KR100501398B1 - Long-Chain Branched α-olefin/cycloolefin/diene Copolymers and Method for Preparing the Same - Google Patents

Abstract

The method for preparing an α-olefin / cyclic olefin / diene random copolymer having a long-chain branch having excellent impact resistance, transparency, and heat resistance may include at least one or more of α-olefin, cyclic olefin, and diene monomer mixtures. Injecting a metallocene catalyst and a cocatalyst to prepare an α-olefin / cyclic olefin / diene terpolymer having an active vinyl group; And a second step of preparing the α-olefin / cyclic olefin / diene random copolymer by injecting the metallocene catalyst and the cocatalyst into the product of the first step and the unreacted mixture and continuing polymerization.

Description

Long-Chain Branched α-olefin / cycloolefin / diene Copolymers and Method for Preparing the Same}

Field of invention

The present invention relates to an α-olefin / cyclic olefin / diene random copolymer having a long-chain branch and a method of manufacturing the same. More specifically, the present invention, in the polymerization of α-olefin / cyclic olefin / diene, by polymerizing in two stages using at least one metallocene catalyst To prepare α-olefin / cyclic olefin / diene random copolymers having excellent impact resistance, transparency, heat resistance, no gelation, stable physical properties, easy control of cyclic olefin and ethylene content, and long branch having high productivity It is about a method.

Background of the Invention

In general, copolymers of ethylene, propylene, and cyclic olefins use metallocene catalysts, and cyclic ring structures such as norbornene are connected to the polymer main chain to have amorphous and high glass transition temperatures, such as transparency and heat resistance. Has excellent properties that cannot be reached with polyethylene or the like. Accordingly, it replaces polycarbonate (PC) or polymethyl methacrylate (PMMA) resin, which is currently used as information recording material, and is an optical material with transparency and low hygroscopicity, which can be used for various purposes such as DVD, CD, lens, and optical fiber. The possibility was opened. Such copolymers can be utilized in the field of optical materials, such as optical memory disks and optical fibers, as described, for example, in Japanese Patent Laid-Open No. 1985-168708.

In addition, Japanese Patent Laid-Open Publication No. 1993-41364 discloses a method of copolymerizing α-olefin and cyclic olefin in the presence of a hydrocarbon elastomer having a polymerizable two bond. However, the defects of these copolymers have a problem that the impact resistance is very weak and commercial value is low.

To compensate for this, Korean Patent Publication No. 1996-22748 and Japanese Patent No. 94-328549 disclose a kind of alloy obtained by copolymerizing α-olefin and cyclic olefin in the presence of an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or a hydrate thereof. (alloy) copolymers have been proposed. However, it is difficult to obtain low activity, price increase and sufficient impact resistance due to the addition of rubbery material.

Accordingly, the present inventors copolymerize α-olefins, cyclic olefins, and dienes in two steps using at least one metallocene catalyst and a cocatalyst, so that the impact resistance is remarkably improved, and the heat resistance is maintained. It has begun to develop α-olefin / cyclic olefin / diene random copolymer having a long branch and a method for producing the same. In addition, the production method of the α-olefin / cyclic olefin / diene random copolymer of the present invention is characterized in that it is easy to control the content of ethylene, cyclic olefin.

An object of the present invention is to provide an α-olefin / cyclic olefin / diene random copolymer having a long branch having 3 or more carbon atoms and a method for producing the same.

Another object of the present invention is to provide an alpha -olefin / cyclic olefin / diene random copolymer having a long branch excellent in impact resistance, while maintaining heat resistance and excellent in molding without gelation, and a method for producing the same.

Still another object of the present invention is to provide a method for preparing α-olefin / cyclic olefin / diene random copolymer having a long branch that is easy to control the content of ethylene and cyclic olefin.

