Production of alpha-olefin polymer

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Background of invention] [Industrial application field]

The present invention relates to a method for producing an α-olefin polymer. More specifically, the present invention relates to a method for producing an α-olefin polymer with a reduced amount of organoaluminum component by using a novel catalyst component.

【0002】

[Conventional technology]

A method for obtaining an α-olefin polymer in a high yield by using a catalyst composed of a Group IVB metallocene compound and methylarmoxane in the periodic table is known (Japanese Patent Laid-Open No. 58-19503 and 60-35007). Each publication). These proposals provide polymers with high activity per transition metal and a narrow molecular weight distribution.

【0003】

Further, by using a specific metallocene compound, polypropylene having stereoregularity can be produced (Japanese Patent Laid-Open Nos. 61-130314, 63-295607, 1-275609, 1-). 301704, 2-41303 and 2-274703). However, although these proposals have made it possible to produce polymers with industrially useful characteristics, the co-catalyst methylalmoxane is very expensive and generally contains large amounts of methylalmoxane. There is an industrial problem with this method because it must be used, the activity per aluminum atom is low, the manufacturing cost is high, and a large amount of aluminum remains in the olefin polymer. Seem.

【0004】

Various proposals have been made for the purpose of solving these problems (Japanese Patent Laid-Open Nos. 61-211307, 63-130601, 64-16803, Japanese Patent Application Laid-Open No. 2-22308, and Japanese Patent Application Laid-Open No. 2-167307. ). Although these proposals have improved the activity per aluminum to some extent, such alumoxane has poor solubility, is difficult to handle, and it is difficult to remove aluminum, so that the quality of the olefin polymer is deteriorated and the hue is deteriorated. It seems that further improvement is needed.

【0005】

As another proposal, a method for coexisting other organoaluminum compounds with methylarmoxane is disclosed (Japanese Patent Laid-Open Nos. 60-260602, 60-130604, 63-89506, 63-178108). , No. 63-218707, No. 64-9206, JP-A 1-315407, No. 2-22306 and No. 2-167310). Although the amount of methylarmoxane used has been reduced by these proposals, the activity per aluminum is insufficient, and further improvement is desired.

【0006】

On the other hand, as a new attempt, a method of activation without using methylarmoxane is disclosed (Publication No. 1-501950, No. 1-502036, JP-A 3-207703, No. 3-207704). , 3-179005, JP-A 3-197513 and 3-197514). Although the use of methylarmoxane is omitted from these proposals, it is considered necessary to remove the transition metal component from the polymer because the activity per transition metal is significantly reduced, and further improvement is desired. ..

【0007】

[Problems to be Solved by the Invention]

The problem to be solved by the present invention is a method for producing a high-quality α-olefin polymer by reducing the amount of methylarmoxane as a co-catalyst without lowering the activity per metallocene compound. Is to provide.

【0008】

[Means for solving problems]

[Outline of Invention] <Purpose> The present invention has been made as a result of studies for achieving the above problems. That is, the method for producing an α-olefin polymer according to the present invention is characterized in that an α-olefin is brought into contact with a catalyst composed of the following components (A) and (B) and polymerized.

【0009】

Ingredient (A) Contact products of the following components (i) to (iii) Ingredient (i) General formula Q_a(C₅H_5-abR¹_b) (C₅H_5-acR²_c) MeXY or general formula A_d(C₅H_5-deR³_e) (R⁴_2-dJ) Transition metal compound represented by MeXY [Here, (C₅H_5-abR¹_b), (C₅H_5-acR²_c) And (C₅H_5-_deR³_e) Are conjugated five-membered ring ligands (where R) coordinate to Me, respectively.¹, R²And R³Are hydrocarbon residues with 1 to 20 carbon atoms, halogen groups, alkoxy groups with 1 to 12 carbon atoms, silicon-containing hydrocarbon groups with 1 to 24 carbon atoms, phosphorus-containing hydrocarbon groups with 1 to 18 carbon atoms, and carbon. It is a monovalent group selected from the group consisting of a nitrogen-containing hydrocarbon group having a number of 1 to 18 and a boron-containing hydrocarbon group having a carbon number of 1 to 18.⁴Is a monovalent group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 24 carbon atoms, and an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms (R).¹And R²May be the same as or different from. Also R¹When there are a plurality of them, they may be the same or different, or they may be connected at the other end of each. Similarly R²(Or R³) May be the same or different, or they may be combined at the other end of each. )), Q is a divalent binding group that crosslinks two conjugated five-membered ring ligands, and A is (C).₅H_5-deR³_e) And (R⁴_2-dA divalent bonding group that bridges J), J is a nitrogen or phosphorus atom that binds to Me, Me is a transition metal of group IVB to VIB in the periodic table, and X and Y are hydrogen, halogen groups, and carbon numbers, respectively. Hydrocarbon groups 1 to 20, alkoxy groups with 1 to 20 carbon atoms, amino groups optionally substituted with up to 2 hydrocarbon groups with 1 to 20 carbon atoms, phosphorus-containing hydrocarbons with 1 to 20 carbon atoms A monovalent group consisting of a group and a silicon-containing hydrocarbon group having 1 to 20 carbon atoms (X and Y may be the same or different), a and d 0 or 1, b and c is an integer of 0 b 5 when a is 0, an integer of 0 c 5, an integer of 0 b 4 when a is 1, an integer of 0 c 4, and e is When d is 0, an integer of 0 e 5 is shown, and when d is 1, an integer of 0 e 4 is shown. ] Ingredient (ii): Lewis acid Ingredient (iii): Organoaluminium compound Ingredient (B) Armoxan.

