KR101660480B1 - Elastic diene terpolymer and preparation method thereof - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a ternary elastomeric copolymer capable of simultaneously satisfying excellent processability and flexibility (flexibility) and a method for producing the same. The ternary elastomeric copolymer is a copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene,
i) a weight average molecular weight as measured by GPC of from 30,000 to 100,000,
ii) The shear thinning, which is the ratio of the dynamic viscosity at an angular frequency of 1.0 rad / s to the dynamic viscosity at an angular frequency of 100.0 rad / s measured by a rubber process analyzer at 125 ° C. is 8 To 40 days.

Description

TECHNICAL FIELD [0001] The present invention relates to a ternary elastomeric copolymer including a diene, and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a three-component elastomeric copolymer which is a copolymer of ethylene, an alpha-olefin and a diene, and a process for producing the same. More specifically, the present invention relates to a ternary elastomeric copolymer capable of simultaneously satisfying excellent processability and flexibility (flexibility), and a method for producing the same.

EPDM rubbers, which are three-component elastomeric copolymers such as alpha-olefins such as ethylene and propylene and dienes such as ethylidene norbornene, have a molecular structure that does not have an unsaturated bond in the main chain, and are superior in weather resistance, chemical resistance and heat resistance to general conjugated diene rubbers And has excellent characteristics. Due to such properties, the ternary elastomeric copolymer such as EPDM rubber is widely used for various automobile parts materials, wire materials, construction and industrial materials such as various hoses, gaskets, belts, blends with bumpers or plastics.

Previously, such a ternary elastomer such as EPDM rubber has been produced by copolymerizing three kinds of monomers using a catalyst containing a vanadium compound, for example, a vanadium-based Ziegler-Natta catalyst. However, such a vanadium-based catalyst is disadvantageous in that it requires the use of an excess amount of catalyst with a low catalytic activity, thereby increasing the residual metal content in the copolymer. Accordingly, catalyst removal and decolorization processes are required after the production of the copolymer, and deterioration of heat resistance, generation of foreign matter, or inhibition of the vulcanization reaction may be caused by residual catalyst components in the resin. In addition, the production of a ternary elastomeric copolymer using the vanadium compound-containing catalyst is not easy to control the reaction temperature due to low polymerization activity and low-temperature polymerization conditions, and it is difficult to control the amount of comonomers to be inhaled such as propylene and diene, It is true that it was difficult to control the molecular structure. Therefore, when a vanadium-based catalyst is used, the production of a three-component elastomer having various physical properties has been limited. Due to these problems, recently, a method of producing a ternary elastomeric copolymer such as an EPDM rubber by using a metallocene type transition metal catalyst of the metallocene type instead of a vanadium-based Ziegler-Natta catalyst has been developed.

Such a four-group transition metal catalyst exhibits a high polymerization activity in the olefin polymerization and not only makes it possible to produce a copolymer having a higher molecular weight, but also easily controls the molecular weight distribution and composition of the copolymer. In addition, there is an advantage that copolymerization of various comonomers is possible. For example, U.S. Patent No. 5,229,478, U.S. Patent No. 6,545,088, and Korean Patent No. 0488833 disclose various metallocene group 4 transition metal catalysts obtained from ligands such as cyclopentadienyl, indenyl or fluorenyl, , It is disclosed that a ternary elastomer having a large molecular weight can be obtained with excellent polymerization activity.

However, when three kinds of monomers are copolymerized using such a conventional four-group transition metal catalyst, the distribution of repeating units derived from each monomer in the copolymer chain becomes uneven due to the high reactivity of alpha-olefins to comonomers and the like Disadvantages have occurred. As a result, it has been difficult to obtain a ternary elastomeric copolymer such as an EPDM rubber having excellent elasticity and flexibility.

In addition, when such an EPDM rubber is applied to various materials described above, it is generally used in the form of crosslinking using sulfur or peroxide. In order to perform crosslinking, a variety of compounding agents are added and mixed with EPDM as a raw material resin in accordance with the purpose. As a blending agent, sulfur or peroxide, which is a crosslinking agent, can be used. Aromatic, naphthenic or paraffinic oil may be used, or carbon black for improving physical properties may be used. In addition, accelerators such as Thiazoles and sulfenamideds for shortening the crosslinking reaction time and activators such as ZnO and stearic acid for maximizing the effect of the crosslinking accelerator by lowering the activation energy can be used. In addition, antioxidants and ozone stabilizers You can mix them together.

The process of mixing the raw EPDM with various compounding agents and forming the final product through a process such as grinding, extrusion or injection is referred to as processing. The raw rubber and the compounding agent are mixed well, and the extrusion characteristics It is said that EPDM having a small molecular weight exhibits better properties than EPDM having a high molecular weight in mixing and extrusion characteristics with a compounding agent.

Therefore, it is continuously required to develop a ternary elastomeric copolymer showing excellent processability and elasticity (flexibility) and a manufacturing method capable of producing the same with high productivity and yield.

U.S. Patent No. 5,229,478 U.S. Patent No. 6,545,088 Korean Patent No. 0488833

Accordingly, the present invention is to provide a ternary elastomeric copolymer capable of simultaneously satisfying excellent processability and flexibility (flexibility).

The present invention also provides a process for producing a ternary elastomeric copolymer capable of producing the ternary elastomeric copolymer with high productivity.

