Elastomeric terpolymer containing diene monomer and production method therefor

The present invention relates to a ternary elastic copolymer which is a copolymer of ethylene, alpha olefin and diene, and a method for producing the same. More specifically, the present invention relates to a ternary elastic copolymer having a long-chain branch capable of simultaneously satisfying processability and elasticity (flexibility), and a method for producing the same.

EPDM rubber, which is a ternary elastic copolymer of alpha olefins such as ethylene and propylene and diene such as ethylidene norbornene, has a molecular structure without unsaturated bonds in the main chain, and has weather resistance, chemical resistance and heat resistance. It has properties superior to those of general conjugated diene rubber. Due to these characteristics, the ternary elastic copolymer such as EPDM rubber can be used for various automobile parts materials, electric wire materials, construction and various hoses, gaskets, belts, bumpers, industrial materials such as blends with plastics, etc. Widely used in.

For a long time, such ternary elastic copolymers such as EPDM rubber have been produced by copolymerizing three kinds of monomers mainly using a catalyst containing a vanadium compound, for example, a vanadium-based Ziegler-Natta catalyst. I came. However, since such a vanadium-based catalyst exhibits low catalytic activity, it is necessary to use an excessive amount of catalyst, which has a disadvantage that the residual metal content in the copolymer is increased. As a result, it is necessary to remove the catalyst and decolorize the copolymer after production, which may cause problems such as deterioration of heat resistance due to the residue of the catalyst in the resin, generation of foreign matter, and inhibition of the vulcanization reaction. In addition, the production of a ternary elastic copolymer using a catalyst containing the vanadium compound exhibits low polymerization activity and low-temperature polymerization conditions, so that it is not easy to control the reaction temperature, and the amount of comonomeric inhalation such as propylene and diene can be adjusted. It is a fact that it was not easy to control the molecular structure of the copolymer. Therefore, when a vanadium-based catalyst is used, there is a limit to the production of a ternary elastic copolymer having various physical characteristics. Due to these problems, a method for producing a ternary elastic copolymer such as EPDM rubber using a metallocene-series Group 4 transition metal catalyst instead of a vanadium-based Ziegler-Natta catalyst has recently been developed.

Such a Group 4 transition metal catalyst exhibits high polymerization activity in olefin polymerization, and not only enables the production of a copolymer having a higher molecular weight, but also makes it easy to adjust the molecular weight distribution and composition of the copolymer. .. In addition, there is an advantage that various co-polymers can be copolymerized. For example, US Pat. No. 5,229,478, US Pat. No. 6,545,088 and Korean Registered Patent No. 0488833 use various metallocene-based Group 4 transition metal catalysts obtained from ligands such as cyclopentadienyl, indenyl or fluorenyl. It is disclosed that a ternary elastic copolymer having a large molecular weight can be obtained with excellent polymerization activity.

However, when copolymerizing three types of monomers using such a conventional Group 4 transition metal catalyst, each monomer is contained in the copolymer chain due to its high reactivity with the comonomer of alpha olefin. There was a disadvantage that the distribution of repeating units derived from was not uniform. As a result, it was difficult to obtain a ternary elastic copolymer such as EPDM rubber having excellent elasticity and flexibility.

In addition, US Pat. No. 5,902,867 and the like disclose a method of widening the molecular weight distribution and lowering the viscosity of the polymer in order to improve the kneading workability and extrusion workability of EPDM. In this case, it is included in the crosslinked rubber product. There is a limit that the polymer is separated during processing by the low molecular weight component and the surface characteristics and low temperature characteristics are deteriorated.

Therefore, there is a continuous demand for the development of a ternary elastic copolymer capable of simultaneously satisfying excellent processability, mechanical properties and elasticity (flexibility), and a manufacturing method capable of producing the ternary elastic copolymer with high productivity and yield. There is.

<p num="0008"><patcit num="1"><text>US Registered Patent No. 5,229,478</text></patcit><patcit num="2"><text>US Registered Patent No. 6,545,088</text></patcit><patcit num="3"><text>Korean Registered Patent No. 0488833</text></patcit><patcit num="4"><text>US Registered Patent No. 5,902,867</text></patcit></p>

<p num="0009"> Therefore, the present invention provides a ternary elastic copolymer having a long-chain branch capable of simultaneously satisfying excellent processability and elasticity (flexibility).</p><p num="0010"> The present invention also provides a method for producing a ternary elastic copolymer capable of producing the ternary elastic copolymer having the long-chain branch with high productivity.</p>