【0010】

<Effect> The effect of the present invention is the pre-contact generation in which the component (i), the component (ii) and the component (iii) are pre-contacted under specific conditions to form an active site efficiently and stably. By polymerizing the olefin with a catalyst consisting of a combination of a substance (component (A)) and an almoxane (component (B)), the amount of component (B) used can be significantly reduced. is there.

【0011】

Although the mechanism by which such an effect is exhibited in the present invention has not yet been fully elucidated, in the conventional system, the component (i) is actually an active species due to the presence of the component (B) (in one theory, a metallocene cation species). It is said that) is formed, but since this reaction is a reversible reaction, the generated active species disappears immediately, and a large amount of component (B) is required to obtain a certain amount or more of active species. On the other hand, by contacting the component (i), the component (ii) and the component (iii) of the present invention under special conditions, the disappearance of the active species is suppressed and the active species is stoichiometrically formed. Therefore, it is expected that the reduction of almoxane will be possible because it is sufficient to use an amount of almoxane that plays a role of preventing poisoning and stabilizing active species. It is understood that such an effect is completely unpredictable from the prior art. It should be noted that the present invention is not limited by such a guess.

【0012】

[Specific Description of the Invention] The method for producing an α-olefin polymer of the present invention comprises polymerizing an olefin using a polymerization catalyst composed of the component (A) and the component (B). Here, "consisting of component (A) and component (B)" means that when component (A) and component (B) are used, any third component coexists as long as the effect is not deteriorated. It is not an exclusion.

【0013】

<Component (A)> Component (A) is a contact product of component (i), component (ii) and component (iii). Ingredient (i) Component (i) is the general formula Q_a(C₅H_5-abR¹_b) (C₅H_5-acR²_c) MeXY or general formula A_d(C₅H_5-deR³_e) (R⁴_2-dJ) Transition metal compound represented by MeXY [Here, (C₅H_5-abR¹_b), (C₅H_5-acR²_c) And (C₅H_5-_deR³_e) Are conjugated five-membered ring ligands (where R) coordinate to Me, respectively.¹, R²And R³Are hydrocarbon residues with 1 to 20 carbon atoms, halogen groups, alkoxy groups with 1 to 12 carbon atoms, silicon-containing hydrocarbon groups with 1 to 24 carbon atoms, phosphorus-containing hydrocarbon groups with 1 to 18 carbon atoms, and carbon. It is a monovalent group selected from the group consisting of a nitrogen-containing hydrocarbon group having a number of 1 to 18 and a boron-containing hydrocarbon group having a carbon number of 1 to 18.⁴Is a monovalent group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 24 carbon atoms, and an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms (R).¹And R²May be the same as or different from. Also R¹When there are a plurality of them, they may be the same or different, or they may be connected at the other end of each. Similarly R²(Or R³) May be the same or different, or they may be combined at the other end of each. )), Q is a divalent binding group that crosslinks two conjugated five-membered ring ligands, and A is (C).₅H_5-deR³_e) And (R⁴_2-dA divalent bonding group that bridges J), J is a nitrogen or phosphorus atom that binds to Me, Me is a transition metal of group IVB to VIB in the periodic table, and X and Y are hydrogen, halogen groups, and carbon numbers, respectively. Hydrocarbon groups 1 to 20, alkoxy groups with 1 to 20 carbon atoms, amino groups optionally substituted with up to 2 hydrocarbon groups with 1 to 20 carbon atoms, phosphorus-containing hydrocarbons with 1 to 20 carbon atoms A monovalent group consisting of a group and a silicon-containing hydrocarbon group having 1 to 20 carbon atoms (X and Y may be the same or different), a and d 0 or 1, b and c is an integer of 0 b 5 when a is 0, an integer of 0 c 5, an integer of 0 b 4 when a is 1, an integer of 0 c 4, and e is When d is 0, an integer of 0 e 5 is shown, and when d is 1, an integer of 0 e 4 is shown.

【0014】

Here, Q is a binding group that crosslinks two conjugated five-membered ring ligands, and A is a conjugated five-membered ring ligand (R).⁴_2-dJ) Represents a binding group that crosslinks a group. Specifically, (a) alkylene groups such as (a) methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group and cyclohexylene group, (b) silylene group, dimethylsilylene group, phenylmethylsilylene group and diphenylcilylene A silylene group such as a group, a disylylene group, a tetramethyldisylylene group, and a hydrocarbon group containing (c) germanium, phosphorus, nitrogen, boron or aluminum [specifically, (CH).₃)₂Ge group, (C₆H₅)₂Ge group, (CH₃) P group, (C₆H₅) P group, (C₄H₉) N groups, (C₆H₅) N groups, (CH₃) B group, (C₄H₉) B group, (C₆H₅) B group, (C₆H₅) Al group, (CH₃O) Al group, etc.] etc.

【0015】

It is preferably an alkylene group and a silylene group. a and d are 0 or 1. In the above general formula, (C₅H_5-abR¹_b), (C₅H_5-acR²_c) And (C⁵H_5-deR³_eThe conjugated five-membered ring ligands represented by) are defined separately, but a and d, b, c and e, and R.¹, R²And R³It goes without saying that these three conjugated five-membered ring groups may be the same or different because the definition of is the same (detailed later).