The present invention relates to a copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene,

i) a weight average molecular weight as measured by GPC of from 30,000 to 100,000,

ii) The shear thinning, which is the ratio of the dynamic viscosity at an angular frequency of 1.0 rad / s to the dynamic viscosity at an angular frequency of 100.0 rad / s measured by a rubber process analyzer at 125 ° C. is 8 To 40. < / RTI >

The present invention also provides a catalyst composition comprising 40 to 70% by weight of ethylene, 15 to 55% by weight of ethylene, Of an alpha-olefin having 3 to 20 carbon atoms and 0.5 to 20% by weight of a diene are fed continuously to a reactor.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R ₁ to R ₁₃ may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; Two adjacent two of R ₁ to R ₁₃ may be linked to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or 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;

Q ₁ and Q _{2, which} may be the same or different, are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

Hereinafter, the ternary elastomeric copolymer according to a specific embodiment of the present invention and a method for producing the same will be described in detail.

First, the term "ternary elastomeric copolymer" used in the present specification can be defined as follows unless otherwise specified. The "ternary elastomeric copolymer" may refer to any elastic copolymer (for example, a crosslinkable random copolymer) in which three kinds of monomers such as ethylene, an alpha olefin having 3 to 20 carbon atoms, and a diene are copolymerized have. Representative examples of such "ternary elastomeric copolymer" include EPDM rubber which is a copolymer of ethylene, propylene and a diene. However, it should be noted that such a " ternary elastomeric copolymer "does not refer to only a copolymer of three monomers, and one or more monomers belonging to the category of alpha olefins and one or more monomers belonging to the category of dienes, It is to be understood that the present invention can include any elastic copolymer. For example, an elastic copolymer obtained by copolymerizing ethylene with two types of alpha-olefins of propylene and 1-butene, and two dienes such as ethylidene norbornene and 1,4-hexadiene is also an ethylene- , And three kinds of monomers respectively belonging to the category of dienes are copolymerized, and thus can be classified into the above-mentioned "ternary elastomeric copolymer ".

On the other hand, according to one embodiment of the present invention, as a copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene,

i) a weight average molecular weight as measured by GPC of from 30,000 to 100,000,

ii) The shear thinning, which is the ratio of the dynamic viscosity at an angular frequency of 1.0 rad / s to the dynamic viscosity at an angular frequency of 100.0 rad / s measured by a rubber process analyzer at 125 ° C. is 8 Lt; / RTI > to 40. < RTI ID = 0.0 >

The ternary elastomeric copolymer of this embodiment is obtained by copolymerizing three kinds of monomers such as ethylene, alpha olefin, and diene in a predetermined content range, and has a molecular weight of about 30,000 to 100,000, or about 35,000 to 95,000, Lt; RTI ID = 0.0 > 95,000. ≪ / RTI > These small weight average molecular weights are achieved due to the excellent activity and the high reaction temperature of the first and second transition metal compounds of the formulas (1) and (2) described later belonging to the group 4 transition metal catalyst, for example, the metallocene series As the ternary elastomeric copolymer of one embodiment has such a small molecular weight, the ternary elastomeric copolymer, for example, EPDM rubber, can exhibit excellent processability.

In addition, the ternary elastomeric copolymer of the embodiment has a dynamic viscosity at an angular frequency of 1.0 rad / s to the dynamic viscosity at an angular frequency of 100.0 rad / s measured at 125 ° C by a rubber process analyzer Shear thinning can have a value of from 8 to 40. [

The ternary elastomeric copolymer of one embodiment satisfying this relationship has a high dynamic viscosity at a low angular velocity which is the actual state of use of the ternary elastomeric copolymer and exhibits excellent mechanical properties and exhibits a low dynamic viscosity at a high angular velocity It has excellent elasticity, flexibility and melt processability and is suitable for extrusion processing.

On the other hand, in the ternary elastomeric copolymer of one embodiment, the shear thinning, which is the ratio of the dynamic viscosity of the ternary elastomeric copolymer of one embodiment to the embodiment, can be determined by using a rubber process analyzer Can be measured. First, after polymerization and production of a ternary elastomeric copolymer, the respective copolymers were melt-kneaded at a temperature (125 DEG C) determined by an RPA2000 MV 2000E Rubber Process Analyzer (Monsanto Co., Ltd.) and an oscillation frequency of 0.1-210 rad / s The dynamic complex viscosity is measured in the range. The ratio of the dynamic viscosity at the angular velocity of 1.0 rad / s to the dynamic viscosity at the measured 100.0 rad / s angular velocity can be calculated by arithmetically calculating the shear thinning.

In this case, when the measured dynamic viscosity at an angular velocity of _100.0 rad / s is defined as? _100.0 and the dynamic viscosity at an angular velocity of _1.0 rad / s is defined as? _1.0 , the shear thinning is expressed by the following general formula Can be displayed.

[Formula 1]

Shear thinning = 侶_1.0 / 侶_100.0

In this way, the shear fluidity of the ternary elastomeric copolymer of one embodiment was calculated. As a result, the ternary elastomeric copolymer exhibited a high value of 8 to 40 as compared with the previously used EPDM rubber of the Group 4 transition metal catalyst, And exhibits excellent mechanical properties due to high dynamic viscosity at low angular speeds in practical use, and exhibits excellent melt processability since it has a low dynamic viscosity at a high angular frequency, which is a pressure injection state.