<p num="0011"> The present invention provides a copolymer of 40-70% by weight ethylene, 15-55% by weight alpha olefin with 3-20% carbon atoms and 0.5-20% by weight diene obtained in the presence of a Group 4 transition metal catalyst. It s a coalescence, i) The weight average molecular weight measured by GPC is 100,000 to 500,000. ii) Δtanδ, which is the difference between the tanδ value at an angular frequency of 0.2 rad / s and the tanδ value at an angular frequency of 100.0 rad / s measured with a Rubber Process Analyzer at 100 ° C, is Provided is a ternary elastic copolymer having a value of 0.5 or less.</p><p num="0012"> The present invention also comprises 40-70% by weight ethylene, 20-70% by weight in the presence of a catalytic composition comprising a first transition metal compound represented by the following Chemical Formula 1 and a second transition metal compound represented by the following Chemical Formula 2. The ternary elastic co-weight including the step of copolymerizing while continuously supplying a monomer composition containing 50% by weight of alpha olefin having 3 to 20 carbon atoms and 2 to 20% by weight of diene to the reactor. Providing a method of manufacturing coalescence:</p><p num="0013"><chemistry num="1"><img id="000002" he="115" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0014"> In the chemical formulas 1 and 2, R₁To R₁₃Are the same or different from each other, and independently hydrogen; alkyl radicals with 1 to 20 carbon atoms; alkenyl radicals with 2 to 20 carbon atoms; aryl radicals with 6 to 20 carbon atoms; silyl radicals; Alkylaryl radicals; arylalkyl radicals with 7 to 20 carbon atoms; or metalloid radicals of Group 4 metals substituted with hydrocarbyl; said R₁To R₁₃Two adjacent and different groups of them can be linked to each other by an alkyl radical having 1 to 20 carbon atoms or an alkylidine radical containing an aryl radical having 6 to 20 carbon atoms to form an aliphatic ring or an aromatic ring. ; M is a Group 4 transition metal; Q₁And Q₂Are the same or different from each other, and independently halogen radicals; alkyl radicals with 1 to 20 carbon atoms; alkenyl radicals with 2 to 20 carbon atoms; aryl radicals with 6 to 20 carbon atoms; alkylaryls with 7 to 20 carbon atoms. Radicals; arylalkyl radicals with 7 to 20 carbon atoms; alkylamide radicals with 1 to 20 carbon atoms; arylamide radicals with 6 to 20 carbon atoms; or alkylidene radicals with 1 to 20 carbon atoms.</p><p num="0015"> Hereinafter, a ternary elastic copolymer according to a specific embodiment of the invention and a method for producing the same will be described in detail.</p><p num="0016"> First, the term "ternary elastic copolymer" used herein can be defined as follows, unless otherwise specified. The "ternary elastic copolymer" is an arbitrary elastic copolymer obtained by copolymerizing ethylene, an alpha olefin having 3 to 20 carbon atoms, and three types of diene monomers (for example, a crosslinkable random). Copolymer) can be referred to. A typical example of such a "ternary elastic copolymer" is EPDM rubber, which is a copolymer of ethylene, propylene and diene. However, such a "ternary elastic copolymer" does not refer only to a copolymer of three monomers, but one or more monomers belonging to the category of alpha olefin together with the above ethylene. And, of course, any elastic copolymer in which one or more monomers belonging to the category of diene are copolymerized can be included. For example, an elastic copolymer obtained by copolymerizing ethylene, two alpha olefins of propylene and 1-butene, and two dienes of etilidennorbornene and 1,4-hexadiene is also an elastic copolymer of ethylene, alpha olefin and diene. Since three types of monomers belonging to each of the above categories are copolymerized, they can belong to the above-mentioned "ternary elastic copolymer" category.</p><p num="0017"> On the other hand, according to one embodiment of the invention, 40-70% by weight ethylene, 15-55% by weight alpha olefin with 3-20 carbon atoms and 0.5-20% by weight obtained in the presence of a Group 4 transition metal catalyst. A copolymer of% by weight diene i) The weight average molecular weight measured by GPC is 100,000 to 500,000. ii) Δtanδ, which is the difference between the tanδ value at an angular frequency of 0.2 rad / s and the tanδ value at an angular frequency of 100.0 rad / s measured by a rubber processing analyzer (Rubber Process Analyzer) at 100 ° C. A ternary elastic copolymer of 0.5 or less is provided.</p><p num="0018"> The ternary elastic copolymer of such one embodiment is obtained by copolymerizing three kinds of monomers of ethylene, alpha olefin and diene within a certain content range, and when measured by GPC, it is about. It has a relatively large weight average molecular weight of 100,000 to 500,000, or about 100,000 to 400,000. Such a large weight average molecular weight is achieved due to the excellent activity of the Group 4 transition metal catalysts, for example, the first and second transition metal compounds of the chemical formulas 1 and 2 described below belonging to the metallocene series. Since the ternary elastic copolymer of one embodiment has such a large molecular weight, the ternary elastic copolymer, for example, EPDM rubber can exhibit excellent mechanical properties.</p><p num="0019"> The ternary elastic copolymer of the above embodiment has a tan δ value at an angular frequency of 0.2 rad / s and 100.0 rad / s measured by a rubber processing analyzer (Rubber Process Analyzer) at 100 ° C. It can be shown that Δtan δ, which is the difference between the tan δ values at the angular frequency of, is 0.5 or less.</p><p num="0020"> In particular, in the ternary elastic copolymer, three kinds of monomers of ethylene, alpha olefin and diene are uniformly and alternately distributed in an appropriate content range, and by containing a specific diene, a long chain branch is included. The difference between the tan δ value at an angular frequency of 0.2 rad / s and the tan δ value at an angular frequency of 100.0 rad / s can be shown to be 0.5 or less, which is accompanied by excellent mechanical properties suitable for extrusion. It is possible to satisfy more improved elasticity and flexibility at the same time.