【0016】

One specific example of this conjugated five-membered ring group is a cyclopentadienyl group with b = 0 (or c = 0, e = 0) (no substituents other than the bridging group Q or A). If this conjugated five-membered ring group is b 0 (or c 0, e 0) and has a substituent, then R¹(Or R², R³One specific example of) is a hydrocarbon group (C).₁~ C₂₀, Preferably C₁~ C₁₂) However, even if this hydrocarbon group is bonded to a cyclopentadienyl group as a monovalent group, or when there are a plurality of these groups, the two are bonded at the other end of each to form a cyclopentadienyl group. A ring may be formed with a part of the enyl group. A typical example of the latter is R¹(Or R², R³) Share the double bond of the cyclopentadienyl group to form a condensed six-membered ring, that is, the conjugated five-membered ring group is an indenyl group, a tetrahydroindenyl group, or a fluorenyl group. is there. That is, typical examples of this conjugated five-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group.

【0017】

R¹, R²And R³Are the above Cs, respectively₁~ C₂₀, Preferably C₁~ C₁₂, Halogen groups (eg fluorine, chlorine, bromine), alkoxy groups (eg C)₁~ C₁₂), Silicon-containing hydrocarbon groups (for example, groups containing silicon atoms in the form of -Si (R) (R) (R) with about 1 to 24 carbon atoms), phosphorus-containing hydrocarbon groups (for example, phosphorus atoms) Is a group having 1 to 18 carbon atoms containing -P (R) (R)), and a nitrogen-containing hydrocarbon group (for example, 1 carbon number containing a nitrogen atom in the form of -N (R) (R')). It is a group of about 18 to 18) or a hydrocarbon group containing boron (for example, a group having a carbon number of about 1 to 18 containing a boron atom in the form of -B (R) (R)). b (or c) is 2 or more and R¹(Or R², R³), They may be the same or different. b and c are integers of 0b5 and 0c5 when a is 0, and integers of 0b4 and 0c4 when a is 1. Yes, e is an integer of 0 e 5 when d is 0, and an integer of 0 e 4 when d is 1.

【0018】

Me is a Group IVB-IVB transition metal of the Periodic Table, preferably titanium, zirconium, and hafnium. J is a nitrogen or phosphorus atom bound to Me. X and Y are hydrogen, halogen group, hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10, alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, amino group, and 1 carbon group, respectively. An alkylamino group of ~ 20, preferably 1-12, a phosphorus-containing hydrocarbon group of 1-20, preferably 1-12 (specifically, a diphenylphosphine group), or a carbon number of 1-20. , Preferably 1 to 12, silicon-containing hydrocarbon groups (specifically, for example, trimethylsilyl group). X and Y may be the same or different. Of these, halogen groups and hydrocarbon groups are preferable. Specific examples of this transition metal compound when Me is zirconium are as follows.

【0019】

(B) A transition metal that does not have a linking group to be crosslinked and has two conjugated five-membered ring ligands, for example. (1) Bis (cyclopentadienyl) zirconium dichloride, (2) Bis (methylcyclopentadienyl) zirconium dichloride, (3) Bis (dimethylcyclopentadienyl) zirconium dichloride, (4) Bis (trimethylcyclopentadienyl) Enyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6) bis (pentamethylcyclopentadienyl) zirconium dichloride, (7) bis (indenyl) zirconium dichloride, (8) bis ( Fluolenyl) zirconium dichloride, (9) bis (cyclopentadienyl) zirconium monohydride, (10) bis (cyclopentadienyl) methylzirconium monohydride, (11) bis (cyclopentadienyl) ethyl zirconium monohydride , (12) Bis (cyclopentadienyl) phenylzirconium monolide, (13) Bis (cyclopentadienyl) zirconium dimethyl, (14) Bis (Cyclopentadienyl) Zirconium Diphenyl, (15) Bis (Cyclopentadienyl) Zirconium Dineopentyl, (16) Bis (Cyclopentadienyl) Zirconium Dihydride, (17) (Cyclopentadienyl) (Indenyl) ) Zirconium dichloride, (18) (cyclopentadienyl) (fluorenyl) zirconium dichloride, etc.

【0020】

(B) A transition metal compound having two 5-membered ring ligands crosslinked with an alkylene group, for example. (1) Methylenebis (Indenyl) Zirconium Dichloride, (2) Ethylenebis (Indenyl) Zirconium Dichloride, (3) Ethylenebis (Indenyl) Zirconium Monohydride Monolide, (4) Ethylenebis (Indenyl) Methylzirconium Monolide, (5) ) Ethylene bis (indenyl) zirconium monomethoxymonolide, (6) ethylene bis (indenyl) zirconium diethoxydo, (7) ethylene bis (indenyl) zirconium dimethyl, (8) ethylene bis (4,5,6,7-) Tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylene (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) Zirconium dichloride, [0021] [0021]

(11) Ethylene (2-methyl-4-tertbutylcyclopentadienyl) (3'-tetr butyl-5'-methylcyclopentadienyl) zirconium dichloride, (12) Ethylene (2,3,5-trimethylcyclo Pentazienyl) (2', 4', 5'-trimethylcyclopentadienyl) zirconidylide, (13) isopropylidenebis (indenyl) zirconidichloride, (14) isopropyridenebis (2,4-dimethylcyclopentadienyl) Enyl) (3', 5'-dimethylcyclopentadienyl) zirconide, (15) isopropylidenebis (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl-5-methylcyclopentadienyl) Dienyl) zirconium dichloride, (16) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (17) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) ) Zyrosine chloride hydride, (18) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (19) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (20) methylene (20) Cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, [0022]