The ternary elastomeric copolymer of one embodiment may be obtained in the presence of a transition metal of Group 4 transition metal. Particularly, the ternary elastomeric copolymer having the above properties can be produced with excellent productivity and yield peculiar to a Group 4 transition metal catalyst belonging to the metallocene series, for example, while satisfying a large molecular weight and hence excellent mechanical properties , And EPDM rubber prepared by the metallocene-type transition metal catalyst of the related art can solve the problems of excellent processability, elasticity and flexibility at the same time.

Also, the copolymer of ethylene, the alpha olefins of 3 to 20 carbon atoms and the diene contains about 40 to 70 wt%, or about 45 to 65 wt% of ethylene, 15 to 55 wt%, or about 30 to 50 wt% 3 to 20 alpha olefins and 0.5 to 20 wt%, or 4 to 10 wt% of a diene. Such copolymers can be prepared by continuously feeding a monomer composition comprising 40 to 70% by weight of ethylene, 15 to 55% by weight of alpha olefins of 3 to 20 carbon atoms and 0.5 to 20% by weight of diene in the presence of the catalyst composition . In particular, as each monomer is contained in the above ratio, it can exhibit more excellent elasticity and flexibility.

In the ternary elastomeric copolymer of one embodiment, the product Re * Rc of the reactive constant, Re, indicating the distribution of ethylene in the copolymer, and the reactive constant Rc, indicating the distribution of alpha olefins in the copolymer, 1, for example, a value of about 0.50 to 0.99.

In this characteristic value, Re = k11 / k12, Rc = k22 / k21, k11 is the growth rate constant when ethylene is bonded after ethylene in the copolymer chain, k12 is the rate constant of ethylene in the copolymer chain K21 is the growth rate constant when the ethylene is bonded after the alpha olefin in the copolymer chain, k22 is the rate constant when the alpha olefin is bonded to the alpha olefin in the copolymer chain Is the growth rate constant of the reaction.

In addition, the growth rate constants k11, k12, k21 and k22 of the k11, k12, k21 and k22 can be measured by analyzing each copolymer using ¹³ C-NMR. For example, the triad sequence analysis by Randall The value of Re * Rc can be calculated from the above ¹³ C-NMR analysis results by the method of Polymer Science: Polymer Physics edition, 1973, 11, 275 to 287 and Kakugo's method [Macromolecules 1982, 15, 1150] .

When the value of Re * Rc is less than about 1, it means that the alpha-olefin is likely to be bonded to ethylene after ethylene in the chain of the copolymer, and the alpha-olefin has high possibility to be bonded with ethylene, Alpha olefins. ≪ / RTI > On the other hand, when the value of Re * Rc is about 1, it can be shown that the copolymer chain has a random polymer between the respective monomers of ethylene and alpha olefin, and the value of Re * Rc is about 1 , It can be shown that the homopolymers are bonded to each other and the copolymer chain has the form of a block copolymer.

As the ternary elastomeric copolymer of this embodiment has a value of Re * Rc of less than about 1, for example, of about 0.50 to 0.99, such a copolymer is such that each monomer is uniformly alternating, And as a result, the copolymer does not form a block, so that the crystallinity of the copolymer is lowered, so that it can exhibit more excellent elasticity and flexibility required for EPDM rubber and the like.

The tri-elastomeric copolymer of one embodiment may have a crystallization temperature of about -55 to 30 ° C, or about -50 to 15 ° C. At this time, the crystallization temperature can be measured by deriving DSC curve data and calculating the average crystallization temperature therefrom. As the copolymer has a crystallization temperature within this range, it can exhibit excellent elasticity and flexibility as EPDM rubber and the like, and further improved processability and heat resistance. If the crystallization temperature is too low, the heat resistance of the ternary elastomeric copolymer may be deteriorated. On the contrary, if the crystallization temperature becomes too high, the elasticity and the like of the ternary elastomeric copolymer may deteriorate.

The ternary elastomeric copolymer of this embodiment may have a density range of about 0.840 to 0.895 g / cm 3, or about 0.850 to 0.890 g / cm 3, for example, such that EPDM rubber or the like can satisfy appropriate physical properties .

In addition, the ternary elastomeric copolymer of one embodiment may have a Mooney viscosity (1 + 4 a) 100 ° C, for example, about 1 MU to 40 MU, or about 2 MU to 30 MU, MU, or a pattern viscosity of about 3 MU to 26 MU.
In addition, the ternary elastomeric copolymer of one embodiment may have a molecular weight distribution of 2 to 4.

In the ternary elastomeric copolymer of one embodiment, examples of the alpha olefin include propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, Heptadecene, 1-heptadecene, 1-nonadecene, 1-nonadecene, 1-undecene, 1-tridecene, 1-decene, 1-methyl-1-decene, 1-decene, 1-decene, 1-methylene-1-decene, Propylene, 1-butene, 1-hexene or 1-octene may suitably be used.