</p><p num="0021"> The ternary elastic copolymer of the above embodiment can be produced, for example, with excellent productivity and yield peculiar to a group 4 transition metal catalyst belonging to the metallocene series, and satisfies a large molecular weight and excellent mechanical properties. However, it is possible to solve the problems of EPDM rubbers conventionally produced with metallocene-based Group 4 transition metal catalysts and simultaneously satisfy excellent elasticity and flexibility.</p><p num="0022"> The ternary elastic copolymer may have a tan δ value of 0.45 to 0.8 at an angular frequency of 0.2 rad / s measured by a rubber processing analyzer (Rubber Process Analyzer) at 100 ° C. An elastic copolymer showing a low tan δ in the above range at an angular frequency of 0.2 rad / s is a polymer having a long chain branch, has excellent workability, and is suitable for extrusion molding, but on the contrary, tan δ is If it exceeds 0.8 and has a high value, it may be a polymer having a linear structure and its workability may be low.</p><p num="0023"> On the other hand, in the ternary elastic copolymer of the above embodiment, δ (delta) indicates a phase angle at a constant angular frequency, means a reaction rate to a stimulus, and Δδ (delta-delta). ) Indicates the change in the phase angle due to the change in the angular frequency. Then, the tan δ and Δ tan δ mean the tangent values of the δ and Δ δ, and when G is the loss modulus and G is the storage modulus, tan δ = G "/ G. Can be indicated by'. The tan δ of each of the above copolymers can be measured using a rubber processing analyzer (Rubber Process Analyzer) of the Monsanto RPA2000 model.</p><p num="0024"> The Δtan δ is the difference between the tan δ value at a low angular frequency and the tan δ value at a high angular frequency, and may be related to the long chain branching degree and the extrusion behavior of the elastic copolymer. More specifically, since the tan δ shows the ratio of the loss elastic modulus proportional to the viscosity and the storage elastic modulus proportional to the elasticity, the viscosity decreases and the elasticity increases as the copolymer has a lower tan δ value. Can be done. A copolymer having a high degree of long-chain branching has a low loss elastic modulus and a high storage elastic modulus, and can exhibit such a low tan δ value. Therefore, the smaller Δtanδ, which is the difference between the tanδ values during deformation, the higher the elasticity is maintained. This is because long-chain branches are present in the copolymer, and the machine has excellent workability and is suitable for extrusion molding. It means that it can show physical characteristics.</p><p num="0025"> That is, the ternary elastic copolymer is produced using a Group 4 transition metal catalyst so as to have excellent productivity, yield and mechanical characteristics, and by containing a specific diene, it has a weight average molecular weight in a certain range. Since it has a Δtan δ value and can exhibit better workability, elasticity, flexibility, etc. required for EPDM rubber, it can be very preferably used as EPDM rubber or the like.</p><p num="0026"> On the other hand, the ternary elastic copolymer of the above embodiment may have a molecular weight distribution (PDI) of 2 to 6, and more preferably a molecular weight distribution of 2 to 4. The molecular weight distribution (PDI) means the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn). If the molecular weight distribution exceeds 6, the processability is excellent, but the low molecular weight polymer is contained, so that the low molecular weight polymer may be separated at the time of processing and the surface characteristics may be deteriorated.</p><p num="0027"> The ternary elastic copolymer of the above embodiment has a density range capable of satisfying appropriate physical properties as EPDM rubber or the like, for example, about 0.840 to 0.895 g / cm.³, Or about 0.850 to 0.890 g / cm³Can have a density of.</p><p num="0028"> Further, the ternary elastic copolymer of the above embodiment has a Mooney viscosity (1 + 4 @ 125 ° C) range that can satisfy appropriate physical properties as EPDM rubber or the like, for example, about 1 to 180, or about. It can have a Mooney viscosity of 5 to 150, or about 20 to 130.</p><p num="0029"> Further, in the ternary elastic copolymer of the above embodiment, as the alpha olefin, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1- Hexene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 9-methyl-1-decene, One or more alpha olefins having 3 to 20 carbon atoms such as 11-methyl-1-dodecene and 12-ethyl-1-tetradecene can be used, and among these, alpha olefins having 3 to 10 carbon atoms are typical. Propylene, 1-butene, 1-hexene or 1-octene can be appropriately used as examples.</p><p num="0030"> Further, as the diene, a non-conjugated diene-based monomer can be used. As a concrete example,<u style="single">1,4-Hexadiene</u>, 1,5-Heptadien, 1,6-octadien, 1,7-Nonadiene, 1,8-Decadien, 1,12-Tetradecadien, 3-Methyl-1,4,-Hexadien, 4-Methyl-1, 4-Hexadien, 5-Methyl-1,4-Hexadien, 4-Ethyl-1,4-Hexadien, 3,3-Dimethyl-1,4-Hexadien, 5-Methyl-1,4-Heptadien, 5-Ethyl- 1,4-Heptadien, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadien, 5-methyl- 1,4-octadien, 4-ethyl-1,4-octadien, 5-ethyl-1,4-octadien, 5-methyl-1,5-octadien, 6-methyl-1,5,-octadien, 5-ethyl -1,5-octadien, 6-ethyl-1,5-octadien, 6-methyl-1,6-octadien, 7-methyl-1,6-octadien, 6-ethyl-1,6-octadien, 6-propyl -1,6-octadien, 6-butyl-1,6-octadien, 7-methyl-1,6-octadien, 4-methyl-1,4-nonadien, etiliden-2-norbornene, 5-methylene-2-norbornene , 5- (2-propenyl) -2-norbornen, 5- (3-butenyl) -2-norbornen, 5- (1-methyl-2-propenyl) -2-norbornen, 5- (4-pentenyl) -2 -Norbornen, 5- (1-methyl-3-butenyl) -2-norbornen, 5- (5-hexenyl) -2-norbornen, 5- (1-methyl-4-pentenyl) -2-norbornen, 5-( 2,3-Dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl- Hexenil) -2-norbornen, 5- (3,4-Dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6- Heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3- Trimethyl-4-pentenyl) -2-norbornene, 5-propyriden-2-norbornene, 5-isopropylidene-2-norbornene, 5-butylidene-2-norbornene, 5-isobutylidene-2-norbornene, 2,3-diisopropi LIDEN-5-norbornene, 2-ethylidene-3-isopropyridene-5-norbornene, or 2-propenyl-2,2-norbornene can be mentioned, and one or more of the selected diene can be used. it can.