Both the above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

The α-olefin / cyclic olefin / diene random copolymer having the long branches of the present invention is injected with at least one metallocene catalyst and a cocatalyst into a mixture of α-olefins, cyclic olefins, and diene monomers to form α-olefins having an active vinyl group. A first step of preparing a / cyclic olefin / diene terpolymer; And a second step of preparing the α-olefin / cyclic olefin / diene random copolymer by injecting the metallocene catalyst and the cocatalyst into the product of the first step and the unreacted mixture and continuing polymerization.

The method for preparing the α-olefin / cyclic olefin / diene random copolymer of the present invention is as shown in the process diagram disclosed in FIG. 1.

In the method of FIG. 1, a metallocene catalyst and a cocatalyst are added to an α-olefin, a cyclic olefin, and a diene compound to prepare a three-way copolymer of α-olefin / cyclic olefin / diene. Consists of a second step reaction of supplying the same or different metallocene catalyst and cocatalyst as the first step and further supplying α-olefin and cyclic olefin to finally prepare α-olefin / cyclic olefin / diene random copolymer do.

Hereinafter, a method of preparing an α-olefin / cyclic olefin / diene random copolymer having a long branch of the present invention will be described in more detail.

The method of FIG. 1 consists of a two step process. In the first step, a three-way copolymer of α-olefin / cyclic olefin / diene is prepared by supplying α-olefin, cyclic olefin, diene compound, metallocene catalyst and cocatalyst to the first reactor. The unreacted mixture is transferred to a second reactor, followed by supplying a metallocene catalyst and a promoter to continue polymerization. In the second step, α-olefin and cyclic olefin may be additionally supplied, and the metallocene catalyst may be the same as or different from the first step. In this method, the second reactor may be the same as the first reactor, and may be polymerized continuously in one reactor, or another reactor may be used.

Examples of the α-olefins used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like, and ethylene and propylene are preferable.

Cycloolefins used in the present invention are cyclobutene, cyclopentene, cyclohexene, 3,4-dimethyl cyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexyl, styrene, α-methyl Styrene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, norbornene, 5-methyl norbornene, 5,6-dimethyl norbornene, 1-methyl norbornene, 5-ethyl Norbornene, 5-n-butyl norbornene, 5-isobutyl norbornene, 7-methyl norbornene, 5-phenyl norbornene, 5-methyl-5-phenyl norbornene, 5-benzyl norbornene, 5-tolyl nord Bonene, 5-ethylphenyl norbornene, 5-isopropylphenyl norbornene, 5-biphenyl norbornene, tetracyclo-3-dodecene, 8-methyl tetracyclo-3-dodecene, 8-ethyl tetracyclo-3 -Dodecene, 8-propyl tetracyclo-3-dodecene, 8-butyl tetracyclo-3-dodecene and the like.

The dienes used in the present invention include all compounds capable of coordination polymerization, 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, dicyclopentadiene, vinylnorbornene, 4-vinyl -1-cyclohexene, 3-vinyl-1-cyclohexene, 2-vinyl-1-cyclohexene, 1-vinyl-1-cyclohexene, o-divinylbenzene, p-divinylbenzene, m -Divinylbenzene is preferred. It is more preferable to use dienes in which a plurality of double bonds (vinyl groups) are bonded via a hydrocarbon group having 6 to 30 carbon atoms containing a single or a plurality of aromatic vinyl ring structures, and various divinyls of ortho, para, and meta Most preferably, benzene and vinylnorbornene, ethyleneden norbornene and mixtures thereof are used.

In the present invention, at least one metallocene catalyst is used. In other words, the metallocene catalyst of α-olefin / cyclic olefin / diene is not limited in use as long as it is a reactive catalyst between α-olefin and cyclic olefin. Among the previously disclosed catalysts, single site coordination polymerization catalysts suitable for coordination polymerization are metallocene catalysts, half metallocene catalysts, constrained geometry catalysts (CGC), and Ziegler- Natta catalysts can be used. Most preferred are metallocene catalysts or catalysts with constrained arrangements.