(21) Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconidichloride, (22) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconindichloride, (23) isopropi Liden (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconidichloride, (24) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconyldichloride, (25) Isopropylidene (cyclopentadienyl) (fluorenyl) zirconyl dichloride, (26) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconyl dichloride, (27) isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (28) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconyl dichloride, (29) ethylene (cyclopentadienyl) (3,5) -Dimethylcyclopentadienyl) Zyrenyldichloride, (30) Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, [0023]

(31) Ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (32) Ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (33) Diphenylmethylene (cyclopentadienyl) Dienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (34) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (35) cyclohexylidene (cyclo) Pentazienyl) (fluorenyl) zirconium dichloride, (36) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3', 4'-dimethyldimethylcyclopentadienyl) zirconium dichloride, etc.

【0024】

(C) A transition metal compound having two 5-membered ring ligands crosslinked with a silylene group, for example. (1) dimethylsilylene bis (indenyl) zirconium dichloride, (2) dimethylsilylene (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylene (2-methylindenyl) zirconium dichloride, (4) ) Dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (5) Dimethylcilylene (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) zirconium dichloride, (6) ) Phenylmethylsilylenebis (indenyl) zirconium dichloride, (7) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (8) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) ) (3'-5'-dimethylcyclopentadienyl) zirconium dichloride, (9) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2,4,5-trimethylcyclopentadienyl) zirconium Zirconium, (10) Phenylmethylsilylenebis (Tetramethylcyclopentadienyl) Zirconium Dichloride, [0025]

(11) Diphenylcilylenebis (Indenyl) Zirconium Dichloride, (12) Tetramethyldisylylenebis (Indenyl) Zirconium Dichloride, (13) Tetramethyldisylylenebis (Cyclopentadienyl) Zirconium Dichloride, (14) Tetramethyldisylylene (3-Methylcyclopentadienyl) (indenyl) zirconium dichloride, (15) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (16) dimethylsilylene (cyclopentadienyl) ) (Trimethylcyclopentadienyl) zirconium dichloride, (17) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (18) dimethylsilylene (cyclopentadienyl) (3,4-diethyl) Cyclopentadienyl) zirconium dichloride, (19) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (20) Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, [0026]

(21) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (22) dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (23) dimethylsilylene (Cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (24) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (25) dimethylsilylene (2,5-dimethylcyclopentadi) Enyl) (fluorenyl) zirconium dichloride, (26) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (27) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (28) diethylsilylene (2-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (29) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2, 7-di-t-butylfluorenyl) zirconium dichloride, (30) Dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, [0027]

(31) dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (32) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride , (33) dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (34) dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (35) dimethylsilylene (Diethylcyclopentadienyl) (Octahydrofluorenyl) Zirconium dichloride, etc.

【0028】

(D) A transition metal compound having a five-membered ring ligand crosslinked with a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, for example. (1) dimethyl germanium bis (indenyl) zirconium dichloride, (2) dimethyl germanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) methylaluminum bis (indenyl) zirconium dichloride, (4) phenylaluminum bis (indenyl) Zirconium Dichloride, (5) Phenylphosphinobis (Indenyl) Zirconium Dichloride, (6) Ethylhoranobis (Indenyl) Zirconium Dichloride, (7) Phenylaminobis (Indenyl) Zirconium Dichloride, (8) Phenylamino (Cyclopentadienyl) ( Phenylolenyl) zirconium dichloride, etc. are exemplified.

【0029】

(E) A transition metal compound having one 5-membered ring ligand, for example (1) Pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride (2) Indenyl-bis (phenyl) aminozirconium dichloride (3) 4,5,6,7-Tetrahydroindenyl-bis (trimethylsilyl) aminozirconium dichloride (4) Pentamethylcyclopentadienyl bisphenylphosphinozirconium dichloride (5) Dimethylsilylene (Tetramethylcyclopentadienyl) Phenylaminozirconium dichloride (6) Dimethylsilylene (Tetrahydroindenyl) decylaminozirconium dichloride (7) Dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) zirconium dichloride (8) Dimethylgerman (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride (9) Phenylmethylsilylene (fluorenyl) (2,6-diisopropylphenyl) aminozirconium dichloride, etc. are exemplified. (F) Further, a compound in which chlorine of the compounds (a) to (e) above is replaced with bromine, iodine, hydride, methyl, phenyl or the like can also be used.

【0030】

Further, in the present invention, as the component (i), a compound in which the central metal of the zirconium compound exemplified in the above (a) to (e) is changed from zirconium to titanium, hafnium, niobium, molybdenum or tungsten can also be used. Of these, zirconium compounds, hafnium compounds and titanium compounds are preferred. More preferred are titanium compounds, zirconium compounds and hafnium compounds crosslinked with an alkylene group or a silylene group.