</p><p num="0031"> Among these diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, or<u style="single">1,4-Hexadiene</u>Can be appropriately used to produce a ternary elastic copolymer that satisfies the weight average molecular weight and Δtan δ of the above embodiment. On the other hand, 5-vinyl-2-norbornene (VNB) or dicyclopentadiene (DCPD), which has been used as the diene in the production of the conventional ternary elastic copolymer, contains two double bonds and the above two. Since the double bond participates in the polymerization reaction and exhibits a crosslinked polymer structure, there is a limit that gel particles are formed in the polymerization process and it is difficult to control the molecular weight of the copolymer and the polymerization reaction.</p><p num="0032"> On the other hand, according to another embodiment of the invention, there is provided a method for producing a ternary elastic copolymer according to the above-mentioned embodiment. The method for producing such a copolymer is 40 to 70% by weight in the presence of a catalyst composition containing the first transition metal compound represented by the following chemical formula 1 and the second transition metal compound represented by the following chemical formula 2. It may include a step of copolymerizing a monomer composition containing ethylene, 20 to 50% by weight of alpha olefin having 3 to 20% of carbon atoms and 2 to 20% by weight of diene while continuously supplying the reactor. it can:</p><p num="0033"><chemistry num="2"><img id="000003" he="113" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0034"> In the chemical formulas 1 and 2, R₁To R₁₃Are the same or different from each other, and independently hydrogen; alkyl radicals with 1 to 20 carbon atoms; alkenyl radicals with 2 to 20 carbon atoms; aryl radicals with 6 to 20 carbon atoms; silyl radicals; Alkylaryl radicals; arylalkyl radicals with 7 to 20 carbon atoms; or metalloid radicals of Group 4 metals substituted with hydrocarbyl; said R₁To R₁₃Two adjacent and different groups of them can be linked to each other by an alkyl radical having 1 to 20 carbon atoms or an alkylidine radical containing an aryl radical having 6 to 20 carbon atoms to form an aliphatic ring or an aromatic ring. ; M is a Group 4 transition metal; Q₁And Q₂Are the same or different from each other, and independently halogen radicals; alkyl radicals with 1 to 20 carbon atoms; alkenyl radicals with 2 to 20 carbon atoms; aryl radicals with 6 to 20 carbon atoms; alkylaryls with 7 to 20 carbon atoms. Radicals; arylalkyl radicals with 7 to 20 carbon atoms; alkylamide radicals with 1 to 20 carbon atoms; arylamide radicals with 6 to 20 carbon atoms; or alkylidene radicals with 1 to 20 carbon atoms.</p><p num="0035"> As is also confirmed through the following examples and the like, a certain content of the monomer, that is, about 40 to 70% by weight, or about 50 to 70% by weight of ethylene, about 15 to 55% by weight, or about 25% by weight. While using up to 45% by weight of alpha olefins having 3 to 20 carbon atoms and about 0.5 to 20% by weight, or about 2 to 10% by weight of diene, each such monomer is used in the above chemical formulas 1 and 2-2. By producing in the continuous polymerization step in the presence of a specific transition metal catalyst of the species, the above-mentioned large molecular weight range and the difference between the tan δ values at the angular frequencies of 0.2 rad / s and 100.0 rad / s satisfy 0.5 or less. It was confirmed that the ternary elastic copolymer of one embodiment can be obtained with high yield and productivity.</p><p num="0036"> This can be mainly due to the excellent catalytic activity and co-monomeric reactivity of the two specific catalysts. The specific catalysts of the first and second transition metal compounds show excellent catalytic activity as group 4 transition metal catalysts, and in particular, excellent selectivity and copolymerization reactivity with respect to co-monometries such as alpha olefin and diene. Can be shown. Furthermore, by using these two types of specific catalysts, it is possible to carry out copolymerization while uniformly distributing the diene in the polymer chain at a relatively high content. This is because the specific catalysts of the chemical formulas 1 and 2 are maintained very stably by the quinoline-based amide group in the pentagonal and hexagonal ring compositions in which the metal element is firmly around the position, whereby the structural monomer is structurally. This is because it has structural properties that make it easy to approach. That is, the specific catalysts of the chemical formulas 1 and 2 can form a macroma having a long-chain branched double bond during the copolymerization of ethylene and alpha olefin based on the structural properties of the catalyst described above. , It can be copolymerized again by the reaction with the catalyst to form a ternary elastic copolymer having a long chain branch.</p><p num="0037"> Further, while using two kinds of specific catalysts such as the first and second transition metal compounds, the copolymerization is carried out while continuously supplying the monomer composition containing each monomer to the polymerization reactor. By performing in a continuous step, the copolymer, particularly the diene, is more uniformly distributed in the polymer chain.</p><p num="0038"> As a result, although the molecular weight is high, each monomer is uniformly and alternately distributed, and a ternary elastic copolymer having a high degree of long-chain branching can be produced with high productivity and yield. The ternary elastic copolymer thus obtained is shown to have excellent mechanical properties due to its molecular weight and a low difference in tan δ value at a specific angular frequency, which results in excellent workability and flexibility. You can satisfy both sexes at the same time.