As the diene, a nonconjugated diene-based monomer may be used. Specific examples thereof include 5-1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12- Methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 3-methyl- Heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, Methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-pentadiene, 1,5-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, Hexadiene, 6-methyl-1,6-octadiene, 6-methyl-1,6-octadiene, Methylidene-2-norbornene, 5-methylene-2-norbornene, 5- (2- Propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (2,3- Pentenyl) -2-norbornene, 5- (3-methyl-hexenyl) 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) Norbornene, 5-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-butylidene- , 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. One or more dienes may be used.

Of these dienes, particularly, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, or 4-hexadiene is suitably used to give a ternary elasticity satisfying the weight average molecular weight and LCB Index of the above- Copolymers can be prepared. On the other hand, 5-vinyl-2-norbornene (VNB) or dicyclopentadiene (DCPD) used as the diene in the preparation of the conventional three-component elastomer includes two double bonds, There is a limitation in that gel particles are formed in the polymerization process, the molecular weight of the copolymer is difficult to control, and the polymerization reaction is also difficult to control since it exhibits a crosslinked polymer structure.

According to another embodiment of the present invention, there is provided a process for producing a three-component elastomeric copolymer of one embodiment described above. The process for producing such a copolymer comprises reacting 40 to 70% by weight of ethylene, 15 to 55% by weight of ethylene in the presence of a catalyst composition comprising a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula By weight of a monomer composition comprising from 3 to 20% by weight of alpha olefins and from 0.5 to 20% by weight of dienes, in continuous feed to the reactor.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R ₁ to R ₁₃ may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; Two adjacent two of R ₁ to R ₁₃ may be linked to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or 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;

Q ₁ and Q _{2, which} may be the same or different, are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

Or about 45 to 65% by weight of ethylene, about 15 to 55% by weight, or about 30 to 50% by weight, based on the total amount of monomers, i.e., about 40 to 70% By weight of an alpha olefin having from 3 to 20 carbon atoms and from about 0.5 to 20% by weight, or from about 4 to 10% by weight of a diene, in the presence of a transition metal catalyst of the above formula 1 or 2 at a high reaction temperature It was confirmed that the tri-elastomeric copolymer of one embodiment, in which the small molecular weight range and the degree of shear fluidization described above meet a specific range, can be obtained with high yield and productivity.

This can be mainly due to the excellent catalytic activity and comonomer reactivity of the two specific catalysts. The specific catalysts of the first and second transition metal compounds exhibit excellent catalytic activity as a transition metal of Group 4, and can exhibit excellent selectivity and copolymerization reactivity with respect to comonomers such as alpha olefins and dienes. Furthermore, by using these two specific catalysts, the copolymer can be distributed while uniformly distributing the dienes in the polymer chain with a relatively high content. This is because the specific catalysts of the above formulas (1) and (2) are stably maintained in a quasi-ringing and hexagonal ring structure around the metal sites by the quinoline amido group and structurally easy to access the monomers . That is, the specific catalysts of Formulas 1 and 2 may form a macromer having a double bond in the form of a long chain branch during the copolymerization of ethylene and an alpha olefin based on the structural characteristics of the catalyst, To form a ternary elastomeric copolymer having a long-chain branch.

Furthermore, by using the two kinds of specific catalysts of the first and second transition metal compounds, and continuing the copolymerization to a continuous process while continuously supplying the monomer composition containing each monomer to the polymerization reactor, the comonomer , In particular dienes, can be more evenly distributed within the polymer chain.

As a result, a ternary elastomeric copolymer having a small molecular weight and uniformly alternating distribution of each monomer can be produced with high productivity and yield. It can be seen that the crystallization temperatures of the three-component elastomer copolymers thus obtained are distributed relatively low relative to the content of ethylene due to the uniformly alternating distribution of the respective monomers.

In addition, the content of each monomer is about 40 to 70 wt%, or about 45 to 65 wt%, alpha olefin about 15 to 55 wt%, or about 30 to 50 wt% and about 0.5 to 20 wt% The distribution in the polymer chain of each monomer can be arranged more evenly alternately as the monomer is adjusted to an optimized range of about 4 to 10 weight percent and this leads to an effective production of a ternary elastomeric copolymer satisfying the characteristics of the embodiment It is possible.

Therefore, according to the production method of another embodiment, the ternary elastomeric copolymer of one embodiment described above can be produced with high productivity and yield, and the ternary elastomeric copolymer is excellent in mechanical properties, 4-group transition metal catalyst, and the like.

However, in the case where the above-mentioned two kinds of specific catalysts are not used, only one of these catalysts is used, or when the content of each of the above-mentioned monomers is out of the appropriate range, particularly the diene content range, The copolymer may not meet the small molecular weight range of one embodiment, or the shear fluidity may be low.

On the other hand, in the method for producing a ternary elastomeric copolymer of another embodiment described above, the first and second transition metal compounds represented by the general formulas (1) and (2) will be described in more detail as follows.

First, hydrocarbyl in Formulas 1 and 2 may refer to a monovalent functional group in which a hydrogen atom is removed from a hydrocarbons. For example, an alkyl group such as ethyl, an aryl group such as phenyl, can do.

In the formulas (1) and (2), the metalloid is an element which is a metalloid and shows intermediate properties between metal and nonmetal, and may be, for example, arsenic, boron, silicon or tellurium. The M may be, for example, a Group 4 transition metal element such as titanium, zirconium or hafnium.

Among these first and second transition metal compounds, at least one compound selected from the group consisting of compounds represented by the following formulas can be suitably used as the first transition metal compound represented by the general formula (1)

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.