Representative examples of the metallocene catalysts used in the present invention are compounds containing a transition metal selected from the group consisting of titanium, zirconium, hafnium, and the like of Group IV B of the periodic table, and are described in US Pat. No. 6,284,701. Novel metallocene catalysts have been disclosed that are very efficient for preparing coalescing. The metallocene catalyst has a structure in which an auxiliary ligand and a functional group of the compound are bonded to each other by a transition metal compound. It is also characterized by having a wide variety of forms depending on the type of transition metal compound, the type of compound having two or more functional groups or the molar ratio of each reactant.

Representative catalyst structural formula is represented by the following formula (1), (C ₅ H ₅ ) ₂ (ZrCl) -O- (C ₆ H ₄ ) ₂ C (CH ₃ ) ₂ -O- (ZrCl) (C ₅ H ₅ ) ₂ [Cp ₂ (ZrCl) -G- (ZrCl) Cp ₂ ], (C ₅ H ₅ ) ₂ (TiCl) -O- (C ₆ H ₄ ) ₂ C (CH ₃ ) ₂ -O- (TiCl) (C ₅ H ₅ ) ₂ [Cp ₂ (TiCl) -G- (TiCl) Cp ₂ ].

[Formula 1]

Wherein M and M 'are independently transition metals of Group IV, V and VI of the periodic table; Cp, Cp', Cp "and Cp '" represent transition metals of Group IV, V and VI of the periodic table. one of the cyclopentadienyl, indenyl, fluorenyl, or derivatives thereof that produces a η ⁵ bond; X ₁ , X ₂ are each independently a hydrogen atom; a hydroxide (—OH); a halogen atom; C _{1 -20} alkyl group, a cycloalkyl group or an alkoxy group; C _6-20 aryl group, alkylaryl group or aryl alkyl group; G is a transition as to connect the metals and other transition metals formula -YR ⁶ each independently Y'- (Y and Y 'in the formula -YR ⁶ Y'- are each independently an oxygen atom, a sulfur atom and -Nr ¹ or -Pr ² , R ⁶ is a formula R _a , R _b -OR _c ,- (R _b -OR _c ) or Wherein R _a , R _b , R _c , R _d and R _e are each independently C _1-20 straight alkyl or branched alkyl group, C _3-20 cycloalkyl group or substituted cycloalkyl group; Or C _6-40 aryl group, alkylaryl group or arylalkyl group, r ³ is a hydrogen atom; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-20 aryl group, alkylaryl group or aryl Alkyl group).

In addition, typical metallocene catalysts applicable to the present invention include rac-ethylenebis (indenyl) zirconium dichloride [rac-Et (Ind) ₂ ZrCl ₂ ] and I-flofilidene (cyclopentadienyl) ( Fluorenyl) zirconium dichloride [i-Pr (Cp) (Flu) ZrCl ₂ ], (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (CGC) .

The metallocene catalyst may be supported on a suitable carrier. Examples of the carrier which can be used as the support include silica, alumina, magnesium compounds and the like.

The metallocene catalyst of the present invention may be used in plural by selecting at least one kind or more.

In the present invention, the use ratio of the metallocene catalyst of the first step and the metallocene catalyst of the second step, that is, the molar ratio of the Group 4 transition metal (eg, titanium, zirconium, hafnium) in the catalyst component (= two-stage transition metal) Mole / stage transition metal mole) is preferably in the range 0.01 to 20, preferably in the range 0.1 to 10, more preferably in the range 0.1 to 5.

In the present invention, the metallocene catalyst is used to polymerize the copolymer together with the cocatalyst. An organic metal compound may be used as a cocatalyst, or a mixture of non-coordinated Lewis acid and alkyl aluminum may be used together. Organometallic compounds usable in the present invention include alkylaluminum oxane or organoaluminum compounds. Representative examples of the alkyl aluminum oxane include methylaluminium oxane and modified methylaluminium oxane.