</p><p num="0039"> In addition, the content of each monomer is about 40-70% by weight or about 50-70% by weight of ethylene, about 15-55% by weight of alphaolefin, or about 25-45% by weight and about 0.5-0.5% of diene. By adjusting to an optimized range of 20% by weight, or about 2 to 10% by weight, the distribution of each monomer in the polymer chain is more evenly alternated, which is a characteristic of the embodiment. Enables the effective production of ternary elastic copolymers that satisfy the above requirements.</p><p num="0040"> Therefore, according to the production method of another embodiment, the ternary elastic copolymer of the above-mentioned one embodiment can be produced with high productivity and high yield, and such a ternary elastic copolymer is an excellent machine. It can be very preferably used as EPDM rubber or the like produced by a group 4 transition metal catalyst that simultaneously satisfies physical characteristics and improved elasticity.</p><p num="0041"> However, when the above-mentioned two specific catalysts are not used, only one of these catalysts is used, or when the content range of each of the above-mentioned monomers, especially the content range of diene, is deviated. In some cases, the finally produced ternary elastic copolymer may not satisfy the high molecular weight range of one embodiment, the range of the Δtan δ value at a specific angular frequency, and the like.</p><p num="0042"> On the other hand, in the method for producing a ternary elastic copolymer of the other embodiment described above, more specific explanations for the first and second transition metal compounds represented by the chemical formulas 1 and 2 are as follows.</p><p num="0043"> First, in the chemical formulas 1 and 2, hydrocarbyl should be pointed out as a monovalent acting group in which a hydrogen atom is removed from a hydrocarboxylic group, and for example, an alkyl group such as ethyl and an aryl group such as phenyl should be comprehensively pointed out. Can be done.</p><p num="0044"> Further, in the chemical formulas 1 and 2, the metalloid is a metalloid and is an element exhibiting intermediate properties between a metal and a non-metal, and for example, arsenic, boron, silicon or tellurium can be designated. Then, the M can refer to a Group 4 transition metal element such as titanium, zirconium or hafnium.</p><p num="0045"> Among these first and second transition metal compounds, as the first transition metal compound of the chemical formula 1, one or more compounds selected from the group consisting of the compounds of the following formulas can be appropriately used:</p><p num="0046"><chemistry num="3"><img id="000004" he="184" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0047"> In the above formula, R₂And R₃Are the same or different from each other, they are independent hydrogen or methyl radicals, M is a Group 4 transition metal, and Q₁And Q₂Are the same or different from each other and are independently methyl radicals, dimethylimide radicals or chlorine radicals, respectively.</p><p num="0048"> Further, as the second transition metal compound of the remaining chemical formula 2, one or more compounds selected from the group consisting of the compounds of the following formulas can be appropriately used:</p><p num="0049"><chemistry num="4"><img id="000005" he="174" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0050"> In the above formula, R₂And R₃Are the same or different from each other, they are independent hydrogen or methyl radicals, M is a Group 4 transition metal, and Q₁And Q₂Are the same or different from each other and are independently methyl radicals, dimethylimide radicals or chlorine radicals, respectively.</p><p num="0051"> On the other hand, the catalyst composition used in the production method of the other embodiment is one or more selected from the group consisting of the following chemical formulas 3, 4 and 5 in addition to the above-mentioned first and second transition metal compounds. Co-catalyst compounds can be further included:</p><p num="0052"><chemistry num="5"><img id="000006" he="12" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0053"> With the above chemical formula 3, R are identical or different from each other and are independent halogens; hydrocarbons with 1 to 20 carbon atoms; or hydrocarbons substituted with halogens with 1 to 20 carbon atoms; n is an integer greater than or equal to 2;</p><p num="0054"><chemistry num="6"><img id="000007" he="12" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0055"> In formula 4, R is as defined in formula 3; D is aluminum or boron;</p><p num="0056"><chemistry num="7"><img id="000008" he="12" wi="160" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0057"> In the chemical formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is the same or different from each other, and each independently has one or more hydrogens. A valence halogen, a hydrocarbon having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with alkoxy or phenoxy.</p><p num="0058"> Examples of such a co-catalyst compound represented by the chemical formula 3 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.</p><p num="0059"> Examples of the compounds represented by the chemical formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, and tricyclopentylaluminum. Tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-trilaluminum, dimethylaluminummethoxydo, dimethylaluminumethoxydo, trimethylboron, triethyl Examples thereof include boron, triisobutylboron, tripropylboron and tributylboron, and among these, trimethylaluminum, triethylaluminum and triisobutylaluminum can be appropriately used.</p><p num="0060"> The compound represented by the chemical formula 5 contains a non-coordinating anion compatible with a cation which is a Bronsted acid. Suitable anions are those containing monocoordinating complex compounds that are relatively large in size and contain metalloids. In particular, compounds containing a single boron atom in the anion moiety are widely used. From this point of view, as the compound represented by the chemical formula 5, a salt containing an anion containing a coordination-bonding complex compound containing a single boron atom can be appropriately used.