(4) Compound represented by the following formula

<chemistry num="24"><img id="000025" he="36" wi="39" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the formula, M³Indicates a transition metal atom of groups 8 to 10 of the periodic table, preferably nickel, palladium, or platinum.

R³⁴~ R³⁷May be the same or different from each other, and may be selected from hydrocarbon groups having 1 to 50 carbon atoms, halogenated hydrocarbon groups having 1 to 50 carbon atoms, organic silyl groups or nitrogen, oxygen, phosphorus, sulfur, and silicon. Indicates a hydrocarbon group substituted with a substituent containing one element.

R³⁴~ R³⁷Two or more of these groups, preferably adjacent groups, may be connected to each other to form a ring. q indicates an integer from 0 to 4.

X⁹Indicates a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, and a nitrogen-containing group. When q is 2 or more, the plurality of groups represented by X may be the same or different from each other.

(5) Compound represented by the following formula

<chemistry num="25"><img id="000026" he="30" wi="45" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> In the formula, M⁴Indicates a transition metal atom of Group 3 to 6 of the periodic table, preferably titanium, zirconium or hafnium.

R³⁸And R³⁹Can be the same or different from each other, and may be hydrogen atoms, hydrocarbon groups with 1 to 50 carbon atoms, halogenated hydrocarbon groups with 1 to 50 carbon atoms or organic silyl groups, or nitrogen, oxygen, phosphorus, sulfur and silicon. Indicates a substituent having at least one element selected from.

m is an integer from 0 to 2. n is an integer from 1 to 5. A indicates an atom of Group 13 to 16 of the periodic table, and specific examples thereof include boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, selenium, and tin, which are carbon or silicon. Is preferable.

When n is 2 or more, the plurality of A's may be the same as or different from each other. E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When there are a plurality of groups represented by E, the plurality of groups represented by E may be the same or different from each other, and two or more groups represented by E are connected to each other to form a ring. You may.

p is an integer from 0 to 4. X¹⁰Indicates a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing machine. .. If p is 2 or more, X¹⁰The plurality of groups indicated by may be the same as or different from each other.

The olefin compounds having 1 to 20 carbon atoms used in the polymerization are linear or branched α-olefins having 2 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, and vinyl, which are the same as those described above. Cyclohexane, diene, polyene, aromatic vinyl compounds and the like can be mentioned. These olefins can be used alone or in combination of two or more.

Further, examples of the olefin used in the present invention include monomers having atoms other than carbon and hydrogen, and specific examples of such monomers include the above-mentioned α, β-unsaturated carboxylic acid, cyclic olefin carboxylic acid and The anhydrides and metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts and calcium salts thereof, α, β-unsaturated carboxylic acid esters, vinyl esters, unsaturated glycidyls, hydrocarbon olefins. , Unsaturated cyano compounds, unsaturated ketones, unsaturated ethers, functional group-containing styrene derivatives, vinyl group-containing heterocyclic compounds and the like.

At least one of the olefins used in the present invention is an olefin consisting only of carbon and hydrogen. The amount ratio of the olefin consisting only of carbon and hydrogen to the total olefin is not particularly limited, and examples thereof include an amount of 5 mol% or more and 100 mol% or less of the total olefin. Further, at least one kind is sufficient if at least one kind of olefin consisting only of carbon and hydrogen is contained in the whole olefin polymer according to the present invention, for example, an olefin polymer composed of a plurality of polymer blocks. If so, any polymer block may contain an olefin consisting only of carbon and hydrogen.

The conditions for polymerizing these olefins include the above-mentioned conditions, and the polymerization temperature is usually in the range of -100 to + 200 ° C, preferably -78 to + 150 ° C. Polymerization pressure is usually normal pressure ~ 100kg / cm², Preferably normal pressure ~ 50kg / cm²Is the range of.

Further, the chain transfer reaction is allowed to proceed by holding it at a predetermined temperature at which the reaction proceeds, or is selected from hydrogen, organoaluminum compounds, organoboron compounds, organozinc compounds, organosilicon compounds, organocadadmium compounds, and organolead compounds. It is characterized by advancing with one or more compounds.

The conditions for advancing the chain transfer may be the same as or different from the above-mentioned olefin polymerization reaction, and the temperature is usually in the range of -100 to + 200 ° C-, preferably -78 to + 150 ° C. is there. Pressure is usually normal pressure ~ 100kg / cm², Preferably normal pressure ~ 50kg / cm²Under the conditions of.

When the chain transfer reaction is allowed to proceed by heat, the olefin compound is polymerized at a temperature at which the chain transfer does not proceed, then the reaction system is kept at a predetermined temperature at which the chain transfer proceeds, the chain transfer reaction proceeds, and then the chain transfer reaction proceeds again. It is preferable to carry out the polymerization at a temperature at which the transfer reaction does not proceed. Further, this operation may be repeated any number of times.

When the chain transfer reaction is carried out using one or more compounds selected from hydrogen, organoaluminum compounds, organoboron compounds, organozinc compounds, organosilicon compounds, organic cadmium compounds, and organolead compounds, these reactants are used. It may coexist from the start of the polymerization, or may be added afterwards at any stage. In the case of producing a tapered polymer or a block copolymer, it is preferable to add a chain transfer agent after the target polymer is produced in the system.

Examples of the chain transfer agent used in the present invention include hydrogen, organoaluminum compounds, organoboron compounds, organozinc compounds, organosilicon compounds, organocadadmium compounds, and organolead compounds. Specifically, for example, the following is used.

General formula R^a_mAl (OR^{b b})_nH_pX_q(In the formula, R^aAnd R^{b b}May be the same or different from each other, and if there are a plurality of them, they may be one kind or two or more kinds, and indicate a hydrocarbon group having 1 to 15, preferably 1 to 6 carbon atoms, and X indicates a halogen atom. , M is 0 &lt;m 3, n is 0 n &lt;3, p is 0 p &lt;3, q is the number 0 q &lt;3, and m + n + p + q = 3. ) Organoaluminium compound represented by.

General formula R^a_mB (OR^{b b})_nH_pX_q(In the formula, R^aAnd R^{b b}May be the same or different from each other, and if there are a plurality of them, they may be one type or two or more types, and indicate a hydrocarbon group having 1 to 15, preferably 1 to 6 carbon atoms, and X indicates a halogen atom. , M is 0 &lt;m 3, preferably 0 &lt;m 2, n is 0 n &lt;3, preferably 0 n &lt;2, p is 0 p &lt;3, preferably 1 p &lt;3, q Is a number of 0 q &lt;3, preferably 0 q &lt;2, and m + n + p + q = 3. ) An organoboron compound represented by.

General formula R^a_mSi (OR^{b b})_nH_pX_q(In the formula, R^aAnd R^{b b}May be the same or different from each other, and if there are a plurality of them, they may be one type or two or more types, and indicate a hydrocarbon group having 1 to 15, preferably 1 to 6 carbon atoms, and X indicates a halogen atom. , M is 0 &lt;m 4, preferably 0 &lt;m 3, n is 0 n &lt;4, preferably 0 n &lt;3, p is 0 p &lt;4, preferably p is 1 p &lt;4 , Q is a number of 0 q &lt;4, preferably 0 q &lt;3, and m + n + p + q = 4. ) Organosilicon compound represented by.

General formula R^a_mPb (OR^{b b})_nH_pX_q(In the formula, R^aAnd R^{b b}May be the same or different from each other, and if there are a plurality of them, they may be one type or two or more types, and indicate a hydrocarbon group having 1 to 15, preferably 1 to 6 carbon atoms, and X indicates a halogen atom. , M is 0 &lt;m 4, n is 0 n &lt;4, p is 0 p &lt;4, q is the number 0 q &lt;4, and m + n + p + q = 4. ) Organolead compound represented by.

General formula R^aR^{b b}M⁴(In the formula, R^aAnd R^{b b}May be the same or different from each other and represent hydrocarbon groups with 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, M.⁴Is Zn or Cd. ) A dialkyl compound of zinc or cadmium represented by.

More specifically as the above compound Trialkylaluminum such as trimethylaluminum, triethylaluminum, trin-butylaluminum, trioctylaluminum, tridecylaluminum, triisopropylaluminum, triisobutylaluminum, dialkylaluminum hydride such as diethylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride; Alkylaluminum dihydrides such as ethylaluminum dihydrides and propylaluminum dihydrides, boranes, borane tetrahydrofuran complexes, borane dimethyl sulfide complexes, borane dimethylamine complexes, borane trimethylamine complexes, borane trimethylphosphine complexes, texylborane, 9-borabicyclo [3.3.1 ] Nonane, triethylborane, trimethylborane, monoalkylsilane, dialkylsilane, trialkylsilane, diethylzinc, dimethylzinc, diethylcadomium, dimethylcadomium, tetraphenyl lead.

It is also possible to use a compound that forms the chain transfer agent in the polymerization system. Among the above compounds, hydrogen, an organosubvessel compound, an organoborone compound, and an organosilicon compound are preferable, and hydrogen, diethylzinc, and a boron hydride compound are particularly preferable.

The chain transfer agents as described above may be used alone or in combination of two or more. However, when this chain transfer agent is used, this reagent is different from the organometallic compound constituting the olefin polymerization catalyst. This is because the present polymerization reaction is characterized in that the living polymerization must proceed when the chain transfer agent is not added, and the chain transfer reaction proceeds only when the chain transfer agent is added.

The molar ratio of this chain transfer agent to the transition metal compound is usually 0.1 to 10000, preferably 1 to 5000. In this case, the olefin polymerization catalyst to be used is preferably a catalyst for olefin polymerization containing the transition metal compound (A), and a production method in which the polymer to be produced is the above-mentioned tapered polymer, olefin copolymer or olefin block copolymer is used. preferable.

According to the production method of the present invention, it is possible to obtain an olephine polymer having a high molecular weight and a narrow molecular weight distribution, a tapered polymer having a precisely controlled structure, or an olefin block copolymer with high polymerization activity with high efficiency.

Various additives may be added to monodisperse polyolefins, olefin copolymers, tapered polymers, olefin block copolymers, or polymers containing functional groups at the ends of these polymers.

Further, monodisperse polyolefins, olefin copolymers, tapered polymers, olefin block copolymers as described above, or polymers containing a functional group at the end of these polymers can be used for various purposes.