The organoaluminum compound includes aluminum oxane having a unit represented by the following formula (2), and these include a chain-shaped aluminum oxane represented by the following formula (3) and a cyclic aluminum oxane represented by the following formula (4):

[Formula 2]

[Formula 3]

[Formula 4]

(In the formula 2, 3 and 4, R 'is an alkyl group of C _1~6, p is an integer from 0 to 100).

Alkyl aluminum in the alkyl aluminum or non-coordinating Lewis acid used as a promoter in the present invention is trimethyl aluminum, triethyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, triisobutyl aluminum, diisobutyl aluminum chloride. , Tri (n-butyl) aluminum, tri (n-propyl) aluminum and triisopropylaluminum; non-coordinated Lewis acids include N, N-dimethyl aniline tetrakis (pentafluorophenyl) borate, triphenyl carbeni Um tetrakis (pentafluorophenyl) borate, ferrocerium tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borate.

In using the organometallic compound which is a cocatalyst and the metallocene catalyst of the 1st and 2nd stage in this invention, the ratio of the aluminum of an organometallic compound and the Group 4 transition metal in a metallocene catalyst component, ie, aluminum: The molar ratio of the transition metal is preferably in the range of 0.1: 1 to 100,000: 1, and more preferably in the range of 1: 1 to 10,000: 1.

In the case of using alkyl aluminum as a promoter in the present invention, the molar ratio of the transition metal of the alkyl aluminum to the metallocene catalyst is preferably in the range of 1: 1 to 100,000: 1, and in the range of 50: 1 to 10,000: 1. More preferably, the range of 100: 1-1,000: 1 is the most preferable. When the non-coordinated Lewis acid is used as the cocatalyst component, the molar ratio of the transition metal in the components of the non-coordinated Lewis acid: metallocene catalyst is preferably in the range of 0.1: 1 to 20: 1, most preferably 1.

The diene weight ratio based on the cyclic olefin is preferably 0.1 to 10,000 ppm (parts per million), more preferably 0.1 to 5,000. The use of too many dienes is undesirable because of the possibility of gelation by unreacted residues.

The use of the α-olefin in the first step and the second step is preferably in the range of 0.1 to 100, more preferably in the range of 1 to 50. And the molar ratio of the α-olefin in the two-step process: α-olefin in the one-step process is preferably in the range of 0.1 to 100, more preferably in the range of 0.1 to 50, and even more preferably in the range of 0.1 to 10.

The at least one metallocene catalyst and the cocatalyst may be mixed or prepared outside the polymerization reactor, or mixed in the polymerization reactor at the time of polymerization. In addition, in the preparation of the copolymer of the present invention, additives, adjuvants, and the like, which are commonly used in polymers, may be included within the range of not impairing the effects of the present invention, and most preferably, antioxidants, lubricants, and plasticizers. plasticizers, ultraviolet absorbers, stabilizers, pigments, dyes and sulfates, asbestos, staining agents, talc, silica, ceramics, inorganic fillers such as ceramics, and / or blowing agents. Can be.

Although the polymerization temperature for copolymerizing using the catalyst system of this invention does not have a restriction | limiting in particular, 0-180 degreeC is preferable and 0-100 degreeC is more preferable. In the present invention, the polymerization time is not particularly limited.

The polymerization method usable in the present invention is not particularly limited, and bulk polymerization, solution polymerization and the like which are generally used are possible.

When using a solvent in this invention, you may use aliphatic hydrocarbons, such as pentane, hexane, heptane, cyclic aliphatic hydrocarbons, such as cyclohexane, and aromatic hydrocarbon solvents, such as benzene, toluene, xylene, and ethylbenzene.

In addition, the shape of the polymerization reactor is not particularly limited, but in general, a stirred tank reactor, a plug-flow reactor capable of mixing and kneading is preferable, and a product The flow of is preferably batch or continuous.

The α-olefin / cyclic olefin / diene random copolymer produced by the method of the present invention has long branches having 3 or more carbon atoms.