</p><p num="0061"> Specific examples of such compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and tripropylammonium tetrakis (pentafluorophenyl) borate in the case of trialkylammonium salts. , Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N- Dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2, 3,5,6-Tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium penta Fluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium Tetrax (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) ) Borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N , N-Dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-Tetrafluorophenyl) borate, decyldimethylammonium tetrakis (pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluoro) Phenyl) borate, octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldidecylammonium tetrakis (pentafluorophenyl) borate, methyldidodecylammonium tetrakis (pentafluorophenyl) borate , Methylditetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, methyldiacosyl ammonium tetrakis (pentafluorophenyl) Borate, tridecylammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, tritetradecylammonium tetrakis (pentafluorophenyl) borate, trihexadecylammonium tetrakis (pentafluorophenyl) borate, trioctadecyl Ammonium tetrakis (pentafluorophenyl) borate, trieicosyl ammonium tetrakis (pentafluorophenyl) borate, decyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, dodecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate , Octadecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N,Examples include N-didodecylanilinium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate.</p><p num="0062"> In the case of dialkylammonium salts, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) borate can be mentioned as examples.</p><p num="0063"> In the case of carbonium salt, tropyrium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) borate and the like can be mentioned as examples.</p><p num="0064"> On the other hand, in the above-mentioned method for producing a ternary elastic copolymer, the catalyst composition containing the above-mentioned first and second transition metal compounds and selectively co-catalyst compounds is, for example, the above-mentioned first and second transitions. It can be produced by a method including a step of contacting the metal compound with the co-catalyst compound of Chemical Formula 3 or 4 to obtain a mixture; and a step of adding the co-catalyst compound of Chemical Formula 5 to the mixture.</p><p num="0065"> Further, in the catalyst composition, the molar ratio of the first transition metal compound: the second transition metal compound can be about 10: 1 to 1:10, and the total transition of the first and second transition metal compounds combined. The molar ratio of the metal compound: the co-catalyst compound of Chemical Formula 3 or 4 can be from about 1: 5 to 1: 500, and the molar ratio of the overall transition metal compound: the co-catalyst compound of Chemical Formula 5 is about 1: 1. It can be from 1:10.</p><p num="0066"> Then, in the method for producing a ternary elastic copolymer, the catalyst composition can additionally contain a reaction solvent, and the reaction solvent is a hydrocarbon solvent such as pentane, hexane or heptane; Examples include, but are not limited to, aromatic solvents such as benzene or toluene.</p><p num="0067"> Further, as already described above, the alpha olefins contained in the monomer composition include propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene and 1-. Hexene, 1-hexene, 1-decene, 1-undecene, 1-dodecene and the like can be used, and a non-conjugated diene-based monomer can be used as the diene. Among these, monomers usually used in the production of EPDM rubber, for example, propylene as the alpha olefin and 5-ethylidene-2-norbornene, 5-methylene-2-norbornene as the diene, or<u style="single">1,4-Hexadiene</u>Non-conjugated diene-based monomers such as, can be appropriately used.</p><p num="0068"> Then, in the above-mentioned method for producing a copolymer of another embodiment, the copolymerization step can be carried out at a temperature of about 100 to 170 ° C, or a temperature of about 100 to 160 ° C. If the copolymerization temperature is too low, it may be difficult to synthesize a ternary elastic copolymer in which the three types of monomers are uniformly alternately distributed, and if the polymerization reaction temperature is too high, the monomer or the product is produced. The copolymer may be thermally decomposed. Further, such copolymerization can be carried out by solution polymerization, particularly by a continuous solution polymerization method. At this time, the above-mentioned catalyst composition can be used in the form of a homogeneous catalyst dissolved in such a solution.</p><p num="0069"> In order to proceed with such continuous solution polymerization, the above-mentioned monomer composition, the first and second transition metal compounds, and the catalyst composition containing selectively the co-catalyst compound are continuously put into a reactor in a solution state. The copolymerization step can be carried out while being supplied in a positive manner, and the copolymerization step can be continuously carried out while the copolymerized ternary elastic copolymer is continuously discharged from the reactor.</p><p num="0070"> By the progress of such continuous solution polymerization, a ternary elastic copolymer satisfying the characteristics of the above embodiment can be obtained more effectively and with high productivity and yield.</p><p num="0071"> As described above, according to the present invention, ternary elasticity having a long chain branch by a group 4 transition metal catalyst which shows excellent processability, improved elasticity and flexibility and can be used very preferably as EPDM rubber or the like. A copolymer is produced.</p><p num="0072"> Further, according to the present invention, there is provided a method for producing a copolymer capable of producing such a ternary elastic copolymer with high productivity and high yield.</p>

