KR101462208B1 - Elastic diene terpolymer and preparation method thereof - Google Patents

Abstract

The present invention relates to a ternary elastic copolymer and a method for producing the same, wherein the ternary elastic copolymer includes a long chain branch which simultaneously has excellent processability and elasticity (flexibility) and is obtained under the presence of a group 4 transition metal catalyst. The ternary elastic copolymer is a copolymer of ethylene, C3 to 20 alpha olefin, and diene, wherein i) a weight average molecular weight measured through GPC is 100,000 to 500,000, and ii) x which is the content (wt%) of ethylene and y which is the density value (g/cm^3) of the copolymer measured when the content of ethylene is x satisfy 0.0000175214x(x-75.65420571)+0.875<= y <=0.0000175214x(x-75.65420571)+0.881.

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 ternary 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 low-temperature properties and elasticity (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.

Further, U.S. Patent No. 5,902,867 discloses a method of lowering the viscosity of a polymer by widening the molecular weight distribution in order to improve the kneadability and extrusion processability of EPDM. In this case, the low molecular weight component contained in the cross- There is a limit that the surface characteristics and low temperature characteristics are deteriorated during processing.

Accordingly, there is a continuing need for a ternary elastomeric copolymer having a long chain branch capable of satisfying excellent processability and elasticity (flexibility) at the same time, 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 U.S. Patent No. 5,902,867

Accordingly, the present invention is to provide a ternary elastomeric copolymer which can simultaneously satisfy excellent low-temperature properties and elasticity (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 obtained in the presence of a transition metal of a transition metal,

i) a weight average molecular weight measured by GPC of 100,000 to 500,000,

ii) the content (% by weight) of ethylene and the density value (g / cm 3) y of the copolymer measured when the content of ethylene is x is 0.0000175214x (x-75.65420571) + 0.875? y? 0.0000175214x 75.65420571) +0.881. &Lt; / RTI &gt;

The present invention also provides a catalyst composition comprising 40 to 80% by weight of ethylene, 15 to 55% by weight of ethylene, 1 to 50% by weight of a transition metal compound, Of an alpha-olefin having 3 to 20 carbon atoms and 4 to 6% 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 connected 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 obtained in the presence of a transition metal of Group 4,

i) a weight average molecular weight measured by GPC of 100,000 to 500,000,

ii) the content (% by weight) of ethylene and the density value (g / cm 3) y of the copolymer measured when the content of ethylene is x is 0.0000175214x (x-75.65420571) + 0.875? y? 0.0000175214x 75.65420571) +0.881, is provided.

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 100,000 to 500,000, or about 150,000 to 400,000, or about 200,000 to 300,000 Of the weight average molecular weight. This large weight average molecular weight is achieved due to the excellent activity of the first and second transition metal compounds of Formulas 1 and 2 described below belonging to a Group 4 transition metal catalyst, e. G., The metallocene family, As the ternary elastomeric copolymer has such a large molecular weight, the ternary elastomeric copolymer, for example, the EPDM rubber, can exhibit excellent mechanical properties.

In the ternary elastomeric copolymer of one embodiment, the content (% by weight) x of ethylene and the density value (g / cm 3) y of the copolymer measured when the content of ethylene is x are 0.0000175214x 75.65420571) + 0.875? Y? 0.0000175214x (x-75.65420571) +0.881.

The ternary elastomeric copolymer of one embodiment that satisfies this relationship may be in an optimized range with a relatively low density value relative to the content of ethylene contained therein. As described above, since the ternary elastomeric copolymer in one embodiment is in the range of the density relative to the content of ethylene, the ternary elastomeric copolymer can satisfy both excellent low-temperature properties and improved elasticity and flexibility at the same time have.

On the other hand, in the ternary elastomeric copolymer of one embodiment, the relationship between the content x of ethylene and the enthalpy of crystallization y can be measured by the following method. First, two or more kinds of ternary elastomeric copolymers having different ethylene contents are polymerized and produced within the content range of each of the above-mentioned monomers, and then each copolymer is subjected to density measurement using, for example, METTLER TOLEDOXS 104 To obtain density data. This density value can be measured, for example, by the Hydrostatic Method in the density measurement method of ASTM D297. These density values can be obtained by measuring each copolymer sample in the form of a size of approximately 3 cm in diameter and 2 mm in thickness, measuring the sample weight in air, the weight of the sample in distilled water, and the temperature of the distilled water have.

Then, the data for each copolymer was displayed with the content of ethylene contained in each copolymer as the x-axis and the density value measured for each of the copolymers as the y-axis, and then the data was linearly regressed The relationship between the content x of the ethylene and the density y can be derived. One example of the relationship between x and y is as shown in Fig.