Further, a composition containing a monodisperse polyolefin, an olefin copolymer, a tapered polymer, an olefin block copolymer or a polymer containing a functional group at the end of these polymers as described above is molded by a known molding method. , Can be used as a molded product.

Among the olefin polymers of the present invention, block copolymers and tapered polymers containing hard blocks and soft blocks have performance as thermoplastic elastomers. These polymers are used in automotive parts such as side moldings, bumpers, weather strips, glass run channels, boots, air duct hoses; industrial parts such as packings, mats, belts, hoses; wires, cords, muffling. Electrical and electronic parts such as gears; sports equipment such as sports shoes and ski shoes; civil engineering and building material applications such as gaskets and water-impervious sheets.

The olefin polymer according to the present invention can contain additives used for thermoplastic resins, fillers, core materials, and polymers in an arbitrary ratio, and can be subjected to secondary modification such as cross-linking and foaming. Good.

Thermoplastic resins include crystalline thermoplastics such as polyolefins, polyamides, polyesters and polyacetals; non-crystalline thermoplastics such as polystyrenes, acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonates, polyphenylene oxides and polyacrylates. Is used. Polyvinyl chloride is also preferably used.

Specifically, the polyolefins include ethylene-based polymers, propylene-based polymers, butene-based polymers, 4-methyl-1-pentene-based polymers, 3-methyl-1-butene-based polymers, and hexene-based polymers. Can be mentioned. Among them, an ethylene-based polymer, a propylene-based polymer, and a 4-methyl-1-pentene-based polymer are preferable, and in the case of an ethylene-based polymer, an ethylene / polar group-containing vinyl copolymer is preferable.

Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; polycaprolactone and polyhydroxybutyrate. Of these, polyethylene terephthalate is particularly preferable.

Specifically, the above-mentioned polyamides include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Can be mentioned. Of these, nylon-6 is particularly preferable.

Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, and polybutylaldehyde. Of these, polyformaldehyde is particularly preferable.

The polystyrene may be a homopolymer of styrene, or may be a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene. The ABS contains a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. ABS containing in an amount of 40 to 60 mol% is preferably used.

Examples of the above polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). ) Examples include polymers obtained from butane and the like. Of these, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.

As the polyphenylene oxide, it is preferable to use poly (2,6-dimethyl-1,4-phenylene oxide). As the polyacrylate, it is preferable to use polymethyl methacrylate or polybutyl acrylate.

The above-mentioned thermoplastic resin may be used alone or in combination of two or more. In addition to the above-mentioned thermoplastic resin, the olefin-based block copolymer according to the present invention further comprises a cross-linking agent, a filler, a cross-linking accelerator, a cross-linking aid, a softening agent, a tackifier, an antiaging agent, a foaming agent, and a processing aid. It may contain an agent, an adhesion imparting agent, an inorganic filler, an organic filler, a crystal nucleating agent, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a coloring agent, a lubricant, a flame retardant, an anti-blooming agent and the like.

<u style="single">Crosslinker</u> Examples of the cross-linking agent include sulfur, sulfur compounds and organic peroxides. Organic peroxides with a 1-minute half-life temperature of 130-200 ° C are preferred, specifically dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5. -Trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane and the like are preferable. .. When an organic peroxide is used as the cross-linking agent, it is preferable to use a cross-linking aid in combination.

Of the various cross-linking agents described above, sulfur or a sulfur-based compound, particularly sulfur, is preferable because a cross-linked product having excellent properties can be obtained, but an organic peroxide is particularly excellent in cross-linking efficiency. More preferred.

<u style="single">Crosslink accelerator</u> Specifically, as a cross-linking accelerator, N-cyclohexyl-2-benzothiazolesulfenamide (CBZ), N-oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide. , 2-Mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole and the like are used.

<u style="single">Crosslinking aid</u> The cross-linking aid is used in the case of organic peroxide cross-linking, and specifically, the cross-linking aid is a quinone-dioxime-based compound such as sulfur; p-quinonedioxime and p, p'-dibenzoylquinonedioxime. Compounds; and (meth) acrylate compounds such as polyfunctional monomers such as trimethylolpropantriacrylate and polyethylene glycol dimethacrylate; allyl compounds such as diallylphthalate and triallyl cyanurate; N, N'-m-phenylenebis Maleimide compounds such as maleimide; divinylbenzene and the like can be mentioned.

<u style="single">Softener</u> As the softening agent, a softening agent conventionally blended in rubber is widely used. Specifically, petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and vaseline; Coultal softeners such as tar pitch; fatty oil softeners such as paraffin oil, flaxseed oil, rapeseed oil and palm oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; stearic acid, palmitic acid , Fatty acids and fatty acid salts such as barium stearate, calcium stearate, zinc laurate; synthetic polymeric substances such as petroleum resin, atactic polypropylene, kumaron inden resin. Of these, petroleum-based softeners are preferably used, and process oils are particularly preferably used.

<u style="single">Foaming agent</u> As the foaming agent, a foaming agent generally used for foam molding of rubber can be widely used, and specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite and the like can be used. Inorganic foaming agent, nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, azodicarboxylicamide, azobisisobutyronitrile, azocyclohexylnitrile , Azo compounds such as azodiaminobenzene, barium azodicarboxylate, benzenesulfonyl hydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3'-disulfonylhydrazide and other sulfonylhydrazides Examples include compounds, azide compounds such as calcium azide, 4,4-diphenyl, disulfonyl azide, p-toluenesulforunyl azide. Of these, nitroso compounds, azo compounds, and azide compounds are preferable.

<u style="single">Foaming aid</u> Further, a foaming aid can be used together with the foaming agent, and when the foaming aid is used in combination, there are effects such as lowering the decomposition temperature of the foaming agent, promoting decomposition, and homogenizing air bubbles. Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea or its derivatives.

<u style="single">Processing aid</u> Processing aids include acids such as ricinoleic acid, stearic acid, partiminic acid, lauric acid, salts of these higher fatty acids, such as barium stearate, zinc stearate, calcium stearate or esters.

<u style="single">Adhesion imparting agent</u> The adhesion-imparting agent improves the adhesion between the crosslinked product and the decorative layer such as a coating film, and includes, for example, an organotin compound, a tertiary amine compound, a hydroxyl group-containing (co) polymer, and a metal hydroxide. And so on.

<u style="single">Inorganic filler</u> Inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pebbles powder, pebbles balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, calcium titanate, barium sulfate, sulfite. Calcium, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide and the like can be mentioned.

Of these, layered compounds are preferable, and clay minerals having swelling and cleavage properties with respect to a dispersion medium are particularly preferably used. Such clay minerals generally have a two-layer structure having an octahedral layer with aluminum, magnesium, etc. as the central metal above the tetrahedral layer of silica, and the tetrahedral layer of silica has aluminum, magnesium, etc. It is classified into a type having a three-layer structure in which the octahedral layer made of the central metal is narrowed from both sides. Examples of the former two-layer structure type include kaolinites and antigolites, and examples of the latter three-layer structure type include smectites, vermiculites, and mica depending on the number of interlayer cations. Can be done.

More specifically, these clay minerals include kaolinite, chlorite, talcite, pyrophyllite, antigolite, phlogopite, pyrophyllite, montmorillonite, biderite, nontronite, saponite, saponite, stalculite, hectrite, and tetra. Examples include silicic mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, and chlorite.

In addition, clay minerals treated with organic substances (hereinafter sometimes referred to as organically modified clay minerals) can also be used as inorganic layered compounds (for clay minerals treated with organic substances, see Asakura Shoten, "Clay See Encyclopedia).

Among the clay minerals, the smectite group, the vermiculite group and the mica group are preferable, and the smectite group is more preferable, from the viewpoint of swelling property or cleavage property. Examples of the smectite tribe include montmorillonite, biderite, nontronite, saponite, saponite, stebunsite, and hectorite.

The dispersion medium for swelling or opening the inorganic layered compound is, for example, water, methanol, ethanol, propanol, isopropanol, ethylene glycol, alcohols such as diethylene glycol, dimethylformamide, dimethylsulfoxide, acetone, etc. in the case of natural swellable clay minerals. Alcohols such as water and methanol are more preferable. In the case of organically modified clay minerals, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as ethyl ether and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, n-pentane and n-hexane. , N-Octane and other aliphatic hydrocarbons, chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, perchloroethylene and other halogenated hydrocarbons, ethyl acetate methacrylate (MMA), phthal Examples include dioctyl acid (DOP), dimethylformamide, dimethylsulfoxide, methylserosolve, silicon oil and the like.

<u style="single">Crystal nucleating agent</u> As the crystal nucleating agent, various conventionally known nucleating agents are used without particular limitation. Examples of the crystal nucleating agent include aromatic phosphoric acid ester salts, benzylidene sorbitol, aromatic carboxylic acids, and rosin-based nucleating agents listed below.

Examples of the aromatic phosphoric acid ester salt include compounds represented by the following formula (1).

<chemistry num="26"><img id="000027" he="53" wi="87" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R⁴¹Indicates a hydrocarbon group with an oxygen atom, a sulfur atom or a carbon atom number of 1 to 10, and R⁴²And R⁴³Indicates a hydrocarbon group with 1 to 10 hydrogen atoms or carbon atoms, R⁴²And R⁴³Can be homologous or heterogeneous, R⁴²R⁴³Mutual or R⁴²And R⁴³And may be bonded to form a ring, M represents a metal atom having a valence of 1 to 3, and n is an integer of 1 to 3. )

6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'- Methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2' -Methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium -Bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl- 6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-bis) Ethylphenyl) Phenyl Phenyl, Potassium-2,2'-Echiliden-Bis (4,6-di-t-Butylphenyl) Phenyl Phenyl, Calcium-Bis [2,2'-Echiliden-Bis (4,6-Di-Bis) t-Butylphenyl) Phenyl Phenyl], Magnesium-Bis [2,2'-Echiliden-Bis (4,6-di-t-Butylphenyl) Phenyl Phenyl], Barium-Bis [2,2'-Echiliden-Bis (2,2'-Echiliden-Bis) 4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate] and aluminum-tris [2,2' -Etilidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more of these can be exemplified. Especially sodium-2,2'-methylene-bis (4,

Examples of the aromatic phosphoric acid ester salt include compounds represented by the following formula (2).