As the second transition metal compound represented by the above formula (2), at least one compound selected from the group consisting of compounds represented by the following formulas can be suitably used:

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.

Meanwhile, the catalyst composition used in the production method of another embodiment may further include at least one cocatalyst compound selected from the group consisting of the following chemical formulas (3), (4) and (5) in addition to the first and second transition metal compounds have:

(3)

- [Al (R) -O] _n -

In Formula 3,

R may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen; n is an integer of 2 or more;

[Chemical Formula 4]

D (R) ₃

In Formula 4, R is as defined in Formula 3; D is aluminum or boron;

[Chemical Formula 5]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

In such a promoter compound, examples of the compound represented by the general formula (3) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

Examples of the compound represented by the general formula (4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- But are not limited to, cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, Trimethylboron, triethylboron, triisobutylboron, tripropylboron or tributylboron. Of these, trimethylaluminum, triethylaluminum or triisobutylaluminum can be suitably used.

The compound represented by the general formula (5) includes a non-coordinating anion which is compatible with a cation which is a Bronsted acid. Suitable anions are relatively large in size and contain a single coordination complex containing a metalloid. Particularly, compounds containing a single boron atom in the anion moiety are widely used. From this viewpoint, as the compound represented by the general formula (5), an anion-containing salt containing a coordination complex containing a single boron atom can be suitably used.

As specific examples of such compounds, there may be mentioned trialkylammonium salts such as trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate (Pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-triisopropylsilyl) -2,3,5,6-tetra Fluorophenyl) borate, N, N-dimethylanilinium N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, (2,3,4,6-tetrafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, Anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) ) Borey , Pentyldimethylammonium tetrakis (pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis Octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldecylammonium tetrakis (pentafluorophenyl) borate, methyldido (Pentafluorophenyl) borate, methyldiotetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylammonium tetrakis Pentafluorophenyl) borate, methyldiacosylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, tridecylammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, trityl tetradecylammonium tetrakis (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, trioctadecylammonium tetrakis (pentafluorophenyl) borate, trieocosyl ammonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, dodecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, octadecyldi (n-butyl) ammonium tetrakis (Pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecyl anilinium tetrakis (Pentafluorophenyl) borate, and the like.

In the case of dialkylammonium salts, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) borate and the like can be mentioned.

Examples of the carbonium salt include tropylium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate or benzene (diazonium) tetrakis (pentafluorophenyl) .

On the other hand, in the above-mentioned method for producing a ternary elastomeric copolymer, the catalyst composition comprising the above-described first and second transition metal compounds and optionally a co-catalyst compound is obtained, for example, Contacting the compound with the promoter compound of Formula 3 or Formula 4 to obtain a mixture; And adding the promoter compound of Formula 5 to the mixture.

In the catalyst composition, the molar ratio of the first transition metal compound: the second transition metal compound may be about 20: 1 to 1:20, and the total transition metal compound The molar ratio of the total transition metal compound to the promoter compound of Formula 5 may be from about 1: 1 to 1: 500, 10 < / RTI >

In addition, in the process for producing the ternary elastomeric copolymer, the catalyst composition may further comprise a reaction solvent, and examples of the reaction solvent include hydrocarbon solvents such as pentane, hexane or heptane; Aromatic solvents such as benzene or toluene, but are not limited thereto.

As already mentioned above, the alpha-olefins contained in the monomer composition include propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, -Heptene, 1-decene, 1-undecene, 1-dodecene and the like can be used. As the diene, a nonconjugated diene monomer can be used. Of these, monomers commonly used in the production of EPDM rubber, for example, propylene as the alpha olefin and 5-ethylidene-2-norbornene, 1,4-hexadiene or dicyclopentadiene as the diene Nonconjugated dienic monomer can be suitably used.

And, in the above-described method of producing a copolymer of another embodiment, the copolymerization step can be carried out at a temperature of about 100 to 200 ° C, or a temperature of about 120 to 180 ° C. When the copolymerization temperature is too low, it may be difficult to synthesize a ternary elastomeric copolymer in which three kinds of monomers are homogeneously alternately distributed. If the polymerization reaction temperature is too high, the monomer or the produced copolymer may be thermally decomposed. Such copolymerization can be carried out by solution polymerization, in particular, continuous solution polymerization. At this time, the above-described catalyst composition can be used in the form of a homogeneous catalyst dissolved in such a solution.

For the progress of such continuous solution polymerization, the copolymerization step can be carried out while continuously supplying the catalyst composition containing the above-mentioned monomer composition, the first and second transition metal compounds and optionally the cocatalyst to the reactor in a solution state continuously And the copolymerization step can be continuously carried out while continuously discharging the copolymerized ternary elastomeric copolymer from the reactor.

By the progress of such continuous solution polymerization, the three-component elastomeric copolymer having the above-mentioned characteristics can be obtained more efficiently in productivity and yield.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a ternary elastomeric copolymer that exhibits excellent processability, improved elasticity and flexibility, and the like, which can be very preferably used as an EPDM rubber or the like, is produced.

Further, according to the present invention, there is provided a process for producing a copolymer capable of producing such a ternary elastomeric copolymer with high productivity and yield.