【0031】

Ingredient (ii) Ingredient (ii) is Lewis acid. In the present invention, any of them can be used as long as the effect of the present invention is recognized. Examples of such things are (a) MgCl.₂, AlCl₃, AlF₃, BCl₃, BF₃And SiCl₄Metal halogen compounds such as (b) alumina and metal oxides such as silica alumina, (c) trimethylboron, triethylboron, triphenylboron, tris (pentafluorophenyl) boron, triisopropylboron, tributylboron, trixysilylboron , Tris (fluorophenyl) boron, tris (difluorophenyl) boron, dimethylphenyl boron, diphenylboron, diphenylmethoxyboron and other boron compounds, (d) triphenylcarbyltetrakis (pentafluorophenyl) boron and other organic boron compounds Is exemplified. Of these, organoboron compounds are preferred. More preferably, it is an arylboron compound, particularly preferably a halogen-substituted phenylborated inclusion, especially a fluorophenylboron compound, particularly tris (pentafluorophenyl) boron.

【0032】

Ingredient (iii) Component (iii) is an organoaluminum compound. As a specific example, R⁵_3-nAlX_nOr R⁶_3-mAl (OR⁷)_m(Here, R⁵And R⁶May be the same or different hydrocarbon residues or hydrogen atoms with about 1 to 20 carbon atoms, R⁷Is a hydrocarbon residue having about 1 to 20 carbon atoms, X is a halogen, and n and m are 0n3 and 0 &lt;m &lt;3, respectively) or expressed by the following general formula (I) or (II). There is something that can be done.

【0033】

[Chemical 1]

<img file="JPH06100613A_D0001.tif" />【0034】

(Here, p is a number from 0 to 40, preferably 2 to 25, and R⁸Indicates a hydrocarbon residue, preferably one having 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms. ) Specifically, (a) trialkylaluminum such as (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochromeide, diisobutylaluminummonochromide, ethyl. Alkyl aluminum halides such as aluminum sesquichloride and ethylaluminum dichloride, alkylaluminum hydrides such as (c) diethylaluminum hydride and diisobutylaluminum hydride, aluminum alkoxides such as (d) diethylaluminum ethoxide and diethylaluminum phenoxide, (e) methylalmo. Examples thereof include aluminum such as xan, ethylalmoxane, isobutylamoxane, and methylisobutylarmoxan. It is also possible to use a mixture of a plurality of these types. Of these, trialkylaluminum, almoxane and the like are preferable.

【0035】

Contact conditions The ratio of the amounts of component (i), component (ii) and component (iii) used is the molar ratio of the transition metal compound (metal atom equivalent) of component (i) to the Lewis acid of component (ii) (component (i). / Component (ii)) is 1/10000 to 10/1, preferably 1/100 to 2/1, and more preferably 1/50 to 1/1. The ratio of the amount of component (i) to component (iii) (aluminum atom equivalent) used is component (i) / component (iii) = 1/10000 to 10/1, preferably 1/100 to 3/1, and further. It is preferably 1/50 to 1/1.

【0036】

The contact temperature is 78 ° C to 200 ° C, preferably -10 ° C to 100 ° C, and more preferably 0 ° C to 50 ° C. The contact can be carried out by a method of contacting a solid with a solid or the like in a bulk state using a pulverizer or the like, by diluting or slurrying with an inert solvent. Of these, the preferred method is the method of diluting with an inert solvent. The dilution concentration of the component (i) is 1 μM / liter or more, preferably 50 μM / liter or more, and more preferably 200 μM / liter or more. The contact is usually carried out in an inert gas atmosphere, but it can also be carried out under the condition of producing a small amount of prepolymerized polymer in the presence of α-olefin.

【0037】

<Component (B)> Component (B) is an armoxane represented by the following formula (III) or (IV).

【0038】

[Chemical 2]

<img file="JPH06100613A_D0002.tif" />【0039】

(Here, q is a number from 0 to 40, preferably 2 to 25, and R⁹Indicates a hydrocarbon residue, preferably one having 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms. ) Almoxane is a product obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water. Specifically, methylarmoxane, ethylalmoxane, butylarmoxane, isobutylarmoxane, etc. obtained from one type of trialkylaluminum, and methylethylalmoxane, methylbutylalmoxan obtained from two types of trialkylaluminum and water. Examples thereof include xan and methylisobutylarmoxane. It is also possible to use a plurality of these almoxane in combination, and it is also possible to use them in combination with other alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride.

【0040】

It is also possible to use a modified alumoxane by reacting two kinds of almoxane or one kind of alumoxane with another organoaluminum compound. Of these, methylarmoxane, isobutylarmoxane, methylisobutylarmoxane and mixtures of these armoxans and trialkylaluminum are preferably used. Particularly preferred are methylarmoxane and methylisobutylarmoxane.

【0041】

These armoxane can be prepared under a variety of known conditions. Specifically, the following methods can be exemplified. (B) A method of directly reacting trialkylaluminum with water using an appropriate organic solvent such as toluene, benzene, ether, etc. (b) Salt hydrate having trialkylaluminum and crystalline water, for example, copper sulfate, aluminum sulfate. Method of reacting with hydrate, (c) Method of reacting trialkylaluminum with water impregnated in silica sulfate, etc., (d) Mixing trimethylaluminum and triisobutylaluminum, suitable for toluene, benzene, ether, etc. A method of directly reacting with water using an organic solvent, (e) a method of mixing trimethylaluminum and triisobutylaluminum and heat-reacting with a salt hydrate having crystalline water, for example, a hydrate of copper sulfate or aluminum sulfate, ( F) A method in which silica sulfate or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum. (G) Methylalmoxane and isobutylarmoxane are synthesized by a known method, and these two components are combined in a predetermined amount. A method of mixing and heating reaction.