<chemistry num="27"><img id="000028" he="23" wi="98" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R⁴⁴Indicates a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M indicates a 1 to 3 valent metal atom, and n is an integer of 1 to 3. )

Specific examples of the compound represented by the formula (2) include sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, and sodium-bis (4-ethylphenyl). ) Phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis ( 4-t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosph Fate and mixtures of two or more of these can be exemplified. In particular, sodium-bis (4-t-butylphenyl) phosphate is preferable.

Examples of the benzylidene sorbitol include a compound represented by the following formula (3).

<chemistry num="28"><img id="000029" he="42" wi="104" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R⁴⁵May be the same or different from each other, indicating a hydrocarbon group having 1 to 10 hydrogen atoms or carbon atoms, and m and n are integers of 0 to 5, respectively. )

Specifically, as the compound represented by the above formula (3), 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene- 2,4-p-Ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene -2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3 , 2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1, 3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1 , 3,2,4-di (2', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxy) Benzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p -Methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethyl Benzyllidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more of these can be exemplified, especially 1,3,2,4-Dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2 , 4-p-Methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof are preferred.

Among the above-mentioned benzylidene sorbitols, the compound represented by the following formula (4) can be mentioned as a preferable example.

<chemistry num="29"><img id="000030" he="43" wi="110" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R⁴⁵May be the same or different from each other and indicate a methyl or ethyl group. ) Examples of the aromatic carboxylic acid include aluminum hydroxydipara t-butylbenzoate represented by the following formula (5).

<chemistry num="30"><img id="000031" he="22" wi="100" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> Examples of the rosin-based crystal nucleating agent include a metal salt of rosin acid, and the metal salt of rosin acid refers to a reaction product of rosin acid and a metal compound. Natural rosins such as gum rosin, tall oil rosin, and wood rosin; various modifications such as disproportionate rosin, hydrogenated rosin, dehydrogenized rosin, polymerized rosin, and α, β-ethylenic unsaturated carboxylic acid modified rosin. Rosin; Examples thereof include a purified product of the natural rosin and a purified product of a modified rosin. Examples of the unsaturated carboxylic acid used for preparing the α, β-ethylenic saturated carboxylic acid-modified rosin include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and acrylic acid. Methacrylic acid and the like can be mentioned. Among these, at least one rosin acid selected from the group consisting of natural rosin, modified rosin, purified product of natural rosin and purified product of modified rosin is preferable. Here, the rosin acid is a plurality of resin acids selected from pimaric acid, sandalacopimaric acid, palastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoavietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid and the like. Includes.

Examples of the metal compound that reacts with the logonic acid to form a metal salt include a compound having a metal element such as sodium, potassium, and magnesium and forming a salt with the logonic acid. Specific examples thereof include chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides of the metals.

Examples of other crystal nucleating agents include refractory polymers, metal salts of aromatic carboxylic acids and aliphatic carboxylic acids, and inorganic compounds. Examples of the refractory polymer include polyvinylcycloalkane such as polyvinylcyclohexane and polyvinylcyclopentane, poly3-methyl-1-pentene, poly3-methyl-1-butene, and polyalkenylsilane.

Examples of the metal salt of the aromatic carboxylic acid or the aliphatic carboxylic acid include aluminum benzoate, pt-butyl aluminum benzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrolecarboxylate.

<u style="single">Molding method</u> The olefin copolymer according to the present invention can be produced by calendar molding, extrusion molding, injection molding, blow molding, press molding, stamping molding and the like.

The olefin copolymer can be molded into a sheet or film (unstretched) by extrusion molding. The stretched film is obtained by stretching the extruded sheet or extruded film (unstretched) as described above by, for example, a tenter method (longitudinal horizontal stretching, horizontal vertical stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method. Inflation films can also be produced from the olefin copolymer according to the present invention.

The filament can be produced, for example, by extruding a molten olefin copolymer through a spinneret. Alternatively, it may be prepared by the melt blown method. The injection-molded article can be produced by injection-molding an olefin-based co-weighted body into various shapes by using a conventionally known injection-molding apparatus and adopting known conditions. The injection-molded article made of the olefin-based copolymer according to the present invention is not easily charged and has excellent rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc., and is a trim material for automobile interiors. , Automotive exterior materials, housings for home appliances, containers, etc. can be widely used.

The blow-molded product can be manufactured by using a conventionally known blow-molding apparatus and adopting known conditions. Further, in injection blow molding, the olefin-based copolymer according to the present invention is injected into a parison mold at a resin temperature of 100 ° C to 300 ° C to form a parison, and then the parison is held in a mold having a desired shape. A hollow molded product can be manufactured by blowing air into the mold and mounting the molded product on the mold.

Examples of the stamping molding include stamping molding. For example, the base material is formed by the above-mentioned olefin-based copolymer when the base material and the skin material are press-molded at the same time and the two are combined and integrally molded (stamping mold molding). be able to.

<u style="single">Use</u> The olefin-based copolymer according to the present invention can be used for various purposes, for example, it can be used for films, sheet laminates, and modifiers.

Examples of the laminate containing at least one layer made of the olefin-based copolymer according to the present invention include agricultural films, wrap films, shrink films, protective films, plasma component separation membranes, and water selective permeation vaporization membranes. There are examples of separation membranes, ion exchange membranes, battery separators, selective separation membranes such as optical separation membranes, and the like.

The olefin copolymer according to the present invention can be used as a modifier for rubber. As rubber, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), ethylene Propylene rubber (EPM, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM, etc.), epichlorohydrin rubber (CO, ECO, etc.), silicone rubber (Q), fluorine rubber (FKM, etc.) ) And other crosslinked rubbers; styrene-based, olefin-based, urethane-based, ester-based, amide-based, vinyl chloride-based and other thermoplastic rubbers can be mentioned.

The olefin-based copolymer according to the present invention includes modifiers for lubricating oils such as gasoline engine oils, diesel engine oils, marine engine oils, gear oils, machine oils, metal processing oils, motor oils, machine oils and spindle oils. It can be used as a lubricating oil such as an insulating oil, as a viscosity modifier, and a freezing point lowering agent.

The olefin copolymer according to the present invention can be used as a modifier for wax. Waxes include mineral waxes such as montan wax, peat wax, ozokerite celesin wax, petroleum wax, polyethylene, Fischer-Tropsch wax, chemically modified hydrocarbon wax, synthetic wax such as substituted amide wax, plant wax, animal wax, etc. Can be mentioned.

The olefin copolymer according to the present invention can be used as a modifier for cement. Examples of cement include air-hardening cement such as lime, gypsum, and magnesia cement, Roman cement, natural cement, water-hardening cement such as Portoland cement, alumina cement, and high sulfate slag cement, acid-resistant cement, fire-resistant cement, water glass cement, and dentistry. There are special cements such as cement for use.

(Viscosity adjuster, moldability improver) The olefin-based copolymer according to the present invention includes inks such as letterpress printing inks, flat plate printing inks, flexo inks, and gravure inks, oil-based paints, fibrous derivative paints, synthetic resin paints, water-based baking paints, powdery water-based paints, and lacquer. It is used as a viscosity modifier and moldability improver for inks and paints.

(Building materials / Civil engineering materials) The olefin-based copolymer according to the present invention includes, for example, floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulating panels, vibration isolators, decorative sheets, skirting boards, asphalt modifiers, gaskets / sealants, roofing sheets, etc. It can be used for building materials such as waterproof sheets, resins for civil engineering, and molded bodies for building materials and civil engineering.

(Car interior / exterior materials and gasoline tanks) It can be used for automobile interior / exterior materials, gasoline tanks, etc. made of the olefin copolymer according to the present invention.

(Electrical / electronic parts) The olefin-based copolymer according to the present invention can be used for electric / electronic parts, and examples of the electric / electronic parts include an electric insulating material; an equipment for processing electronic parts; a magnetic recording medium, a binder for the magnetic recording medium, and an electric circuit. Encapsulants, home appliances, container equipment such as microwave containers; microwave films, polymer electrolyte substrates, conductive alloy substrates, etc. Electrical and electronic components include connectors, sockets, resistors, relay case switch coil bobbins, capacitors, variable condenser cases, optical pickups, optical connectors, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, and speakers. , Microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related parts, etc. Parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademarks) / compact discs, lighting parts, refrigerator parts, air conditioner parts, Household and office electrical product parts such as typewriter parts and word processor parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, electromagnetic shield materials, speaker cone materials, speaker vibration elements, etc. is there.

(Aqueous emulsion) The aqueous emulsion containing the olefin-based copolymer according to the present invention can be used as an adhesive for polyolefins having excellent heat-sealing properties.

(Medical and hygiene materials) The olefin-based copolymer according to the present invention includes non-woven fabrics, non-woven fabric laminates, electlets, medical tubes, medical containers, infusion bags, prefill syringes, medical supplies such as syringes, medical materials, artificial organs, artificial muscles, etc. It can be used for filter membranes, food hygiene / health products; retort bags, freshness-preserving films, etc.

(Miscellaneous goods) The olefin-based copolymer according to the present invention includes desk mats, cutting mats, rulers, pen barrels / grips / caps, grips such as scissors and cutters, magnet sheets, pen cases, paper folders, binders, label stickers, and tapes. , Stationery such as whiteboards; clothing, curtains, sheets, rugs, entrance mats, bath mats, buckets, hoses, bags, planters, air conditioner and exhaust fan filters, tableware, trays, cups, lunch boxes, funnels for coffee siphons, glasses Daily necessities such as frames, containers, storage cases, hangers, ropes, laundry nets; shoes, goggles, skis, rackets, balls, tents, underwater glasses, fins, fishing rods, cooler boxes, leisure seats, sports Sporting goods such as nets: Toys such as blocks and cards; Containers such as kerosene cans, drums, bottles such as detergents and shampoos; Labels such as signs, pylon, plastic chains, etc.

(Filler modifier) The olefin-based copolymer according to the present invention can be suitably used for applications such as a filler dispersibility improving material and an additive for preparing a filler having improved dispersibility.

(Compatible agent) Among the olefin-based copolymers according to the present invention, those having a functional group at the terminal can be used as a compatibilizer. When the olefin-based copolymer according to the present invention is used as a compatibilizer, the polyolefin and the thermoplastic resin containing a polar group can be mixed at an arbitrary ratio. Since the olefin-based copolymer has a polyolefin segment and a functional group, components that were originally incompatible with each other can be mixed.

(Other) In addition to the above, the olefin copolymer according to the present invention can be used for microcapsules, blister packs, chemical valves, drug delivery systems and the like.