The ternary elastomeric copolymer obtained according to the present invention can overcome the limitations of the previously known metallocene type 4 transition metal catalyst, such as EPDM rubber, and is excellent in workability and can satisfy elasticity and flexibility with other physical properties , EPDM rubber or the like, while taking advantage of the advantages inherent to the Group 4 transition metal catalyst.

The invention will be described in more detail in the following examples. It is to be understood, however, that the invention is not limited to the following examples.

< Ligand  And Transition Metal Compounds &gt;

All ligands and catalyst synthesis were carried out using standard Schlenk and Blove-box techniques under a nitrogen atmosphere to block the contact of air and moisture, and the organic reagents and solvents used in the reaction were obtained from Aldrich and Merck And purified by standard methods. The synthesized ligand and catalyst structure were confirmed using a 400 MHz nuclear magnetic resonance (NMR) and X-ray spectroscopy.

Examples of the first and second transition metal compounds in the following examples are [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kepa-N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kapa-N] titanium dimethyl and [(2-methylindolin-7-yl) tetramethylcyclopentadienyl- (2-methylindolin-7-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl was used as the cocatalyst compound and N, N-dimethylanilinium tetrakis Phenyl) borate and triisobutyl aluminum were used. The first and second transition metal compounds were prepared and used in the same manner as in Examples 2 and 14 of Korean Patent No. 0,976,131, and the co-catalyst compound was used in the same manner as in Example 9 of Korean Patent No. 0,820,542 A co-catalyst compound was prepared and used.

< Example  1 to 20> ethylene, propylene and 5- Ethylidene -2- Nobonen Triplet  Preparation of elastic copolymer

A ternary copolymerization reaction of ethylene, propylene and 5-ethylidene-2-norbornene was continuously carried out using a 2 L pressure reactor. Hexane as a polymerization solvent was continuously fed from the lower part of the reactor at a feeding rate of 5.5 to 6.5 kg per hour, and the polymerization solution was continuously withdrawn from the upper part of the reactor.

As the first and second transition metal compounds, there may be mentioned [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kepa-N] titanium dimethyl and [ 7-yl) tetramethylcyclopentadienyl-eta 5, kepa-N] titanium dimethyl was used in the state of being dissolved in hexane and charged into the reactor at a rate of 20 to 60 μmol per hour. The above-mentioned N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used as the co-catalyst compound in the state of being dissolved in toluene, and the reactor was charged at a rate of 100 to 200 μmol per hour. The above-mentioned triisobutylaluminum was used as an additional promoter compound in a state of being dissolved in hexane, and the reactor was charged at a rate of 2000 to 4000 占 퐉 ol per hour.

The copolymerization proceeded while continuously feeding the monomer as a monomer at a rate of 800 to 950 g per hour, at a rate of 900 to 1500 g of propylene and at a rate of 90 to 170 g per hour at a rate of 90 to 170 g per hour. The copolymerization temperature in the reactor was 150 to 190 ° C. The reaction conditions such as the amount of each monomer, the amount of the catalyst, and the polymerization temperature are summarized in Table 1 below.

The copolymerization was carried out by continuous solution polymerization under the above-mentioned conditions to continuously produce the ternary elastomeric copolymers of Examples 1 to 20 in a uniform solution state. The polymerization solution continuously discharged from the upper portion of the reactor was subjected to polymerization reaction under ethanol After stopping, it was finally dried in a vacuum oven at 60 DEG C under reduced pressure to prepare the copolymers of Examples 1 to 20.

< Comparative Example  1 > Commercialized ethylene, propylene and 5- Ethylidene -2- Nobonen Triplet  Elastic copolymer

EPT X-4010M of Mitsui Co., which is a commercially available EPDM rubber, was used as the ternary elastomeric copolymer of Comparative Example 1.

The content of each monomer in the copolymer thus obtained is summarized in Table 2 below. At this time, the content of each monomer was measured using a 600 MHz Avance III HD NMR from Bruker. At this time, the temperature was 373 K and the sample was subjected to ¹ H NMR measurement using ODCB-d4 solution.

Example Ethylene input
(g / hr) Propylene
input
(g / hr) 5-ethylidene-2-norbornene charge
(g / hr) Hexane charge
(kg / hr) Catalyst 1
(μmol / hr) Catalyst 2
(μmol / hr) Co-catalyst
(μmol / hr) TIBAL
(mmol / hr) Hydrogen
(L / hr) Polymerization temperature
(° C) One 900    900 166 5.5 48 3 180 2 0 178.7 2 800  1,150 153 6.0 54 3 180 3 One 175.4 3 800  1,150 153 6.0 54 3 180 3 One 175.6 4 800  1,250 156 5.5 54 3 180 3 0 185.3 5 800  1,250 156 5.5 54 3 180 2.5 One 185.4 6 800  1,250 156 5.5 54 3 180 2 0 185.3 7 830  1,100 148 6.0 54 3 180 3 3 172.3 8 830  1,100 148 6.0 54 3 180 3 3 170.1 9 830  1,100 150 6.0 54 3 180 3 3 169.7 10 940  1,190 107 6.5 27 3 120 2 0 173.5 11 940  1,190 113 6.5 27 3 120 2 0 173.8 12 940  1,190 118 6.5 27 3 120 2 0 175.1 13 940  1,190 134 6.5 27 3 120 2 0 174.5 14 940  1,190 113 6.5 27 3 150 3 0 158.8 15 860  1,340 104 6.5 27 3 150 2 0 174.5 16 860  1,340 98 6.5 27 3 150 2 0 174.5 17 860  1,340 109 6.5 27 3 150 2 0 176 18 860  1,340 104 6.5 24 6 150 4 0 164 19 860  1,340 104 6.5 24 6 150 3 0 168.5 20 860  1,300 104 6.5 24 9 150 4 0 152.5