<p num="0073"> The long-chain branched ternary elastic copolymer obtained by the present invention overcomes the limitations of EPDM rubber produced with previously known metallocene-based Group 4 transition metal catalysts, and has excellent elasticity and flexibility. Can be used together with other physical properties, so it can be very preferably used as EPDM rubber, etc., while taking advantage of the advantages peculiar to Group 4 transition metal catalysts.</p>

<figref num="1">It is a dynamic viscosity graph by the angular frequency of the ternary elastic copolymer produced in Example 1 and Comparative Example 1.</figref><figref num="2">It is a tan δ graph by the angular frequency of the ternary elastic copolymer produced in Example 1 and Comparative Example 1.</figref><figref num="3">It is a surface photograph of an extruded product obtained by extruding the copolymer produced in Example 1 with a Gervey die at a rotor rotation speed of 60 rpm.</figref><figref num="4">It is a surface photograph of an extruded product obtained by extrusion of the copolymer produced in Comparative Example 1 with a rotor speed of 60 rpm.</figref>

The invention will be described in more detail with reference to the following examples. However, the following examples merely exemplify the invention, and the content of the invention is not limited by the following examples.

The following examples and comparative examples are carried out using a standard Schlenk and a glove-box in a nitrogen atmosphere that blocks contact between air and moisture, and the organic solvent used in the reaction is purified by the standard method. And used. The synthesized ligand and catalyst were confirmed using a 400 MHz nuclear magnetic resonator (NMR) and an X-ray spectrometer.