In this way, the relationship between x and y of the ternary elastomeric copolymer of one embodiment is derived. As a result, the ternary elastomeric copolymer has a density relative to the content of ethylene, such as EPDM rubber, (X-75.65420571) + 0.875? Y? 0.0000175214x (x-75.65420571) + 0.881 at the low level. As a result, it has been confirmed that the ternary elastomeric copolymer of one embodiment can satisfy excellent mechanical properties due to a large molecular weight, excellent low temperature properties, elasticity and flexibility at the same time.

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.

The copolymer of ethylene, the alpha olefins of 3 to 20 carbon atoms and the diene may contain 40 to 80 wt%, or 50 to 70 wt% of ethylene, 15 to 55 wt% of alpha olefins of 3 to 20 carbon atoms, and 4 to 6 By weight of a diene copolymer. Such copolymers may be prepared by continuously feeding a monomer composition comprising 40 to 80% by weight of ethylene, 15 to 55% by weight of alpha olefins of 3 to 20 carbon atoms and 4 to 6% 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 addition, the ternary elastomeric copolymer of the present invention can be used for a fifth harmonic of a storage elastic modulus measured by a Rubber Process Analyzer at 125 ° C using a LAOS (Large Angles of Oscillation and High Strains) The LCB Index, which is the ratio of the first harmonic of the storage elastic modulus, can have a positive value, preferably about 0 to 5, or about 0.01 to 3.5.

The ternary elastomeric copolymer of this embodiment that satisfies this relationship has a long chain branching degree to such a value that the LCB Index can exhibit a positive value, so that it exhibits excellent processability, is suitable for extrusion processing, and has improved elasticity and flexibility And excellent mechanical properties at the same time.

The LCB Index can be measured by a Rubber Process Analyzer using the LAOS (Large Angles of Oscillation and High Strains) method as follows. First, after the polymerization and production of the ternary elastomeric copolymer, the temperature (125 ° C) and the frequency (0.2 Hz) determined by a SIS V-50 Rubber Process Analyzer of SCARABAEUS Instruments SystemSS were measured for each copolymer, And the behavior of the shear storage modulus is measured by varying the strain from 0.2% to 1250%. The ratio of the first harmonic of the storage elastic modulus to the fifth harmonic can be calculated by the LCB Index after deriving the first harmonic and the fifth harmonic by FT transforming the measured storage elastic modulus.

At this time, When the first harmonic (1sr harmonics) and the fifth harmonic of the storage elastic modulus are defined as G ' ₁ and G' ₅ , respectively, the LCB Index can be expressed by the following general formula (1).

[Formula 1]

LCB Index = G ' ₁ / G ' ₅

In this way, LCB Index of the ternary elastomeric copolymer of one embodiment was calculated. As a result, the ternary elastomeric copolymer exhibited higher long chain branching index than EPDM rubber, which was used in the previously used Group 4 transition metal catalyst, Was found to have a positive value. It has been confirmed that the ternary elastomeric copolymer having the long long chain branching and the positive LCB Index can satisfy both excellent mechanical properties due to a large molecular weight, excellent elasticity, flexibility and melt processability at the same time.

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. &Lt; / RTI &gt; 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, , Whereby the copolymer can exhibit more excellent elasticity and flexibility required for EPDM rubber and the like.

The ternary elastomeric copolymer of one embodiment has a density of about 0.840 to 0.895 g / cm ³ , or about 0.850 to 0.890 g / cm ³ , for example, a density range capable of satisfying appropriate physical properties as EPDM rubber or the like .

In addition, the ternary elastomeric copolymer of one embodiment may have a Mooney viscosity (1 + 4 @ 125 ° C) range, for example, about 1 MU to 180 MU, or about 5 MU to 150 M MU, or a pattern viscosity of about 20 MU to 130 MU. The pattern viscosity (1 + 4 @ 125 ° C) can be measured using a Monsanto alpha 2000 instrument based on ASTM D1646-04. When the pattern viscosity is less than 20 MU, the pattern viscosity is 130 When it exceeds MU, although it can be produced by the present invention, it is not economically advantageous because the resin productivity is low due to high viscosity.

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 is characterized by comprising, 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 80% by weight of ethylene, By weight of a monomer composition comprising from 3 to 20% by weight of an alpha olefin and from 4 to 6% by weight of a diene, continuously feeding 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 connected 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.

As can be seen from the following examples and the like, a certain amount of monomer, that is, about 40 to 80 wt%, or about 50 to 70 wt% of ethylene, about 15 to 55 wt% of alpha-olefin having 3 to 20 carbon atoms And about 4 to 6% by weight of a diene, and each of these monomers is produced by a continuous polymerization process in the presence of the transition metal catalyst of the above formula (1) or (2) to satisfy the above-mentioned specific relationship between the ethylene content and the density It was confirmed that the ternary elastomeric copolymer of the embodiment of the present invention 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, it is possible to produce a ternary elastomeric copolymer having a long molecular weight and a homogeneous alternating distribution of monomers and a long chain branch, with high productivity and yield. Since the three-component elastomer copolymer thus obtained is uniformly alternately distributed in the respective monomers, the density of the ethylene relative to the ethylene content is not so high, and the characteristics of the above-described embodiment, for example, the ethylene content x and A relationship such as 0.0000175214x (x-75.65420571) + 0.875? Y? 0.0000175214x (x-75.65420571) +0.881 of the density y, and a characteristic such that Re * Rc becomes smaller than 1 can be satisfied.