< Test Example  1> Dynamic viscosity  ( dynamic complex viscosity )

The dynamic complex viscosity was measured using a Rubber Process Analyzer according to ASTM D6204-01. A sample of the RPA2000 MV 2000E equipment manufactured by Monsanto was used. A sample of the copolymer treated with an antioxidant (Irganox 1076) was made into a sheet using a press mold, which was subjected to a 7% strain at 125 DEG C and a strain of 0.1-210 rad / s. &lt; / RTI &gt; The dynamic viscosities of the respective copolymers of the examples at an angular velocity of 1.0 rad / s and 100.0 rad / s were measured, and when they were respectively designated as eta _1.0 and eta _100.0 , shear fluidity values were calculated according to the following general formula Table 2 shows the results.

[Formula 1]

Shear thinning = 侶_1.0 / 侶_100.0

< Test Example  2> Re * Of Rc  Measure

The respective growth rate constants of k11, k12, k21 and k22 were determined by analyzing each copolymer of the examples using ¹³ C-NMR. At this time, a 600 MHz Bruker DRX 600 instrument was used as a measuring instrument, and each copolymer was dissolved in an ortho-dichlorobenzene-d4 solvent and analyzed at 100 ° C.

From the analysis results of the above ¹³ C-NMR by the triad sequence analysis by Randall's method [Journal of Polymer Science: Polymer Physics edition, 1973, 11, 275-287] and Kakugo's method [Macromolecules 1982, 15, The values of Re * Rc were calculated based on the equation of Re = k11 / k12 and Rc = k22 / k21. The values of Re * Rc calculated for each copolymer are shown together in Table 2 below.

< Test Example  3> Measurement of weight average molecular weight

The weight average molecular weights of the copolymers obtained in the Examples were measured by PL-GPC 220 from Polymer Laboratory equipped with three linearly mixed bed columns and are shown in Table 2 below. At this time, the temperature was 160 캜, and 1,2,4-trichlorobenzene was used as a solvent at a flow rate of 1.0 ml / min.

< Test Example  4> Measurement of crystallization temperature

DSC curve data were derived for the copolymers obtained in the examples using a PerkinElmer DSC 6000 DSC measuring instrument. More specifically, each copolymer sample was heated from about 0 ° C to about 100 ° C at a rate of about 20 ° C / min, held at about 100 ° C for about 2 minutes, and then at about -10 ° C / DSC analysis was carried out while cooling to 150 ° C.

The average crystallization temperature (Tc;?) Of each copolymer was calculated from the DSC curve data, and the average crystallization temperature was defined as the crystallization temperature of each copolymer. The crystallization temperatures for each copolymer are summarized in Table 2 below.

< Test Example  5> Pattern Viscosity Measurement

The pattern viscosity of the copolymer obtained in the examples was measured using a Monsanto MV 2000E instrument at 100 ?. The measured pattern viscosities are summarized in Table 2 below.

Ethylene content
(weight%) Propylene content
(weight%) 5-ethylidene-2-norbornene content (% by weight) Pattern viscosity
(1 + 4 a &lt; Weight average molecular weight
(kg / mol) crystallization
Temperature (℃) Re * Rc Shear fluidization degree Example 1 64.3 31.4 4.2 14.4 78K 2.2 0.93 22.8 Example 2 53.5 39.2 7.3 6.5 58K -28.3 0.84 10 Example 3 53.4 39.3 7.3 5.2 56K -28.5 0.83 9.5 Example 4 54.4 38.2 7.4 4.0 51K -27.8 0.86 9.1 Example 5 54.4 38.2 7.4 3.6 42K -27.7 0.86 8.9 Example 6 54.4 38.2 7.4 3.7 49K -27.7 0.85 8.9 Example 7 54.6 38.5 6.9 7.5 60K -27.6 0.86 11.7 Example 8 54.2 38.9 6.9 8.5 65K -28.1 0.84 13.8 Example 9 53.1 39.7 7.2 8.2 63K -28.9 0.81 12.9 Example 10 56.9 38.4 4.7 19.1 88K -16.8 0.61 27.5 Example 11 56.6 38.6 4.8 19 87K -19.8 0.62 27.4 Example 12 56.7 38.4 4.9 19.8 85K -18.9 0.66 28.1 Example 13 56.6 38 5.4 20.5 86K -20.1 0.63 28.7 Example 14 51.7 43.3 4.9 25 94K -33.3 0.61 32.1 Example 15 51.9 43.9 4.2 10.1 68K -35.8 0.61 17.7 Example 16 51.8 44 4.2 10.5 69K -36.8 0.61 18.4 Example 17 51.5 44 4.6 8.4 64K -37.0 0.61 13.5 Example 18 48.1 47.7 4.2 12.6 74K -46.0 0.59 20.2 Example 19 50.3 45.5 4.2 10 68K -40.8 0.59 17.5 Example 20 46.7 48.8 4.5 20.9 92K -47.5 0.59 29.1 Comparative Example 1 54.6 39.8 5.6 7.4 53K -12.4 1.63 5.0

Referring to Table 2, it can be confirmed that the copolymers of Examples 1 to 20 have a low weight average molecular weight of 30,000 to 100,000 and a shear fluidity value of 8 to 40. [ Also, it can be confirmed that the Re * Rc value has a value of 0.5 to 0.99 smaller than 1.