<p num="0439"> Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The structure of the compound obtained in the synthetic example is¹It was determined using 1 H-NMR and FD-mass spectrometry (JEOL SX-102A).</p><p num="0440"><u style="single">Synthesis example 1</u> A fully nitrogen-substituted 100 ml reactor was charged with 100 ml of toluene, 10.34 g (56.5 mmol) of pentafluoroaniline, 6.68 g (75.4%, 28.2 mmol) of 3-t-butyl salicylaldehyde and a small amount of acetic acid as a catalyst. Heating, reflux and stirring were continued for 7 hours. After allowing to cool to room temperature, a small amount of p-toluenesulfonic acid was further added as a catalyst, and the mixture was refluxed and stirred for 2.5 hours. After allowing to cool to room temperature, the catalyst was removed by filtration and concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 8.47 g (yield 88%) of a yellow solid represented by the following formula (a).</p><p num="0441"><chemistry num="31"><img id="000032" he="48" wi="65" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.043 g (3.00 mmol) of the compound (a) obtained above and 30 ml of anhydrous diethyl ether were charged into a 50 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. To this, 2.05 ml of n-butyllithium (n-hexane solution, 1.54N, 3.15 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 3 hours, it was gradually added to an ether slurry of 3.00 ml (heptane solution, 0.5 M, 1.50 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The obtained dark red slurry was filtered, and the filtrate was concentrated under reduced pressure until the liquid volume became about 5 ml. The precipitated solid was collected and washed with hexane. The obtained solid was dried under reduced pressure to obtain 0.381 g (yield 32%) of a brown compound represented by the following formula (1). The result of FD-mass spectrometry of compound (1) was 802 (M +).</p><p num="0442"><chemistry num="32"><img id="000033" he="48" wi="78" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 2</u> 100 ml of toluene, 3.82 g (26.0 mmol) of 2,4,6-trifluoroaniline, 2.32 g (13.0 mmol) of 3-t-butyl salicylaldehyde and a small amount of p-toluene as a catalyst in a 200 ml reactor fully substituted with nitrogen. Sulfonic acid was charged, and heating under reflux stirring was continued for 4 hours. After allowing to cool to room temperature, the catalyst was removed by filtration and concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 3.79 g (yield 95%) of a yellow oil represented by the following formula (b).</p><p num="0443"><chemistry num="33"><img id="000034" he="44" wi="60" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.23 g (4.00 mmol) of the compound (b) obtained above and 30 ml of anhydrous diethyl ether were charged into a 50 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. 2.63 ml of n-butyllithium (n-hexane solution, 1.60 N, 4.20 mmol) was added dropwise thereto over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, it was gradually added to an ether slurry of 4.00 ml (heptane solution, 0.5 M, 2.00 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The obtained dark red slurry was filtered, and the filtrate was concentrated under reduced pressure. 5 ml of ether and 30 ml of hexane were added to collect the precipitated solid, which was washed with hexane. The obtained solid was dried under reduced pressure to obtain 0.550 g (yield 38%) of a reddish brown compound represented by the following formula (2). The result of FD-mass spectrometry of compound (2) was 730 (M +).</p><p num="0444"><chemistry num="34"><img id="000035" he="45" wi="79" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 3</u> A fully nitrogen-substituted 100 ml reactor was charged with 30 ml of ethanol, 5.16 g (40.0 mmol) of 2,6-difluoroaniline, 3.58 g (20.0 mmol) of 3-t-butyl salicylaldehyde and a small amount of acetic acid as a catalyst. Heating, reflux and stirring were continued. Reflux stirring was carried out for a total of 150 hours while additionally charging a small amount of acetic acid. After allowing to cool to room temperature, it was concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 4.76 g (yield 82.2%) of a yellow solid represented by the following formula (c).</p><p num="0445"><chemistry num="35"><img id="000036" he="42" wi="61" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.16 g (4.00 mmol) of the compound (c) obtained above and 20 ml of anhydrous diethyl ether were charged into a 30 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. To this, 2.50 ml of n-butyllithium (n-hexane solution, 1.6 N, 4.00 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 3 hours, it was gradually added to an ether slurry of 4.00 ml (heptane solution, 0.5 M, 2.00 mmol) of titanium tetrachloride cooled to -78 ° C. After the addition, the temperature was slowly raised to room temperature. The resulting dark red slurry was filtered and the solid washed with a small amount of methylene chloride. The solid obtained by concentrating the filtrate and washings under reduced pressure was collected, suspended in 15 ml of ether, the precipitate was filtered, and then washed with a small amount of ether and hexane. The obtained solid was dried under reduced pressure to obtain 1.059 g (yield 76%) of a brown compound represented by the following formula (3). The result of FD-mass spectrometry of compound (3) was 694 (M +).</p><p num="0446"><chemistry num="36"><img id="000037" he="42" wi="77" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 4</u> A 200 ml reactor fully substituted with nitrogen was charged with 100 ml of toluene, 2.89 g (26.0 mmol) of o-fluoroaniline, 2.32 g (13.0 mmol) of 3-t-butyl salicylaldehyde, and a small amount of p-toluenesulfonic acid as a catalyst. Then, heating and reflux stirring was continued for 5 hours. After allowing to cool to room temperature, the catalyst was removed by filtration and concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 3.45 g (yield 98%) of a yellow oil represented by the following formula (d).</p><p num="0447"><chemistry num="37"><img id="000038" he="40" wi="57" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.01 g (4.00 mmol) of the compound (d) obtained above and 30 ml of anhydrous diethyl ether were charged into a 30 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. 2.63 ml of n-butyllithium (n-hexane solution, 1.60 N, 4.20 mmol) was added dropwise thereto over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, it was gradually added to an ether slurry of 4.00 ml (heptane solution, 0.5 M, 2.00 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The obtained dark red slurry was filtered, and the filtrate was concentrated under reduced pressure. 5 ml of ether and 30 ml of hexane were added to collect the precipitated solid, which was washed with hexane. The obtained solid was dried under reduced pressure to obtain 0.530 g (yield 40%) of a reddish brown compound represented by the following formula (4). The result of FD-mass spectrometry of compound (4) was 658 (M +).</p><p num="0448"><chemistry num="38"><img id="000039" he="41" wi="79" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 5</u> 100 ml of toluene, 3.19 g (8.0 mmol) of 1H, 1H-perfluorooctylamine, 1.43 g (8.0 mmol) of 3-t-butyl salicylaldehyde and a small amount of p-toluenesulfone as a catalyst in a 200 ml reactor fully substituted with nitrogen. The acid was charged, and heating, refluxing and stirring were continued for 14 hours. After allowing to cool to room temperature, the catalyst was removed by filtration, and the mixture was concentrated under reduced pressure to obtain 4.04 g (yield 90%) of a yellow solid represented by the following formula (e).</p><p num="0449"><chemistry num="39"><img id="000040" he="33" wi="68" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.12 g (2.00 mmol) of the compound (e) obtained above and 30 ml of anhydrous diethyl ether were charged into a 30 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. To this, 1.31 ml of n-butyllithium (n-hexane solution, 1.60 N, 2.10 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, it was gradually added to an ether slurry of 2.00 ml (heptane solution, 0.5 M, 1.00 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The obtained dark red slurry was filtered, and the filtrate was concentrated under reduced pressure. 3 ml of ether and 20 ml of hexane were added to collect the precipitated solid, which was washed with hexane. The obtained solid was dried under reduced pressure to obtain 0.183 g (yield 15%) of a reddish brown compound represented by the following formula (5). The result of FD-mass spectrometry of compound (5) was 1234 (M +).</p><p num="0450"><chemistry num="40"><img id="000041" he="31" wi="74" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 6</u> Toluene 100 ml, 4-trifluoromethyl-2,3,5,6-tetrafluoroaniline 4.66 g (20.0 mmol), 3-t-butyl salicylaldehyde 1.78 g (10.0 mmol) in a fully nitrogen-substituted 200 ml reactor A small amount of p-toluenesulfonic acid was charged as a catalyst, and heating and reflux stirring was continued for 53 hours. Since the raw material was confirmed by GC analysis, 2.33 g (10.0 mmol) of 2,3,5,6-tetrafluoro-4-trifluoromethyl-aniline was further added, and heating under reflux stirring was continued for 7 hours. After allowing to cool to room temperature, the catalyst was removed by filtration and concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 2.53 g (yield 64%) of a pale yellow solid represented by the following formula (f).</p><p num="0451"><chemistry num="41"><img id="000042" he="49" wi="58" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 0.15 g (23.80 mmol) of sodium hydride was charged into a 100 ml reactor sufficiently substituted with argon, washed twice with 10 ml of hexane, and then 30 ml of diethyl ether was added and suspended. While stirring the suspension at room temperature, 20 ml of the diethyl ether solution containing the compound (f) obtained above was added dropwise over 20 minutes, and the mixture was further stirred for 2 hours. The solution was cooled to 78 ° C. and 3.75 ml of titanium tetrachloride (heptane solution, 0.5 M, 1.88 mmol) was added dropwise over 5 minutes. After completion of the dropping, the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the selected dark red slurry was filtered and the filtrate was concentrated under reduced pressure. The solid precipitated by adding ether was collected and dried under reduced pressure to obtain 0.76 g (yield 45%) of a reddish brown powder compound represented by the following formula (6). The result of FD-mass spectrometry of compound (6) was 902 (M +).</p><p num="0452"><chemistry num="42"><img id="000043" he="49" wi="83" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 7</u> A 200 ml reactor fully nitrogen-loaded was charged with 16.2 ml of ethylmagnesium bromide (ether solution, 3M, 48.6 mmol) and 50 ml of anhydrous tetrahydrofuran. A solution prepared by dissolving 11.2 g (46.2 mmol) of 2- (1-adamantyl) -4-methylphenol in 50 ml of anhydrous tetrahydrofuran was added dropwise over 20 minutes under ice-cooling. After completion of the dropping, the mixture was stirred at room temperature, 300 ml of toluene was added, and the mixture was heated and stirred to distill off tetrahydrofuran and diethyl ether. After cooling to room temperature, 3.80 g (127 mmol) of paraformaldehyde and 7.1 g (70.2 mmol) of triethylamine were added, and the mixture was heated and stirred at 80 to 90 ° C for 20 minutes. After cooling to room temperature and further ice-cooling, 200 ml of 10% hydrochloric acid was added. Diethyl ether 300 was added to separate the liquids, and the organic layer was washed twice with 200 ml of water and subsequently with an aqueous sodium hydrogen carbonate solution. After drying over anhydrous sodium sulfate, the crystals obtained by concentration under reduced pressure were dried under reduced pressure, and 10.5 g (yield 84%) of a yellow compound represented by the following formula (g) (Adm in the formula indicates an adamantyl group) was added. )Obtained.