【0042】

<Production of α-olefin polymer> In the production of the α-olefin polymer of the present invention, the polymerization catalyst composed of the above components (A) and (B) is polymerized in the polymerization tank in the presence of a monomer to be polymerized. This is done by mixing and contacting with. The amount of the component (A) and the component (B) used in the present invention is arbitrary, but the conditions for fully exerting the effect of the present invention are the aluminum atom of the almoxane of the component (B) and the component (A). The atomic ratio (Al / Me) of the transition metal compound with the metal atom is 0.01 to 10000, preferably 0.1 to 3000, more preferably 1 to 2000, and particularly preferably 20 to 1000.

【0043】

As described above, the catalyst of the present invention may contain other components in addition to the components (A) and (B), but can be added to the components (A) and (B). Examples of the three components (optional components) include (a) active hydrogen-containing compounds such as water, methanol, ethanol and butanol, (b) electron-donating compounds such as ether, ester and amine, and (c) phenyl borate and dimethyl. Alkoxy-containing compounds such as methoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane can be exemplified.

【0044】

The catalyst for olefin polymerization according to the present invention is of course applied to ordinary slurry polymerization, but is also applied to liquid phase solventless polymerization, solution polymerization or gas phase polymerization method which does not substantially use a solvent. It is also applied to a method of performing continuous polymerization, batch polymerization or prepolymerization. Therefore, the method for producing an α-olefin polymer according to the present invention, which comprises catalyzing an olefin with this catalyst and polymerizing it, adopts each of the above polymerization methods or polymerization modes. As the polymerization solvent in the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used. The polymerization temperature is about 78 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., and hydrogen can be used as a supplementary molecular weight modifier at that time. At the time of slurry polymerization, the amount of the component (A) used is preferably in the range of 0.0001 to 1.0 gram component (A) / liter solvent.

【0045】

The α-olefins polymerized in the catalyst system according to the present invention (in the present invention, ethylene is included), in other words, the α-olefins brought into contact with the catalyst according to the present invention have the general formula R-CH = CH.₂(Here, R is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms and may have a branching group.). Specifically, there are olefins such as ethylene, propylene, butene-1, penten-1, hexene-1, 4-methylpentene-1, decene-1, and hexadecene-1. Ethylene and propylene are preferred. In the case of these polymerizations, copolymerization with the above olefins of up to 50% by weight, preferably up to 20% by weight of ethylene can be carried out and up to 30% by weight of the above olefins with respect to propylene, especially ethylene. , Butene-1, hexene-1, decene-1, hexadecene-1, and the like. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefin, etc.) can also be carried out.

【0046】

[Example]

[Example 1] <Manufacturing of component (A)> Ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, J. Orgmet. Chem. (288) 63 ~ 67 Synthesized according to 1985. Then, 100 ml of dehydrated and deoxidized diethyl ether and 1.28 g (3 mM) of ethylene bis [4,5,6,7-tetrahydroindenyl] zirconium dichloride synthesized above were introduced into a 300 ml flask fully nitrogen-substituted. Then methyllithium (1.6M / L) (Diluted diethyl ether solution) 3.8 ml (6 mM) was added dropwise at -50 ° C or lower over 10 minutes. After keeping this at -50 ° C or lower for 1 hour, the temperature was raised to room temperature over 2 hours. After the temperature was raised, the reaction was carried out at room temperature for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. Toluene (50 ml) was added to the mixture, the insoluble material was filtered, concentrated to 20 ml, and left at -5 ° C overnight. As a result of filtering and drying the produced crystals, 0.95 g of ethylene bis [4,5,6,7-tetrahydroindenyl] zirconium dimethyl (component (i)) was obtained. In a 300 ml flask fully substituted with nitrogen, 100 ml of dehydrated and degassed toluene, and 43 mg (0.1 mM) of ethylene bis [4,5,6,7-tetrahydroindenyl] zirconium dimethyl (component (i)) synthesized above. And 110 mg (0.20 mM) of tris (pentafluorophenyl) boron as component (ii), then 36 mg (0.5 mM) of trimethylaluminum as component (iii), and mixed at room temperature for 30 minutes. A diluted solution of the target component (A) was obtained.

【0047】

<Propene polymerization> In a stainless steel autoclave with an internal volume of 1.0 liter equipped with a stirrer and temperature control device, 400 ml of fully dehydrated and deoxidized toluene and 0.06 g of Schelling's methylarmoxane as component (B) ( 1 mM: aluminum atom equivalent) and 2 ml of the component (A) obtained above (2 μM in terms of component (i)) were introduced, and propylene pressure = 7 kg / cm.²The polymerization operation was carried out at G and a polymerization temperature of 40 ° C for 2 hours. After completion of the polymerization, the polymerization solution was extracted into 1 liter of ethanol, the polymer was filtered off, and dried to recover 77 grams of the polymer. As a result of gel permeation chromatography measurement, this one has a number average molecular weight (Mn) of 22.6 × 10.³The molecular weight distribution was 2.03 in terms of weight average molecular weight / number average molecular weight ratio. By JEOL.FX-200¹³As a result of measuring C-NMR, the [mm] fraction of triad was 0.926.