From these results, it can be concluded that the ternary elastomeric copolymers of the above-mentioned Examples exhibit excellent mechanical properties because they have high dynamic viscosities at low angular velocities in use, and also have low weight average molecular weights and low dynamic viscosities at high angular velocities, It was confirmed that it exhibited better melt processability.

Claims (17)

A copolymer of ethylene, an alpha-olefin having 3 to 20 carbon atoms and a diene, obtained in the presence of a catalyst mixture comprising a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula (2)
i) a weight average molecular weight as measured by GPC of from 30,000 to 100,000,
ii) The shear thinning, which is the ratio of the dynamic viscosity at an angular frequency of 1.0 rad / s to the dynamic viscosity at an angular frequency of 100.0 rad / s measured by a rubber process analyzer at 125 ° C. is 8 &Lt; / RTI &gt; to 40, ternary elastomeric copolymer:
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R ₁ to R ₁₃ may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; Two adjacent two of R ₁ to R ₁₃ may be linked to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or 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;
Q ₁ and Q _{2, which} may be the same or different, are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.
The ternary elastomeric copolymer according to claim 1, wherein a product Re * Rc of the reactive constant, Re, indicative of the distribution of ethylene in the copolymer, and the reactive constant Rc, which indicates the distribution of alpha olefins in the copolymer,
In this case, Re = k11 / k12, Rc = k22 / k21, k11 is the growth rate constant when ethylene is bonded to ethylene in the copolymer chain, k12 is the rate constant when ethylene is bonded to ethylene in the copolymer chain, K21 is the growth rate constant when the ethylene is bonded after the alpha olefin in the copolymer chain, k22 is the growth reaction rate constant when the alpha olefin is bonded to the alpha olefin in the copolymer chain, It is a rate constant.
The ternary elastomeric copolymer according to claim 2, wherein the Re * Rc is 0.70 to 0.95.
delete The composition of claim 1, wherein the copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene comprises 40 to 70% by weight of ethylene, 15 to 55% by weight of an alpha olefin having 3 to 20 carbon atoms, and 0.5 to 20% A copolymer of dienes, and a ternary elastomeric copolymer.
The ternary elastomeric copolymer according to claim 1, having a crystallization temperature of -55 to 30 캜.
2. The ternary elastomeric copolymer according to claim 1, having a pattern viscosity of 1 to 40 MU (1 + 4 ai100 deg. C).
The ternary elastomeric copolymer according to claim 1, which has a molecular weight distribution of 2 to 4.
The process according to claim 1, wherein the alpha olefin is at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene and the diene is at least one selected from the group consisting of 5-ethylidene- Norbornene and 4-hexadiene, wherein the ternary elastomeric copolymer is at least one selected from the group consisting of norbornene and 4-hexadiene.
In the presence of a catalyst composition comprising a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula (2): 40 to 70% by weight of ethylene, 15 to 55% Of an alpha-olefin and 0.5 to 20% by weight of a diene are continuously supplied to a reactor, wherein the monomer composition is fed continuously to the reactor.
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R ₁ to R ₁₃ may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; Two adjacent two of R ₁ to R ₁₃ may be linked to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or 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;
Q ₁ and Q _{2, which} may be the same or different, are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.
11. The method according to claim 10, wherein the first transition metal compound is at least one selected from the group consisting of compounds represented by the following formula:

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.
The method for producing a ternary elastomeric copolymer according to claim 10, wherein the second transition metal compound is at least one selected from the group consisting of compounds represented by the following formulas:

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.
11. The method for producing a ternary elastomeric copolymer according to claim 10, wherein the catalyst composition further comprises at least one promoter compound selected from the group consisting of the following chemical formulas (3), (4) and (5)
(3)
- [Al (R) -O] _n -
In Formula 3,
R may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen; n is an integer of 2 or more;
[Chemical Formula 4]
D (R) ₃
In Formula 4, R is as defined in Formula 3; D is aluminum or boron;
[Chemical Formula 5]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
11. The process according to claim 10, wherein the alpha olefin is at least one member selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene and the diene is at least one member selected from the group consisting of 5-ethylidene- Norbornene, and 4-hexadiene, wherein the ternary elastomeric copolymer is at least one selected from the group consisting of norbornene and 4-hexadiene.
11. The method for producing a ternary elastomeric copolymer according to claim 10, wherein the monomer composition, the first and second transition metal compounds, and the cocatalyst are copolymerized while continuously supplying the solution in a reactor.
16. The process for producing a ternary elastomeric copolymer according to claim 15, wherein the copolymerization step is continuously carried out while continuously discharging the copolymerized ternary elastomeric copolymer from the reactor.
The method for producing a ternary elastomeric copolymer according to claim 10, wherein the copolymerization step is carried out at a temperature of 100 to 200 ° C.