</p><p num="0453"><chemistry num="43"><img id="000044" he="34" wi="74" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 80 ml of toluene, 2.75 g (15.0 mmol) of pentafluoroaniline, 4.07 g (99.7%, 15.0 mmol) of the compound (g) obtained above and a small amount of p-toluenesulfone as a catalyst in a 100 ml reactor fully substituted with nitrogen. The acid was charged, and heating under reflux and stirring was continued for 5 and a half hours. After allowing to cool to room temperature, the solvent was distilled off under reduced pressure. 50 ml of methanol was added and stirred, and the solid obtained by filtration was dried under reduced pressure to obtain 4.38 g (yield 67%) of a yellow solid represented by the following formula (g').</p><p num="0454"><chemistry num="44"><img id="000045" he="48" wi="66" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.35 g (3.00 mmol) of the compound (g') obtained above and 20 ml of anhydrous diethyl ether were charged into a 50 ml reactor well substituted with argon, cooled to 78 ° C., and stirred. 1.89 ml of n-butyllithium (n-hexane solution, 1.59N, 3.00 mmol) was added dropwise to this over 5 minutes, and the mixture was stirred for 2 hours and then slowly warmed to room temperature. After stirring at room temperature for 3 hours, this solution was added dropwise to 20 ml of a tetrahydrofuran solution of 3.00 ml (heptane solution, 0.5 M, 1.50 mmol) of titanium tetrachloride cooled to 78 ° C. After completion of the dropping, the temperature was slowly raised to room temperature, the mixture was stirred at room temperature for 12 hours, and then the solvent was distilled off under reduced pressure. 40 ml of methylene chloride was added to the obtained solid, and the mixture was stirred and filtered, and the filtrate was concentrated under reduced pressure. The precipitated solid was reprecipitated with hexane, and the obtained solid was dried under reduced pressure to obtain 0.334 g (yield 23%) of a brown compound represented by the following formula (7). The result of FD-mass spectrometry of compound (7) was 986 (M +).</p><p num="0455"><chemistry num="45"><img id="000046" he="50" wi="82" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 8</u> 100 ml of toluene, 4.19 g (26.0 mmol) of o-trifluoromethylaniline, 2.32 g (13.0 mmol) of 3-t-butyl salicylaldehyde and a small amount of p-toluenesulfonic acid as a catalyst in a 200 ml reactor fully substituted with nitrogen. The mixture was charged and heated under reflux and stirred for 5 hours. After allowing to cool to room temperature, the catalyst was removed by filtration and concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 3.20 g (yield 77%) of a yellow oil represented by the following formula (h).</p><p num="0456"><chemistry num="46"><img id="000047" he="42" wi="65" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.29 g (4.00 mmol) of the compound (h) obtained above and 30 ml of anhydrous diethyl ether were charged into a 30 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. 2.63 ml of n-butyllithium (n-hexane solution, 1.60 N, 4.20 mmol) was added dropwise thereto over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, it was gradually added to an ether slurry of 4.00 ml (heptane solution, 0.5 M, 2.00 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The obtained dark red slurry was filtered, and the filtrate was concentrated under reduced pressure. 5 ml of ether and 30 ml of hexane were added to collect the precipitated solid, which was washed with hexane. The obtained solid was dried under reduced pressure to obtain 0.80 g (yield 53%) of a reddish brown compound represented by the following formula (8). The result of FD-mass spectrometry of compound (8) was 758 (M +).</p><p num="0457"><chemistry num="47"><img id="000048" he="41" wi="78" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 9</u> 55 ml of ethanol and 3.44 g (15.0 mmol) of 3,5-ditrifluoromethylaniline were charged into a 100 ml reactor fully substituted with nitrogen and stirred. 1.79 g (10.0 mmol) of 3-t-butyl salicylaldehyde was charged into this solution, and the mixture was stirred at room temperature for 19 hours, then 6.00 g of Molecular Sieve 4A was added, and the mixture was heated under reflux for 5 hours. The solid was removed by filtration and the solution was concentrated. The solid was purified using a silica gel column to obtain 0.92 g (yield 72%) of a yellow solid represented by the following formula (i).</p><p num="0458"><chemistry num="48"><img id="000049" he="43" wi="60" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> A fully nitrogen-substituted 30 ml reactor was charged with 0.779 g (2.00 mmol) of compound (i) obtained above and 20 ml of anhydrous diethyl ether, cooled to 78 ° C., and stirred. To this, 1.43 ml of n-butyllithium (n-hexane solution, 1.54N, 2.20 mmol) was added dropwise over 5 minutes, and the mixture was stirred for 3 hours. Then, the mixture was stirred slowly for 5 hours while slowly warming to room temperature, and then gradually added to an ether slurry of 2.00 ml (heptane solution, 0.5 M, 1.00 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The resulting dark red slurry was filtered and the solution concentrated to 10 ml. The crystals selected by filtration were washed with hexane and dried under reduced pressure to obtain 0.269 g (yield 30.1%) of the reddish brown compound represented by the following formula (9). The result of FD-mass spectrometry of compound (9) was 894 (M +).</p><p num="0459"><chemistry num="49"><img id="000050" he="45" wi="91" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 10</u> 100 ml of toluene and 3.36 g (26.0 mmol) of 3,5-difluoroaniline were charged into a 200 ml reactor fully substituted with nitrogen and stirred. To this solution was charged 2.32 g (13.0 mmol) of 3-t-butyl salicylaldehyde and a small amount of p-toluenesulfonic acid, and the mixture was heated under reflux and stirred for 6.5 hours. The solid was removed by filtration and the solution was concentrated. The concentrate was purified using a silica gel column to obtain 3.32 g (yield 89%) of a yellow solid represented by the following formula (j).</p><p num="0460"><chemistry num="50"><img id="000051" he="44" wi="60" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> 1.16 g (4.00 mmol) of the compound (j) obtained above and 30 ml of anhydrous diethyl ether were charged into a 50 ml reactor fully substituted with nitrogen, cooled to 78 ° C., and stirred. To this, 2.63 ml of n-butyllithium (n-hexane solution, 1.60 N, 4.20 mmol) was added dropwise over 5 minutes. Then, the mixture was stirred slowly for 12 hours while slowly warming to room temperature, and then gradually added to an ether slurry of 4.00 ml (heptane solution, 0.5 M, 2.00 mmol) of titanium tetrachloride cooled to 78 ° C. After the addition, the temperature was slowly raised to room temperature. The obtained dark red slurry was filtered and the solution was concentrated. The crystals selected by filtration were washed with hexane and dried under reduced pressure to obtain 0.958 g (yield 69%) of the reddish brown compound represented by the following formula (10). The result of FD-mass spectrometry of compound (10) was 694 (M +).</p><p num="0461"><chemistry num="51"><img id="000052" he="44" wi="87" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Synthesis example 11</u> A 100 ml reactor fully nitrogen-substituted was charged with 2.00 g (5.27 mmol) of hafnosendichloride and 40 ml of anhydrous diethyl ether, cooled to 0 ° C., and stirred. To this, 9.6 ml of methyllithium (ether solution, 1.14N, 10.9 mmol) was added dropwise over 45 minutes, and the mixture was stirred for 2 hours. After that, the temperature was slowly raised to 0 ° C. After stirring at 0 ° C for 30 minutes, insoluble matter was removed by filtration. The filtrate was concentrated, 10 ml of ether was added and suspended, the insoluble material was removed again, and the solution was concentrated under reduced pressure to obtain 1.79 g (quantitative) of the pale yellow compound shown in (11).</p><p num="0462"><chemistry num="52"><img id="000053" he="33" wi="65" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><u style="single">Reference example 1 </u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently substituted with nitrogen, and the liquid phase and the gas phase were saturated with a mixed gas of 50 liters / hr of ethylene and 150 liters / hr of propylene. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.005 mmol of titanium compound (1) was subsequently added to initiate polymerization. After polymerizing at 50 ° C for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol.</p><p num="0463"> The resulting polymer solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate the polymer. The precipitated polymer was washed with methanol and then dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer weighed 0.794 g, and the polymerization activity per 1 mmol of titanium was 1.91 kg / hr. The propylene content measured by IR was 13.3 mol%, the molecular weight (Mn) measured by GPC was 159,000, and the molecular weight distribution (Mw / Mn) was 1.09.</p><p num="0464"><u style="single">Reference example 2</u> In Reference Example 1, the polymerization was carried out in the same manner except that the polymerization time was 10 minutes, and 1.318 g of an ethylene / propylene copolymer was obtained. The polymerization activity per 1 mmol of titanium was 1.58 kg / hr. The propylene content measured by IR was 15.0 mol%, the molecular weight (Mn) measured by GPC was 233,000, and the molecular weight distribution (Mw / Mn) was 1.16.</p><p num="0465"><u style="single">Reference example 3</u> In Reference Example 1, the polymerization was carried out in the same manner except that the polymerization time was 20 minutes, and 2.225 g of an ethylene / propylene copolymer was obtained. The polymerization activity per 1 mmol of titanium was 1.34 kg / hr. The propylene content measured by IR was 15.4 mol%, the molecular weight (Mn) measured by GPC was 345,000, and the molecular weight distribution (Mw / Mn) was 1:29.</p><p num="0466"><u style="single">Reference example 4</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with ethylene. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.0005 mmol of titanium compound (1) was subsequently added to initiate polymerization. After reacting at 25 ° C for 0.5 minutes under a normal pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was put into a large amount of methanol to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 0.149 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 35.8 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 191,000 and 219,000, respectively, and Mw / Mn was 1.15.</p><p num="0467"><u style="single">Reference example 5 ~ 22</u> Polymerization was carried out in the same manner except that the amount of catalyst, the polymerization time and the polymerization temperature were changed as shown in Table 1. Table 1 shows the polymerization activity, the molecular weight of the obtained polymer, and the molecular weight distribution.</p><p num="0468"><tables num="1"><img id="000054" he="224" wi="151" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><u style="single">Example 23</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with propylene. Then, 2.50 mmol of methylaluminoxane was added in terms of aluminum atom, and then 0.01 mmol of titanium compound (1) was added to initiate polymerization. After reacting at 25 ° C for 30 minutes, polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was put into methanol containing a small amount of hydrochloric acid to precipitate the entire amount of the polymer, and then filtered through a glass filter. The polymer was dried under reduced pressure at 80 ° C. for 10 hours to give 0.4 mg of polypropylene (PP). The number average molecular weight (Mn, PP equivalent) and weight average molecular weight (Mw, PP equivalent) of the obtained PP were 4,200 and 4,400, respectively, and Mw / Mn was 1.05.