【0048】

[Example 2] <Polymerization of propylene> The polymerization operation was carried out under the same conditions as in Example 1 except that 0.036 g (0.6 mM) of methylarmoxane (manufactured by Schelling Co., Ltd.) as a component (B) was used. The results are shown in Table 1.

【0049】

[Comparative Examples 1 and 2] <Production of component (A)> When the component (A) is produced in Example 1, all examples except that the tris (pentafluorophenyl) boron of the component (ii) or the trimethylaluminum of the component (iii) is not used. The polymerization operation was carried out under the same conditions as in 1. <Polymerization of Propene> The polymerization operation was carried out under the same conditions as in Example 1 except that the component (A) produced above was used. The results are shown in Table 1.

【0050】

[Comparative Example 3] <Polymerization of Propene> Using the apparatus used in Example 1, instead of using the component (A) of Example 1, the ethylene bis [4,5,6,7-tetrahydroindenyl] zirconium dimethyl of the component (i) Add 0.86 mg (2 μM) of tris (pentafluorophenyl) boron 2.20 mg (4 μM) of component (ii), and 0.72 mg of trimethylaluminum of component (iii), followed by methylarmoxane (shering) of component (B). 0.06 g of (manufactured by the company) was introduced, and the polymerization operation was carried out under the same conditions as in Example 1. The results are shown in Table 1.

【0051】

[Comparative Example 4] <Polymerization of Propene> Introduced 0.86 mg of ethylenebis (4,5,6,7-tetrahydroindenyl] zirconium dimethyl of component (i) and 0.06 g of methylarmoxane (manufactured by Schelling) of component (B). The polymerization operation was carried out under the same conditions as in Example 1 except for the above. The results are as shown in Table 1.

【0052】

[Examples 3 to 9] <Manufacturing of component (A)> In the production of component (A) of Example 1, except that the amount of each component used and the types of component (ii) and component (iii) are changed as shown in Table 2. The component (A) was produced under the same conditions as in Example 1. <Polymerization of Propene> The polymerization operation was carried out under the same conditions as in Example 1 except that the component (A) produced above was used. The results are shown in Table 2.

【0053】

[Example 10] <Production of component (i)> Dimethylsilylbis (tetrahydroindenyl) zirconium dichloride was synthesized according to J. Orgmet. Chem. (342) 21-29 1988 and J. Orgmet. Chem. (369) 359-370 1989. .. Specifically, in a nitrogen-substituted 300 ml flask, 5.4 g of bis (indenyl) dimethylsilane is diluted to 150 ml of tetrahydrofuran, cooled to -50 ° C or lower, and then n-butyllithium (1.6 M / L) is added. 23.6 ml was added dropwise over 30 minutes. After completion of the dropping, the temperature was raised to room temperature over 1 hour, and the reaction was carried out at room temperature for 4 hours to synthesize a reaction solution A.

【0054】

200 ml of tetrahydrofuran was introduced into a nitrogen-substituted 500 ml flask, cooled to -50 ° C or lower, and then 4.38 g of zirconium tetrachloride was slowly introduced. Then, after introducing the entire amount of the reaction solution A, the temperature was slowly raised to room temperature over 3 hours. After reacting at room temperature for 2 hours, the temperature was further raised to 60 ° C. and the reaction was carried out for 2 hours. After completion of the reaction, the solvent was evaporated under reduced pressure, dissolved in 100 ml of toluene, and re-distilled to obtain 3.86 grams of crude dimethylsilylbis (indenyl) zirconium dichloride crude crystals. The crude crystals were then dissolved in 150 ml of dichloromethane, introduced into a 500 ml autoclave, 5 grams of platinum-carbon (0.5 wt% platinum-supported) catalyst introduced, and then H.₂= 50Kg / cm²The hydrogenation reaction was carried out for 5 hours under the conditions of G and 50 ° C. After completion of the reaction, the catalyst was filtered off, the solvent was evaporated under reduced pressure, the mixture was extracted with toluene and recrystallized to obtain 1.26 g of the desired dimethylsilylbis (tetrahydroindenyl) zirconium dichloride.

【0055】

<Production of component (A)> The component (A) was produced under the same conditions as in Example 1 except that the component (i) synthesized above was used. <Polymerization of Propene> All polymerization was carried out under the same conditions as in Example 1 except that the above component (A) was used. The results are shown in Table 3.

【0056】

[Comparative Example 5] The polymerization operation was carried out under the same conditions as in Comparative Example 4 except that the component (i) produced in Example 10 was used. The results are shown in Table 3.

【0057】

[Example 11] <Manufacturing of component (i)> Production of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride 200 ml of THF and 16.5 g of fluorene were introduced into a 500 ml flask fully substituted with nitrogen, cooled to -50 ° C or lower, and 67 ml of a diluted solution of methyllithium diethyl ether (1.4 M) was added dropwise over 30 minutes, and then gradually. The temperature was raised to room temperature and the reaction was carried out for 3 hours. Then, after cooling to -50 ° C or lower again, 10 grams of 6,6-dimethylfulvene was added dropwise over 30 minutes. After completion of the dropping, the temperature was slowly raised to room temperature, and the reaction was carried out for 2 days and nights. After the reaction is completed, H₂Add 60 ml of O to stop the reaction, separate the ether layer, anhydrous DDL₄After dehydration using the above, the ether was evaporated and dried to obtain 17.6 grams of 2-cyclopentadienyl 2-fluorenylpropane crude crystals.