&lt;Synthesis of ligands and transition metal compounds&gt; In the examples below, the first and second transition metal compounds are [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kappa-N] titanium dimethyl, respectively. ([(1,2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl) and [(2-methylindrin-7-yl) tetramethylcyclopentadienyl-eta 5, Kappa-N] Titanium Dimethyl ([(2-Methylindolin-7-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl) was used, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triisobutylaluminum were used as co-catalyst compounds. The first and second transition metal compounds are manufactured and used in the same manner as in Examples 2 and 14 of Korean Patent Registration Nos. 0,976 and 131, and the co-catalyst compound is such Korean Patent Registration No. 0,820,542. The same co-catalyst compound used in Example 9 of No. 9 was produced and used.

<p num="0078"> &lt;Examples 1 to 6&gt; Production of ternary elastic copolymer of ethylene, propylene and 5-ethylidene-2-norbornene Using a 2L pressure reactor, a ternary copolymerization reaction of ethylene, propylene and 5-ethylidene-2-norbornene was continuously carried out. Hexane as a polymerization solvent was continuously added from the lower part of the reactor at a supply rate of 6.7 kg per hour, and the polymerization solution was continuously taken out from the upper part of the reactor.</p><p num="0079"> Examples of the first and second transition metal compounds include the above-mentioned [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kappa-N] titanium dimethyl and [(2). -Methylindoline-7-yl) Tetramethylcyclopentadienyl-eta 5, kappa-N] Titaniumdimethyl was used in a dissolved state in hexane and charged into the reactor at a rate of 24 to 60 μmol per hour. As the co-catalyst compound, the above-mentioned N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used in a state of being dissolved in toluene, and was charged into the reactor at a rate of 105 to 270 μmol per hour. Further, as an additional co-catalyst compound, the above-mentioned triisobutylaluminum was used in a state of being dissolved in hexane, and charged into the reactor at a rate of 1800 to 3200 μmol per hour.</p><p num="0080"> The above-mentioned copolymerization was carried out while continuously supplying ethylene as a monomer at a rate of 890 to 900 g per hour, propylene at 450 to 550 g, and 5-ethylidene-2-norbornene at a rate of 80 to 250 g per hour. It was.</p><p num="0081"> The copolymerization temperature in the reactor was adjusted between 130 and 160 ° C while increasing the supply rate of 5-ethylidene-2-norbornene from 1 mL / min to 0.5 mL / min at around 160 ° C.</p><p num="0082"> Under the above conditions, copolymerization was carried out by continuous solution polymerization to continuously produce the ternary elastic copolymers of Examples 1 to 6 in a uniform solution state, and the ternary elastic copolymers were continuously discharged from the upper part of the reactor. After the polymerization reaction was stopped under ethanol, the polymerization solution was dried under reduced pressure in a vacuum oven at 60 ° C. to finally produce the copolymer of Examples 1 to 6.</p><p num="0083"> &lt;Comparative Examples 1 and 2&gt; Commercialized ternary elastic copolymers of ethylene, propylene and 5-ethylidene-2-norbornene DOW4570, which is a commercialized EPDM rubber produced with a metallocene catalyst, was used as the ternary elastic copolymer of Comparative Example 1, and DOW4640 was used as the ternary elastic copolymer of Comparative Example 2.</p><p num="0084"> The content of each monomer in the copolymers obtained in the above Examples and Comparative Examples, the activity of the catalyst, the weight average molecular weight and the molecular weight distribution (PDI) of the copolymers are as arranged in Table 1 below. .. At this time, the weight average molecular weight of each copolymer was measured by PL-GPC220 of Polymer Laboratory, which was equipped with three linearly mixed bed columns. The measurement was performed at a temperature of 160 ° C. using 1,2,4-trichlorobenzene as a solvent at a flow rate of 1.0 ml / min.</p><p num="0085"><tables num="1"><img id="000009" he="70" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0086"> &lt;Test Example 1&gt; Measurement of dynamic complex viscosity and tan δ Dynamic complex viscosity and tan δ were measured by ASTM D6204-01 using a Rubber Process Analyzer. Using Monsanto's RPA2000MV2000E equipped model, the measurement sample was a copolymer sample treated with an antioxidant (Irganox 1076) and made into a sheet using a press mold, which was deformed by 7% at 100 ° C. Dynamic complex viscosity and tan δ were measured in the frequency range of (strain) and 0.1-210 rad / s. The dynamic complex viscosity graphs for changes in the angular frequency of each of the copolymers of Examples and Comparative Examples are shown in FIG. Then, the tan δ values for the angular frequency changes of the copolymers of Examples and Comparative Examples are shown in Table 2 and FIG. 2 below.</p><p num="0088"> As shown in FIGS. 1 and 2, Example 1 and Comparative Example 1 have similar changes in dynamic viscosity with respect to the angular frequency, but Example 1 has angular vibration as compared with Comparative Example 1. It was confirmed that the degree of change in tan δ due to the change in the number was remarkably small. In particular, it can be confirmed that Example 1 and Comparative Example 1 show a very large difference in the tan δ value at the 0.2 rad / s angular frequency.</p><p num="0089"> Further, as shown in Table 2, not only the first embodiment but also the second to sixth embodiments show that the degree of change in tan δ due to the change in the angular frequency is significantly smaller than that in the comparative examples 1 and 2. In particular, it can be confirmed that the difference between the tan δ values at 0.2 rad / s and 104.7 rad / s is 0.5 or less, which is very small.</p><p num="0090"> As a result, from the above results, the comparative example having a high Δtan δ at 0.2 rad / s and 104.7 rad / s has a linear structure, but the copolymers of Examples 1 to 6 showing a low Δtan δ of 0.5 or less are long. It can be inferred that the EPDM structure has a chain branch.</p><p num="0091"> Further, if the group 4 transition metal catalyst and the specific polymerization system are applied to the 5-ethylidene-2-norbornene monomer, which has been shown to have low processability without forming a long-chain branch by the existing EPDM polymerization from the above-mentioned example, the long-chain It was confirmed that a ternary elastic copolymer having a branch can be produced.</p><p num="0092"> &lt;Test Example 2&gt; Garvey-Die Extrusion Experiment Extrusion workability was evaluated by the Garvey Die extrusion method according to ASTM 2230. Samples for the Gervey die extrusion test were prepared as follows. Parel Co., Ltd. used 75 parts by weight of paraffin oil, 125 parts by weight of carbon black, 5 parts by weight of ZnO, and 1 part by weight of stearic acid with respect to 100 parts by weight of the copolymers produced in Examples 1 and 2 and Comparative Examples 1 and 2. The mixture was kneaded at a rotor rotation speed of 60 rpm for 6 minutes at 100 to 120 ° C. using 1.6 L of the Banbury mixer. Then, the kneaded compound was extruded through a Gervey die extruder at a die temperature of 105 ° C at a rotor speed of 45 or 60 rpm, and the surface and peripheral characteristics were evaluated by ASTM 2230. The results of the Garvey die test of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 3, and the surface photographs of the Gervey die extrusions of the copolymers of Examples 1 and 1 are shown in FIGS. 3 and 4.</p><p num="0093"><tables num="3"><img id="000010" he="62" wi="159" file="JP6000458B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0094"> Examples 1 and 2 and Comparative Examples 1 and 2 are samples having similar compositions and Mooney viscosities, and when a Garvey die extrusion test was performed on the samples, as shown in Table 3 above, extrusion production and Although the die expansion index is similar, it can be confirmed that the surface properties of the extruded product are remarkably superior in Examples 1 and 2 as compared with Comparative Examples 1 and 2.</p><p num="0095"> In addition, it can be confirmed from FIGS. 3 and 4 which are extruded photographs of Example 1 and Comparative Example 1 that the surface characteristics and peripheral morphology of Example 1 are shown more uniformly and smoothly as compared with Comparative Example 1. did it.</p><p num="0096"> That is, the ternary elastic copolymers of Examples 1 and 2 contain a specific diene, and by uniformly introducing a long-chain branch using a specific Group 4 transition metal catalyst used in the present invention, conventionally 5- It can be confirmed that it exhibits excellent extrusion processability and surface properties as compared with a copolymer containing vinyl-2-norbornene (VNB) or dicyclopentadiene (DCPD) as a diene.</p>