The invention may be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1

(1) First step: 850 ml of purified toluene and 400 g of norbornene were dissolved in a 2 L high pressure reactor. 1.2 ml of vinyl norbornene and 49 mmol of triisobutylaluminum (based on aluminum) were added thereto, and the mixture was stirred and heated to 40 ° C. Under nitrogen atmosphere, MAO 56.6 mmol (based on aluminum) and 18.9 μmol (C ₅ H ₅ ) ₂ (ZrCl) -O- (C ₆ H ₄ ) ₂ C (CH ₃ ) ₂ -O- (ZrCl based on zirconium (C ₅ H ₅ ) ₂ (hereinafter referred to as catalyst A) was simultaneously injected with 2 atmospheres of ethylene to initiate one-step polymerization. After 60 minutes, ethylene gas was discharged to sufficiently remove ethylene in the system.

(2) Second step: 56.6 mmol of MAO (based on aluminum) and 18.9 μmol of catalyst A based on zirconium were injected into the reactor, followed by initiation of two-step polymerization while injecting 2 atmospheres of ethylene, followed by polymerization for 60 minutes. Ethylene gas was then discharged. Hydrochloric acid / methanol mixed solution was added to stop the reaction and washed, and the resulting polymer was recovered. It dried over 120 hours under reduced pressure at 120 degreeC, and obtained 96 g of polymers.

Example 2

Except for using 1.1 ml of divinylbenzene (Aldrich, 80% by weight) instead of vinyl norbornene was carried out in the same manner as in Example 1, the polymer produced was 100 g.

Example 3

Except that the ethylene pressure of 4.5 atm in the second step was carried out in the same manner as in Example 1, the produced polymer was 228g.

Example 4

Example 1 except that (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (hereinafter referred to as catalyst B) was introduced in the second step. It carried out in the same manner as, the produced polymer was 83g.

Example 5

Example 1 except that rac-ethylene bis (indenyl) zirconium dichloride [rac-Et (Ind) ₂ ZrCl ₂ ] (hereinafter catalyst C) was injected in place of catalyst A in the first and second steps. It carried out in the same manner as 1, the polymer was 95g.

Example 6

The catalyst C was injected in the first step instead of the catalyst A, and the catalyst B was injected in the second step. The same method as in Example 1 was carried out, and the prepared polymer was 80 g.

Comparative Example 1

850 mL of purified toluene and 400 g of norbornene are dissolved in a 2 L high pressure reactor. 1.2 ml of vinyl norbornene and 49 mmol of triisobutylaluminum (based on aluminum) were added thereto, and the mixture was stirred and heated to 40 ° C. In a nitrogen atmosphere, 56.6 mmol of MAO (based on aluminum) and 18.9 μmol of catalyst A based on zirconium were injected, followed by injecting 2 atmospheres of ethylene to initiate one-step polymerization. After 60 minutes, ethylene gas was discharged to sufficiently remove ethylene in the system. Post-treatment was carried out in the same manner as in Example 1 to obtain 59 g of a polymer.

Comparative Example 2

Except for injecting the catalyst B instead of the catalyst A was carried out in the same manner as in Comparative Example 1, the produced polymer was 45g.

For the polymers prepared in Examples 1-6 and Comparative Examples 1-2, the content of ethylene, norbornene and vinylnorbornene in the polymer was measured by 1 H-NMR and 13 C-NMR analysis, and the weight average of the polymer in terms of polyethylene Obtain the molecular weight and the number average molecular weight, measure the melting point of the polymer with a differential scanning calorimeter, prepare a test specimen at a molding temperature of 200 ° C. in a mold according to ASTM D-256, and then 1/8 "notch. Izod impact strength was measured by specimens, and the results are shown in Table 1.