【0058】

Then, 10 grams of the crude crystals were diluted to 100 ml of THF, cooled to -50 ° C or lower, and 46.0 ml (0.0736 mol) of n-butyllithium was added dropwise over 10 minutes. The mixture was returned to room temperature over 1 hour and reacted at room temperature for 2 hours. Next, the solvent was evaporated and dried under a nitrogen stream, 100 ml of dichloromethane was added, and the mixture was cooled to -50 ° C or lower. Next, a solution prepared by mixing 8.16 grams of zirconium tetrachloride with 50 ml of dichloromethane in advance at low temperature was fed at once. After mixing, the temperature was slowly raised over 3 hours, and the reaction was carried out at room temperature for a whole day and night. After completion of the reaction, the solid matter was filtered off, and the filtrate was concentrated and recrystallized to obtain 4.68 grams of red isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride. <Production of component (A)> The component (A) was produced under the same conditions as in Example 1 except that the component (i) produced above was used. <Polymerization of Propene> The polymerization operation was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. The results are shown in Table 3.

【0059】

[Comparative Example 6] The polymerization operation was carried out under the same conditions as in Comparative Example 4 except that the component (i) produced in Example 11 was used. The results are shown in Table 3.

【0060】

[Example 12] <Production of component (i)> Dimethylsilylene (tetramethylcyclopentadienyl) tert-butylaminotitanium dichloride was synthesized according to Example 2 of JP-A-3-163088. <Production of component (A)> The component (A) was produced under the same conditions as in Example 1 except that the component (i) produced above was used. <Polymerization of Propene> The polymerization operation was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. The results are shown in Table 3.

【0061】

[Comparative Example 7] The polymerization operation was carried out under the same conditions as in Comparative Example 4 except that the component (i) produced in Example 12 was used. The results are shown in Table 3.

【0062】

[Example 13] <Ethylene polymerization> In an autoclave made of stainless steel with an internal volume of 1.0 liter equipped with a stirrer and temperature control device, 400 ml of fully dehydrated and deoxidized toluene and 0.06 g of Schelling's methylarmoxane as component (B) ( After introducing 2 ml (2 μM in terms of component (i)) of the component (A) obtained in 1 mM) and Example 1 and 50 ml of hydrogen, ethylene pressure = 5 kg / cm.²The polymerization operation was carried out at G and a polymerization temperature of 70 ° C. for 1 hour. After completion of the polymerization, the polymer slurry was extracted into 1 liter of ethanol, the polymer was filtered off and dried, and as a result, 45 grams of the polymer was recovered. The activity per component (i) was 52,000 (gram polyethylene / gram component (i)) and 750 grams polyethylene / gram MAO per methylarmoxane). The MI (2.16 kg load) was 1.5 at 190 ° C.

【0063】

[Comparative Example 8] Instead of using the component (A) of Example 1, all examples except that 0.86 mg (2 μM) of ethylene bis [4,5,6,7-tetrahydroindenyl] zircounimdimethyl was used. Polymerization was carried out under the same conditions as in 12. As a result, 21 grams of polymer was recovered. The activity was 24,400 (gram polyethylene / gram component (i)) and 350 per methylarmoxane (gram polyethylene / gram MAO). The MI was 1.4.

【0064】

[Example 14] <Propene / Hexene Copolymerization> Toluene 400 ml, 1-Hexene 10 ml, fully dehydrated and deoxidized in a stainless steel autoclave with an internal volume of 1.0 liter equipped with a stirring and temperature control device, components obtained in Example 1. 2 ml (2 μM) of (A) and 0.06 g (1 μM) of Schelling methylarmoxane were introduced, and propylene pressure = 5 kg / cm.²The polymerization operation was carried out for 2 hours at G and the polymerization temperature = 40 ° C. After completion of the polymerization, the polymerization solution was extracted into 3 liters of methanol, the polymer was filtered off and dried, and 52.3 grams of the polymer was recovered. As a result of gel permeation chromatography measurement, this one has a number average molecular weight (Mn) of 2.45 × 10.³The molecular weight distribution was 1.91 in terms of weight average molecular weight / number average molecular weight. The triad [mm] fraction was 0.918 and the hexene content was 3.8 mol%.

【0065】

[Comparative Example 9] Polymerization under the same conditions as in Example 13 except that 0.86 mg (2 μM) of ethylenebis [4,5,6,7-tetrahydroindenyl] zircounimdimethyl was used instead of the component (A). The operation was performed. As a result, 17.8 grams of polymer was recovered. Number average molecular weight (Mn) 2.33 × 10³The molecular weight distribution was Mw / Mn = 1.93, the triad [mm] fraction was 0.920, and the hexene content was 3.9 mol%.

【0066】

[table 1]

<img file="JPH06100613A_D0003.tif" />【0067】

(B) Ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl [0068]

[Table 2]

<img file="JPH06100613A_D0004.tif" />【0069】

[Table 3]

<img file="JPH06100613A_D0005.tif" />【0070】

(B) Dimethylcilylene (4,5,6,7-tetrahydroindenyl) zirconium dichloride (C) Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride (D) Dimethylcilylene (tetramethylcyclopentadienyl) tert-butylaminotitanium dichloride [0071]

[Effect of the invention]

According to the present invention, the amount of almoxane used can be significantly reduced, as described above in the section of "Overview of the Invention".