</p><p num="0469"><u style="single">Example 24</u> 96 mg of polypropylene (PP) was obtained in the same manner except that the polymerization time was extended to 3 hours in Example 23. The number average molecular weight (Mn, PP equivalent) and weight average molecular weight (Mw, PP equivalent) of the obtained PP were 20,500 and 22,400, respectively, and Mw / Mn was 1.09.</p><p num="0470"><u style="single">Example 25</u> 180 mg of polypropylene (PP) was obtained in the same manner except that the polymerization time was extended to 5 hours in Example 23. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PP were 28,500 and 31,600, respectively, and Mw / Mn was 1.11. The melting point of this polymer was measured by DSC and found to be 139 ° C.</p><p num="0471"><u style="single">Example 26</u> In Example 23, titanium compound (6) was used instead of titanium compound (1), and 37.6 mg of polypropylene (PP) was obtained in the same manner as in Example 23 except that the polymerization time was extended to 5 hours. The number average molecular weight (Mn, PP equivalent) and weight average molecular weight (Mw, PP equivalent) of the obtained PP were 52,000 and 66,200, respectively, and Mw / Mn was 1.27.</p><p num="0472"><u style="single">Example 27</u> A 1 liter stainless steel autoclave fully nitrogen-substituted was charged with 380 ml of heptane and saturated with propylene at 25 ° C to saturate the gas and liquid phases. After that, 2.5 mmol of methylaluminoxane in terms of aluminum atom and 0.01 mmol of titanium compound (1) were added, and the propylene pressure was 5 kg / cm.²Polymerization was carried out in G for 3 hours.</p><p num="0473"> 1.5 liters of methanol containing a small amount of hydrochloric acid was added to the obtained polymer suspension to precipitate the polymer, which was filtered through a glass filter, the solvent was removed, the mixture was washed with methanol, and dried under reduced pressure at 80 ° C. for 10 hours. did. The obtained polypropylene weighed 0.691 g, Mn (PP equivalent) measured by GPC was 78,000, Mw / Mn was 1.15, and Tm was 134.8 ° C.</p><p num="0474"><u style="single">Example 28</u> Polymerization was carried out in the same manner as above except that the polymerization time was set to 5 hours. The obtained polypropylene weighed 1.125 g, Mn (PP equivalent) measured by GPC was 138,000, Mw / Mn was 1.11 and Tm was 130.5 ° C.</p><p num="0475"><u style="single">Example 29</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently replaced with nitrogen, and a mixed gas of ethylene and butene (ethylene: 40 liters / h and butene: 60 liters / h) was blown into the autoclave for 20 minutes with stirring. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.001 mmol of titanium compound (1) was subsequently added to initiate polymerization. After reacting at 25 ° C. for 5 minutes while blowing the mixed gas, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was added to methanol in which a small amount of hydrochloric acid was dissolved to precipitate a polymer, which was then filtered through a glass filter. The polymer was dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.056 g of an ethylene / butene copolymer. The polymerization activity per 1 mmol of titanium was 0.67 kg. The number average molecular weight (Mn) of the obtained polymer was 49,100, the molecular weight distribution (Mw / Mn) was 1.14, and the butene content was 8.4 mol%.</p><p num="0476"><u style="single">Examples 30-33</u> Polymerization was carried out in the same manner as in Example 29, except that the ethylene and butene flow rates, the polymerization time, and the polymerization temperature were changed as shown in Table 2. Table 2 shows the polymerization activity, the molecular weight of the obtained polymer, and the molecular weight distribution.</p><p num="0477"><tables num="2"><img id="000055" he="65" wi="159" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><u style="single">Example 34</u> 200 ml of dry toluene was charged into a glass autoclave with an internal volume of 500 ml sufficiently nitrogen-substituted, 1-butene was circulated at 100 l / h for 40 minutes, the polymerization temperature was maintained at 25 ° C, and methylaluminoxane was converted to aluminum. 5.00 mmol was added. Subsequently, 0.05 mmol of titanium compound (1) was added, and the gas was switched to a mixed gas of ethylene and 1-butene (ethylene: 20 liters / h, 1-butene: 80 liters / h), stirred for 60 minutes, and then isobutyl alcohol. 20 ml was added to stop the reaction. Subsequently, 10 ml of 1N hydrochloric acid solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes, the polymerization solution was poured into 1.5 L of methanol, and the polymer was precipitated and then stirred with a magnetic stirrer overnight. The polymer was collected by filtration through a glass filter and dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.79 g of an ethylene / 1-butene copolymer polymer. As a result of GPC analysis, the number average molecular weight was 29,000, and Mw / Mn was 1.15 (polyethylene equivalent). According to IR analysis, the amount of 1-butene introduced was 22.8 mol%.</p><p num="0478"><u style="single">Example 35</u> 200 ml of dry toluene was charged into a glass autoclave with an internal volume of 500 ml sufficiently nitrogen-substituted, 1-butene was circulated at 100 liter / h for 40 minutes, the polymerization temperature was maintained at 25 ° C, and methylaluminoxane was converted to aluminum. 5.00 mmol was added. Subsequently, 0.05 mmol of the catalyst was added, and the gas was switched to a mixed gas of ethylene and 1-butene (ethylene: 40 liters / h, 1-butene: 60 liters / h), stirred for 30 minutes, and then 20 ml of isobutyl alcohol was added. The reaction was stopped. Subsequently, 10 ml of 1N hydrochloric acid solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes, the polymerization solution was poured into 1.5 liters of methanol, and the polymer was precipitated and then stirred with a magnetic stirrer overnight. The polymer was collected by filtration through a glass filter and dried under reduced pressure at 80 ° C. for 10 hours to obtain 5.15 g of an ethylene / 1-butene copolymer polymer. As a result of GPC analysis, the number average molecular weight was 73,000, and Mw / Mn was 1.16 (polyethylene equivalent). In addition, the amount of 1-butene introduced was 14.5 mol% from IR analysis.</p><p num="0479"><u style="single">Example 36</u> 200 ml of dry toluene was charged into a glass autoclave with an internal volume of 500 ml sufficiently nitrogen-substituted, 1-butene was circulated at 100 liter / h for 40 minutes, the polymerization temperature was maintained at 25 ° C, and methylaluminoxane was converted to aluminum. 5.00 mmol was added. Subsequently, 0.05 mmol of the catalyst was added, and the gas was switched to a mixed gas of ethylene and 1-butene (ethylene: 60 liters / h, 1-butene: 40 liters / h), stirred for 10 minutes, and then 20 ml of isobutyl alcohol was added. The reaction was stopped. Subsequently, 10 ml of 1N hydrochloric acid solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes, the polymerization solution was poured into 1.5 liters of methanol, and the polymer was precipitated and then stirred with a magnetic stirrer overnight. The polymer was collected by filtration through a glass filter and dried under reduced pressure at 80 ° C. for 10 hours to obtain 2.38 g of an ethylene / 1-butene copolymer polymer. As a result of GPC analysis, the number average molecular weight was 38,800, and Mw / Mn was 1.18 (polyethylene equivalent). In addition, the amount of 1-butene introduced was 11.3 mol% from IR analysis.</p><p num="0480"><u style="single">Example 37</u> 200 ml of toluene and 50 ml of 1-hexene were charged into a glass autoclave having an internal volume of 500 ml sufficiently substituted with nitrogen, and the liquid and gas phases were saturated with ethylene with stirring. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.0025 mmol of titanium compound (1) was subsequently added to initiate polymerization. After reacting at 25 ° C for 5 minutes while blowing ethylene, polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was added to methanol in which a small amount of hydrochloric acid was dissolved to precipitate a polymer, which was then filtered through a glass filter. The polymer was dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.304 g of an ethylene / hexene copolymer. The polymerization activity per 1 mmol of titanium was 1.46 kg. The number average molecular weight (Mn) of the obtained polymer was 95,600, Mw / Mn was 1.17, and the hexene content was 2.7 mol%.</p><p num="0481"><u style="single">Example 38</u> The same procedure as in Example 37 was carried out except that the titanium compound (1) was changed to 0.001 mmol, toluene was changed to 225 ml, and 1-hexene was changed to 25 ml. 0.241 g of ethylene / hexene copolymer was obtained. The polymerization activity per 1 mmol of titanium was 2.89 kg. The number average molecular weight (Mn) of the obtained polymer was 152,000, Mw / Mn was 1.22, and the hexene content was 1.7 mol%.</p><p num="0482"><u style="single">Reference example 39</u> 250 ml of toluene was placed in a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, the liquid phase and the gas phase were once saturated with ethylene, and then only the gas phase was nitrogen-substituted. Polymerization was started by adding 2.5 mmol of methylaluminoxane in terms of aluminum atom and then 0.01 mmol of titanium compound (1). After reacting at 25 ° C for 5 minutes, a small amount of methanol was added to stop the reaction. Hydrochloric acid and a large amount of methanol were added to precipitate the polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure to obtain 0.800 g of polyethylene (PE). The number average molecular weight (Mn, PP equivalent) of the obtained polyethylene was 115,000, and Mw / Mn was 1.10. When converted from the polymer yield, ethylene in the system was consumed quantitatively.</p><p num="0483"><u style="single">Reference example 40</u> In Reference Example 39, ethylene was reacted at 25 ° C. for 5 minutes to completely consume it, and then reacted for 20 minutes while blowing propylene gas (30 liters / h), blocking propylene and reacting for another 280 minutes. The reaction was stopped by adding a small amount of methanol, and the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.135 g of the polymer. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 136,000, Mw / Mn was 1.15, and the propylene content was 14.6 mol%.</p><p num="0484"> Compared with the polyethylene prepolymer produced in Reference Example 39, the molecular weight increased while the molecular weight distribution was narrow, and propylene was incorporated into the polymer, so that a polyethylene-polypropylene diblock copolymer was quantitatively produced. I was able to confirm that.</p><p num="0485"><u style="single">Reference example 41</u> In Reference Example 39, after reacting ethylene at 25 ° C for 5 minutes, the reaction was carried out for 3 minutes while blowing ethylene gas (25 liters / h) and propylene gas (75 liters / h), and the mixed gas was shut off. It was allowed to react for 3 minutes. The reaction was stopped by adding a small amount of methanol, and the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.700 g of the polymer. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 211,000, the molecular weight distribution (Mw / Mn) was 1.16, and the propylene content was 6.4 mol%.