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 high molecular weight range of one embodiment, or the ethylene content and density may not meet certain relationships.

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 10: 1 to 1:10, and the total transition metal compound : The molar ratio of the promoter compound of Formula 3 or Formula 4 may be from about 1: 5 to 1: 500, and the molar ratio of the total transition metal compound to the promoter compound of Formula 5 is about 1: 1 to 1: 10 &lt; / RTI &gt;

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 non-conjugated 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 may be carried out at a temperature of about 100 to 170 ° C, or a temperature of about 100 to 160 ° 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 the continuous solution polymerization, the ternary elastomeric copolymer having a long chain branch can be obtained more efficiently in productivity and yield.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a ternary elastomeric copolymer having excellent low-temperature properties, improved elasticity and flexibility, and the like can be used as EPDM rubber and the like highly preferably.

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 EPDM rubber and the like manufactured by the previously known metallocene-type transition metal catalyst, and can satisfy the low temperature properties, 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.

1 is a graph showing the relationship between the ethylene content and the density of the ternary elastomeric copolymer prepared in Examples and Comparative Examples.

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 7> 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 7.6 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 51 to 54 μmol per hour. The above-mentioned N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used as a co-catalyst compound in a state dissolved in toluene, and charged into the reactor at a rate of 255 to 270 μmol per hour. The above-mentioned triisobutylaluminum was used as an additional promoter compound in a state dissolved in hexane, and the reactor was charged at a rate of 4080 to 4200 占 퐉 ol per hour.

The copolymerization proceeded while continuously supplying 950 g / hour of ethylene, 820 to 950 g / hr of propylene, and 86 to 129 g / hour of monomer, which are monomers, to the reactor.

The copolymerization temperature in the reactor was adjusted to be between 120 and 140 ° C while increasing the feed rate of 5-ethylidene-2-norbornene from 1 mL / min to 0.5 mL / min at about 140 ° C.

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 7 in a uniform solution state. The polymerization solution continuously discharged from the upper portion of the reactor was subjected to polymerization reaction under ethanol And then dried under reduced pressure in a vacuum oven at 60 DEG C to finally prepare the copolymer of Examples 1 to 7.

< Comparative Example  1 to 4> Commercial ethylene, propylene and 5- Ethylidene -2- Nobonen Triplet  Elastic copolymer

4520, 4640, 4760, 4770 of DOW, a commercialized EPDM rubber known to be made of a metallocene catalyst, were sequentially made into a ternary elastomeric copolymer from Comparative Examples 1 to 4.

The content of each monomer in the thus-obtained copolymer is as shown in Table 1 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.

Ethylene Propylene 5-ethylidene-2-norbornene wt% wt% wt% Example 1 52.1 43.2 4.7 Example 2 52.7 42.2 5.1 Example 3 53.9 41.3 4.8 Example 4 56.9 38.4 4.7 Example 5 62.8 29.9 5.1 Example 6 65.0 29.9 5.1 Example 7 70.0 25.1 4.9 Comparative Example 1 47.1 47.3 5.6 Comparative Example 2 51.2 43.6 5.2 Comparative Example 3 65.0 30.1 4.9 Comparative Example 4 69.9 25.0 5.1

< Test Example  1> Density measurement and derivation of the relationship between the content of ethylene and the density

For the copolymers of the above examples and comparative examples, density data were obtained using a density measuring instrument of METTLER TOLEDO XS 104, and the density measurement method was the Hydrostatic Method in the density measurement method of ASTM D297. More specifically, the water temperature was measured to determine the density of water, and then the weight of the sample was measured in air and water, respectively. A support was used to measure the weight of the water-rising sample in water, and the density was derived using the following general formula (1).

[Formula 1]

Density [g / cm3] = D * A / {A- (B-C)}

A = weight of sample in air [g]

B = weight of sample in water and weight of support [g]

C = weight of support in water [g]

D = density of water

The density values of the thus derived Examples and Comparative Examples are shown in Table 2. Then, the data for each copolymer was displayed on the x-axis with the content of ethylene contained in each copolymer in the examples and the density measured on each of the copolymers as the y-axis, and then the data was linearly regressed , The relationship between the content x of the ethylene and the density y was derived. This relationship is shown in Fig. 1, and for comparison with the embodiment, the data of Comparative Examples 1 and 4 are also shown in Fig.