</p><p num="0486"> Compared with the polyethylene prepolymer produced in Reference Example 39, the molecular weight increased while the molecular weight distribution was narrow, and propylene was incorporated into the polymer. Therefore, the polyethylene-ethylene / propylene diblock copolymer was quantitatively produced. It was confirmed that it was generated. The propylene content of the second block component (ethylene-propylene copolymer portion) calculated from the molecular weight and the propylene content in the total polymer was 14.6 mol%.</p><p num="0487"><u style="single">Reference example 42</u> In Reference Example 39, after reacting ethylene at 25 ° C for 5 minutes, the reaction was carried out for 3 minutes while blowing ethylene gas (25 liters / h) and propylene gas (75 liters / h), and the mixed gas was shut off. It was allowed to react for 3 minutes. Subsequently, the reaction was carried out while blowing propylene (30 liters / h) for 20 minutes, the propylene was blocked, and the reaction was carried out for another 280 minutes. The reaction was stopped by adding a small amount of methanol, and the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.814 g of the polymer. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 235,000, the molecular weight distribution (Mw / Mn) was 1.15, and the propylene content was 14.1 mol%.</p><p num="0488"> Compared with the polyethylene-ethylene / propylene diblock copolymer prepolymer produced in Reference Example 41, the molecular weight is increased while the molecular weight distribution is narrow, and the propylene content in the polymer is increased. It was confirmed that the propylene copolymer-polypropylene block triblock copolymer was quantitatively produced. The increase in propylene content was in agreement with the calculated value assuming that the third block component introduced in this example was polypropylene.</p><p num="0489"><u style="single">Reference example 43</u> In Reference Example 39, after reacting ethylene at 25 ° C for 5 minutes, the reaction was carried out for 3 minutes while blowing ethylene gas (25 liters / h) and propylene gas (75 liters / h), and the mixed gas was shut off. It was allowed to react for 3 minutes. Subsequently, the reaction was carried out for 1 minute while blowing ethylene gas (100 liters / h), and a small amount of methanol was added to stop the reaction. The reaction was added to 1 liter of methanol containing a small amount of hydrochloric acid and stirred to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.998 g of a polyethylene-ethylene / propylene copolymer-LLDPE block polymer. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 272,000, Mw / Mn was 1.13, and the propylene content was 6.6 mol%.</p><p num="0490"> Compared with the polyethylene-ethylene / propylene diblock copolymer prepolymer produced in Reference Example 41, the molecular weight is increased while the molecular weight distribution is narrow, and the ethylene content in the polymer is increased. It was confirmed that the propylene copolymer-LLDPE triblock copolymer was quantitatively produced. The propylene content of the third block component (LLDPE portion) calculated from the molecular weight and the propylene content in the total polymer was 7.3 mol%.</p><p num="0491"><u style="single">Reference example 44</u> In Reference Example 39, polymerization was carried out in the same manner except that the amount of catalyst was changed to 0.02 mmol. 0.800 g of polyethylene (PE) was obtained. The number average molecular weight (Mn, PP equivalent) of the selected polyethylene was 78,200, and the molecular weight distribution (Mw / Mn) was 1.14. Furthermore, in this example, ethylene was reacted at 25 ° C for 5 minutes, then reacted for 3 minutes while blowing ethylene gas (20 liters / h) and butene gas (80 liters / h), and the mixed gas was shut off for another 3 minutes. It was reacted. The reaction was stopped by adding a small amount of methanol, and the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid and stirred to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.416 g of a polyethylene-ethylene / butene copolymer block polymer. The number average molecular weight (Mn, PP equivalent) of the polymer was 120,600, and the molecular weight distribution (Mw / Mn) was 1.13. The butene content in the total polymer was 1.9 mol%.</p><p num="0492"> Compared with the polyethylene prepolymer produced in Reference Example 39, the molecular weight increased while the molecular weight distribution was narrow, and butene was incorporated into the polymer, so that a polyethylene-LLDPE diblock copolymer was quantitatively produced. I was able to confirm that. The butene content of the second block component (LLDPE portion) calculated from the molecular weight and the butene content in the total polymer was 5.6 mol%.</p><p num="0493"><u style="single">Reference example 45</u> In Reference Example 39, after reacting ethylene at 25 ° C for 5 minutes, the reaction was carried out for 3 minutes while blowing ethylene gas (20 liters / h) and butene gas (80 liters / h), and the mixed gas was shut off for another 3 minutes. Reacted for minutes. Subsequently, the reaction was carried out for 1 minute while blowing ethylene gas (100 liters / h), and a small amount of methanol was added to stop the reaction. The reaction was added to 1 liter of methanol containing a small amount of hydrochloric acid and stirred to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.921 g of a polyethylene-LLDPE-HDPE block polymer. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 141,400, and the molecular weight distribution (Mw / Mn) was 1.14. The butene content in the total polymer was 2.0 mol%.</p><p num="0494"> Compared with the polyethylene-LLDPE diblock copolymer prepolymer produced in Reference Example 44, the molecular weight increased while the molecular weight distribution was narrow, and the ethylene content in the polymer changed. It was confirmed that the block copolymer was quantitatively produced. The butene content of the third block component (HDPE portion) calculated from the molecular weight and the butene content in the total polymer was 2.6 mol%.</p><p num="0495"><u style="single">Example 46</u> 250 ml of toluene was placed in a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid and gas phases were saturated with propylene at 25 ° C. Then, 2.5 mmol of methylaluminoxane was added in terms of aluminum atom, and then 0.01 mmol of titanium compound (1) was added to initiate polymerization. After reacting at 25 ° C for 180 minutes, a small amount of methanol was added to stop the reaction. The reaction was added to 1 liter of methanol containing a small amount of hydrochloric acid and stirred to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 8 hours to obtain 0.100 g of polypropylene. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 17,200, and Mw / Mn was 1.15.</p><p num="0496"><u style="single">Reference example 47</u> In Example 46, after reacting propylene for 180 minutes, the reaction was further carried out for 3 minutes while blowing ethylene gas (20 liters / h), and a small amount of methanol was added to stop the reaction. The reaction was added to 1 liter of methanol containing a small amount of hydrochloric acid and stirred to precipitate a polymer. The polymer was filtered, washed with methanol, and dried under reduced pressure to obtain 0.481 g of a polypropylene-ethylene / propylene copolymer block polymer. The number average molecular weight (Mn, PP equivalent) of the obtained polymer was 99,000, Mw / Mn was 1.06, and the ethylene content was 70.9 mol%.</p><p num="0497"> Compared with the polypropylene prepolymer produced in Example 46, the molecular weight is increased while the molecular weight distribution is narrow, and ethylene is incorporated into the polymer. Therefore, the polypropylene-ethylene / propylene diblock copolymer is quantitatively produced. It was confirmed that it was generated. The ethylene content of the second block component (ethylene-propylene copolymer portion) calculated from the molecular weight and the propylene content in the total polymer was 18.4 mol%.</p><p num="0498"><u style="single">Reference example 48</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and propylene was circulated at 100 liters / hr to saturate the inside of the system. Next, 2.5 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.02 mmol of titanium compound (1) was added to initiate polymerization at room temperature (24 ° C). After polymerization for 5 hours, the supply of propylene was stopped and the supply of ethylene was started at 1.5 liters / hr. After polymerizing at room temperature for 40 minutes, the polymerization was stopped by adding a small amount of isobutanol. The entire amount of the obtained polymer slurry was put into 1.5 liters of methanol, a small amount of hydrochloric acid was added, and then the polymer was collected by filtration. The obtained polymer was washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours. The polymer yield after drying was 2.53 g. As a result of measuring this polymer by GPC, the number average molecular weight was 160,300 and Mw / Mn was 1.51.</p><p num="0499"> 50 mg of the obtained polymer was dissolved in 0.5 ml of a mixed solvent of orthodichlorobenzene / deuterium benzene (mixing ratio is 8/1 by volume) at 110 ° C., and a JEOL LA500 nuclear magnetic resonance apparatus was used. It was measured at 125.8 MHz in proton complete decay mode under the following conditions.</p><p num="0500"> Pulse angle 45 °. Pulse repetition 5.5 sec., Spectral width 22000Hz, Number of scans 16000, Temperature 120 ° C, Deta points 32K. As a result, the monomer unit M¹The ethylene, monomer unit M²When is propylene, [M¹] Is 59.7 mol%, [M²] Is 40.3 mol%, [M¹ M²] Is 43.4 mol%, [M¹ M¹] Is 38.1 mol%, [M² M²] Is 18.6 mol%, [M¹ M²] / (2 × [M¹] × [M²]) Value is 0.90 [M¹ M²]²/ (4 × [M¹ M¹] × [M² M²]) Was 0.66.</p><p num="0501"> The distribution of n consecutive methylene n was as follows. [n = 1] = 37.87 mol%, [n = 2] = 14.59 mol%, [n = 3] = 9.96 mol%, [n = 4] = 6.94 mol%, [n = 5] = 7.41 mol%, [n 6] = 23.23 mol% n = 3, 5, 6 or more methylene is an isolated monomer unit M, respectively.¹, Only two consecutive monomer units M¹, 3 or more consecutive monomer units M¹Indicates that has been detected.</p><p num="0502"><u style="single">Reference example 49</u> 250 ml of dry toluene was charged into a glass autoclave with an internal volume of 500 ml sufficiently nitrogen-substituted, and after circulating propylene at 100 liters / h for 20 minutes, the polymerization temperature was maintained at 25 ° C, and methylaluminoxane was 5.00 in terms of aluminum. mmol was added. Subsequently, 0.05 mmol of titanium compound (1) was added, and the gas was switched to a mixed gas of ethylene and propylene (ethylene: 35 liters / h, propylene: 65 liters / h), stirred for 3 minutes and 20 seconds, and then 20 ml of isobutyl alcohol. Was added to stop the reaction. Subsequently, 10 ml of 1N hydrochloric acid solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes, the polymerization solution was poured into 1.5 liters of methanol, and the polymer was precipitated and then stirred with a magnetic stirrer overnight. The polymer was collected by filtration through a glass filter and dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.19 g of an ethylene / propylene copolymer polymer. As a result of GPC analysis, Mn = 25,100 and Mw / Mn was 1.07. In addition, the amount of propylene introduced was 24.4 mol% according to IR analysis.