< Test Example  2> LCB Index Measurement of

The copolymers obtained in Examples and Comparative Examples were subjected to strain at a temperature (125 ° C) and a frequency (0.2 Hz) determined by a SIS V-50 Rubber Process Analyzer of SCARABAEUS Instruments SystemSS from 0.2% to 1250 %, And the behavior of shear storage modulus was measured. The ratio of the first harmonic of the storage elastic modulus to the fifth harmonic is calculated by the LCB Index after deriving the first harmonic and the fifth harmonic by FT conversion of the measured storage modulus, Respectively.

At this time, The first harmonic (1sr harmonics) and the fifth harmonic of the storage elastic modulus are G ' ₁ , G' ₅ , The LCB Index can be represented by the following general formula (2).

[Formula 2]

LCB Index = G ' ₁ / G ' ₅

< Test Example  3> Re * Of Rc  Measure

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

Ethylene content density LCB Index Re * Rc wt% g / cm3 Example 1 52.1 0.857 1.55 0.573 Example 2 52.7 0.858 1.33 0.642 Example 3 53.9 0.859 0.80 0.631 Example 4 56.9 0.858 0.29 0.713 Example 5 62.8 0.862 0.94 0.770 Example 6 65.0 0.865 0.78 0.843 Example 7 70.0 0.870 0.82 0.942 Comparative Example 1 47.1 0.859 -1.69 1.608 Comparative Example 2 51.2 0.860 -1.23 1.449 Comparative Example 3 65.0 0.871 -1.13 1.458 Comparative Example 4 69.9 0.876 -1.10 1.516

Referring to Table 2 and FIG. 1, the copolymers of Examples 1 to 7 had a relationship between the content x of ethylene and the density y of 0.0000175214x (x-75.65420571) + 0.875? Y? 0.0000175214x (x-75.65420571) + 0.881, the LCB Index has a positive value, and Re * Rc is less than 1.

In contrast, the copolymers of Comparative Examples 1 to 4 exhibited higher densities of copolymers having a content of ethylene similar to those of the Examples, so that 0.0000175214x (x-75.65420571) + 0.875? Y? 0.0000175214x (x-75.65420571) + 0.881, the LCB index has a negative value, and Re * Rc is greater than 1.

From these results, it was found that the three-component elastomeric copolymers of Examples 1 to 7 exhibited low density compared to the ethylene content and excellent low-temperature properties, elasticity and flexibility compared with the comparative examples because each monomer was uniformly distributed in the polymer chain in an alternating arrangement .

Claims (18)

A copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene, obtained in the presence of a transition metal catalyst,
i) a weight average molecular weight measured by GPC of 100,000 to 500,000,
ii) the content (% by weight) of ethylene and the density value (g / cm 3) y of the copolymer measured when the content of ethylene is x is 0.0000175214x (x-75.65420571) + 0.875? y? 0.0000175214x 75.65420571) +0.881. &Lt; / RTI &gt;
The method according to claim 1, wherein the first-order harmonic of the storage elastic modulus for the fifth-order harmonic of the storage elastic modulus measured by a rubber process analyzer at 125 ° C is measured using LAOS (Large Angles of Oscillation and High Strains) Wherein the ratio LCB Index has a positive value.
The ternary elastomeric copolymer according to claim 2, wherein the LCB Index has a value of more than 0 and 5 or less.
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.
5. The ternary elastomeric copolymer according to claim 4, wherein the Re * Rc is 0.60 to 0.99.
The composition according to claim 1, wherein the copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene comprises 40 to 80% by weight of ethylene, 15 to 55% by weight of an alpha olefin having 3 to 20 carbon atoms and 4 to 6% A copolymer of dienes, and a ternary elastomeric copolymer.
The ternary elastomeric copolymer according to claim 1, having a density of 0.840 to 0.895 g / cm &lt; ³ &gt;.
The ternary elastomeric copolymer according to claim 1, having a pattern viscosity of 5 to 180 (1 + 4 a) 125 ° 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 80% by weight of ethylene, 15 to 55% Of an alpha-olefin and 4 to 6% 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 connected 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.
12. The method according to claim 11, wherein the first 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.
12. The method according to claim 11, 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.
12. The method of claim 11, 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 .
12. The process according to claim 11, 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.
12. The method for producing a ternary elastomeric copolymer according to claim 11, wherein the monomer composition, the first and second transition metal compounds, and the cocatalyst are copolymerized while continuously supplying the solution in a reactor.
The process for producing a ternary elastomeric copolymer according to claim 16, wherein the copolymerization step is continuously carried out while continuously discharging the copolymerized ternary elastomeric copolymer from the reactor.
12. The method for producing a ternary elastomeric copolymer according to claim 11, wherein the copolymerization step is carried out at a temperature of 100 to 170 ° C.

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