</p><p num="0503"><u style="single">Reference example 50</u> 250 ml of dry toluene was charged into a glass autoclave with an internal volume of 500 ml sufficiently nitrogen-substituted, and after circulating propylene at 100 liters / h for 20 minutes, the polymerization temperature was maintained at 25 ° C, and methylaluminoxane was 5.00 in terms of aluminum. mmol was added. Subsequently, 0.05 mmol of the titanium compound (1) was added, the gas was switched to a mixed gas of ethylene and propylene (ethylene: 35 liter / h, propylene: 65 liter / h), and the mixture was stirred for 3 minutes and 20 seconds, and then the composition was different. The reaction was stopped by switching to a mixed gas of ethylene and propylene (ethylene: 60 liters / h, propylene: 40 liters / h), stirring for 1 minute and 50 seconds, and then adding 20 ml of isobutyl alcohol. Subsequently, 10 ml of 1N hydrochloric acid solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes, the polymerization solution was poured into 1.5 liters of methanol, and the polymer was precipitated and then stirred with a magnetic stirrer overnight. The polymer was collected by filtration through a glass filter and dried under reduced pressure at 80 ° C. for 10 hours to obtain 2.29 g of AB diblock copolymer. As a result of GPC analysis, the number average molecular weight was 40,600 and Mw / Mn was 1.09. In addition, the amount of propylene introduced was 23.1 mol% according to IR analysis.</p><p num="0504"><u style="single">Reference example 51</u> 250 ml of dry toluene was charged into a glass autoclave with an internal volume of 500 ml sufficiently nitrogen-substituted, and after circulating propylene at 100 liters / h for 20 minutes, the polymerization temperature was maintained at 25 ° C, and methylaluminoxane was 5.00 in terms of aluminum. mmol was added. Subsequently, 0.05 mmol of the titanium compound (1) was added, the gas was switched to a mixed gas of ethylene and propylene (ethylene: 35 liters / h, propylene: 65 liters / h), and the mixture was stirred for 3 minutes and 20 seconds, and then the composition was different. Switch to (ethylene: 60 liters / h, propylene: 40 liters / h), stir for 1 minute and 50 seconds, switch to ethylene gas 100 liters / h, stir for 1 minute and 10 seconds, and then add 20 ml of isobutyl alcohol. The reaction was stopped. Subsequently, 10 ml of 1N hydrochloric acid solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes, the polymerization solution was poured into 1.5 liters of methanol, and the polymer was precipitated and then stirred with a magnetic stirrer overnight. The polymer was collected by filtration through a glass filter and dried under reduced pressure at 80 ° C. for 10 hours to obtain 3.79 g of ABC triblock copolymer. As a result of GPC analysis, the number average molecular weight was 59,000 and Mw / Mn was 1.11. In addition, the amount of propylene introduced was 19.5 mol% according to IR analysis.</p><p num="0505"><u style="single">Reference example 52</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with ethylene. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.0002 mmol of titanium compound (2) was subsequently added to initiate polymerization. After reacting at 50 ° C. for 2 minutes under a normal pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, a small amount of hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate the entire amount of the polymer, and then the polymer was filtered. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 0.213 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 3.20 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 73,300 and 79,900, respectively, and Mw / Mn was 1.08.</p><p num="0506"><u style="single">Reference example 53</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently replaced with nitrogen, and 100 liters / h of ethylene and 5 liters / h of hydrogen were blown into the autoclave with stirring for 10 minutes. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.0002 mmol of titanium compound (2) was subsequently added to start polymerization. After reacting at 50 ° C. for 2 minutes while blowing ethylene and hydrogen, polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, a small amount of hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate the entire amount of the polymer, and then the polymer was filtered. The polymer was dried under reduced pressure at 80 ° C. for 10 hours to give 0.195 g of polyethylene (PE). The polymerization activity per 1 mmol of titanium was 2.93 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 59,500 and 69,700, respectively, and Mw / Mn was 1.17.</p><p num="0507"><u style="single">Reference example 54 ~ 58</u> Polymerization was carried out in the same manner as in Reference Example 53, except that the amount of catalyst, the flow rate of hydrogen, and the polymerization time were changed as shown in Table 3. Table 3 shows the polymerization activity, the molecular weight of the obtained polymer, and the molecular weight distribution. It was confirmed that hydrogen acts as a chain transfer agent because the molecular weight decreases when the amount of hydrogen added is increased and the molecular weight of the produced polymer hardly increases even if the polymerization time is extended. Further, since the polymerization activity did not decrease even when the polymerization time was extended, it was confirmed that the polymerization was further advanced by the active species produced by the chain transfer reaction.</p><p num="0508"><tables num="3"><img id="000056" he="222" wi="77" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><u style="single">Reference example 59</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with ethylene. Then, 1.25 mmol of methylaluminoxane and 0.08 mmol of diethylzinc in terms of aluminum atom, and subsequently 0.002 mmol of titanium compound (2) were added to initiate polymerization. After reacting at 50 ° C. for 2 minutes under a normal pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, a small amount of hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate the entire amount of the polymer, and then the polymer was filtered. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 0.209 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 3.14 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 51,500 and 70,300, respectively, and Mw / Mn was 1.37.</p><p num="0509"><u style="single">Reference example 60 ~ 62</u> Polymerization was carried out in the same manner as in Reference Example 59 except that the amount of diethylzinc and the polymerization time were changed as shown in Table 4. Table 4 shows the polymerization activity, the molecular weight of the obtained polymer, and the molecular weight distribution.</p><p num="0510"> It was confirmed that the zinc compound acts as a chain transfer agent because the molecular weight decreases when the addition amount of the zinc compound is increased and the molecular weight of the produced polymer hardly increases even if the polymerization time is extended. Further, since the polymerization activity did not decrease even when the polymerization time was extended, it was confirmed that the polymerization was further advanced by the active species produced by the chain transfer reaction.</p><p num="0511"><tables num="4"><img id="000057" he="213" wi="50" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><u style="single">Reference example 63</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with ethylene. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.002 mmol of titanium compound (3) was subsequently added to initiate polymerization. After reacting at 50 ° C. for 10 minutes under a normal pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, a small amount of hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate the polymer, which was then filtered and washed with methanol. The polymer was dried under reduced pressure at 80 ° C. for 10 hours to give 0.247 g of polyethylene (PE). The polymerization activity per 1 mmol of titanium was 0.74 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 88,500 and 98,800, respectively, and Mw / Mn = 1.12.</p><p num="0512"><u style="single">Reference example 64</u> In Reference Example 63, polymerization was carried out in the same manner except that the titanium compound (3) was changed to 0.001 mmol and the polymerization time was changed to 15 minutes to obtain 0.161 g of polyethylene (PE). The polymerization activity per 1 mmol of titanium was 0.64 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 145,000 and 167,000, respectively, and Mw / Mn = 1.15.</p><p num="0513"><u style="single">Comparative example 1</u> 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with ethylene. Then, 1.25 mmol of methylaluminoxane was added in terms of aluminum atom, and 0.0005 mmol of zirconosendichloride was subsequently added to start polymerization. After reacting at 25 ° C for 0.5 minutes under a normal pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, a small amount of hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate the entire amount of the polymer, which was then filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 0.229 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of zirconium was 55.0 kg. The number average molecular weight of the obtained PE was 114,000, and Mw / Mn was 1.99.</p><p num="0514"><u style="single">Comparative example 2</u> In Comparative Example 1, the polymerization was carried out in the same manner except that the polymerization time was changed to 1 minute. 0.433 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of zirconium was 52.0 kg. The number average molecular weight of the obtained PE was 136,000, and Mw / Mn was 2.26.</p><p num="0515"><u style="single">Comparative example 3</u> In Comparative Example 1, 0.253 g of polyethylene (PE) was obtained by carrying out the same polymerization except that the titanium compound (9) was 0.00025 mmol instead of the zirconium compound and the polymerization time was changed to 1 minute. The polymerization activity per 1 mmol of titanium was 60.7 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 184,000 and 370,000, respectively, and Mw / Mn = 2.01.</p><p num="0516"><u style="single">Comparative example 4</u> In Comparative Example 1, the polymerization was carried out in the same manner except that the titanium compound (10) was changed to 0.0005 mmol and the polymerization time was changed to 1 minute instead of the zirconium compound, and 0.267 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 32.0 kg. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained PE were 129,000 and 229,000, respectively, and Mw / Mn = 1.78.</p><p num="0517"><u style="single">Comparative example 5</u> 50 ml of toluene was charged into a fully nitrogen-substituted reactor with an internal volume of 100 ml, cooled to 0 ° C., and the liquid and gas phases were saturated with ethylene. Then, 0.0125 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was added, followed by 0.0125 mmol of hafnium compound (11) to initiate polymerization. After reacting at 0 ° C. for 1 minute under a normal pressure ethylene atmosphere, a small amount of methanol was added to terminate the polymerization. The reaction was poured into a large amount of methanol to precipitate a polymer, which was filtered and then washed with methanol. It was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.290 g of polyethylene (PE). The number average molecular weight (Mn) of the obtained PE was 132,400, and Mw / Mn = 1.85.</p><p num="0518"><u style="single">Comparative example 6</u> In Reference Example 5, the polymerization was carried out in the same manner except that the hafnium compound (12) and the dimethylanilinium tetrakis (pentafluorophenyl) borate were changed to 0.005 mmol and the polymerization temperature was changed to 50 ° C. 0.148 g of polyethylene (PE) was obtained. The number average molecular weight (Mn) of the obtained PE was 98,800, and Mw / Mn = 1.91. Complex structure parameter calculation example</p><p num="0519"><chemistry num="53"><img id="000058" he="111" wi="152" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> H of each catalyst^B-Z distance (r (H)^B-Z)) and electrostatic interaction energy (ES (H)^B-Z)))</p><p num="0520"><tables num="5"><img id="000059" he="31" wi="154" file="JP5773852B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p>