Example Comparative example One 2 3 4 5 6 One 2 Stage 1 Catalyst type Catalyst A Catalyst A Catalyst A Catalyst A Catalyst C Catalyst C Catalyst A Catalyst B Supply amount (μmol) 18.9 18.9 18.9 18.9 18.9 18.9 18.9 18.9 Ethylene (atmospheric pressure) 2 2 2 2 2 2 2 2 Diene type VN DVB VN VN VN VN VN VN Tier 2 Catalyst type Catalyst A Catalyst A Catalyst A Catalyst B Catalyst C Catalyst B - - Supply amount (μmol) 18.9 18.9 18.9 18.9 18.9 18.9 - - Ethylene (Pressure) 2 2 4.5 2 2 2 - - Yield (g) 96 100 228 83 95 80 59 45 Tg (℃) 143.4 144.6 118.4 142.1 142.9 141.7 141.6 140.1 Izod (kg f / cm / cm) 3.7 4.5 3.5 4.0 3.1 3.5 1.6 1.7 Diene content (% by weight) 0.30 0.47 0.25 0.39 0.18 0.27 0.33 0.42

Catalyst A: (C ₅ H ₅ ) ₂ (ZrCl) -O- (C ₆ H ₄ ) ₂ C (CH ₃ ) ₂ -O- (ZrCl) (C ₅ H ₅ ) ₂

Catalyst B: (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride

Catalyst C: rac-ethylene bis (indenyl) zirconium dichloride [rac-Et (Ind) ₂ ZrCl ₂ ]

VN: vinyl norbornene, DVB: divinylbenzene

The present invention copolymerizes α-olefins, cyclic olefins, and dienes in two steps using at least one metallocene catalyst and a cocatalyst, so that the impact resistance is significantly improved, and the heat resistance is maintained. It has the effect of the invention which has a branch, and is easy to adjust the content of ethylene and a cyclic olefin, the olefin / cyclic olefin / diene random copolymer, and its manufacturing method.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

1 is a process chart showing a method for producing a long-chain α-olefin / cyclic olefin / diene random copolymer according to the present invention.

Claims (20)

a first step of preparing an α-olefin / cyclic olefin / diene terpolymer having an active vinyl group by injecting at least one metallocene catalyst and a promoter into the α-olefin, cyclic olefin, and diene monomer mixture; And A second step of preparing a -olefin / cyclic olefin / diene random copolymer by injecting a metallocene catalyst and a cocatalyst into the product and the unreacted mixture of the first step and continuing polymerization; The diene weight ratio based on the cyclic olefin is 0.1 to 10,000 ppm (parts per million), and the use of the α-olefin in the first step and the second step is a molar ratio of the cyclic olefin to the α-olefin. It is in the range of 0.1 to 100, the molar ratio of the α-olefin in the two-step process: the α-olefin in the one-step process is in the range 0.1 to 100, wherein the metallocene catalyst is represented by the following formula (1) Process for the preparation of -olefin / cyclic olefin / diene copolymer: [Formula 1] Wherein M and M 'are independently transition metals of Group IV, V and VI of the periodic table; Cp, Cp', Cp "and Cp '" represent transition metals of Group IV, V and VI of the periodic table. one of the cyclopentadienyl, indenyl, fluorenyl, or derivatives thereof that produces a η ⁵ bond; X ₁ , X ₂ are each independently a hydrogen atom; a hydroxide (—OH); a halogen atom; C ₁ An alkyl group, a cycloalkyl group or an alkoxy group of _-20 ; an aryl group, an alkylaryl group, or an arylalkyl group of C _6-20 ; G is a linking of one transition metal to another transition metal, each independently of the formula -YR ⁶ Y ' (Y and Y 'in the formula -YR ⁶ Y'- are each independently an oxygen atom, a sulfur atom and -Nr ¹ or -Pr ² , R ⁶ is a formula R _a , R _b -OR _c ,- (R _b -OR _c ) or Wherein R _a , R _b , R _c , R _d and R _e are each independently C _1-20 straight alkyl or branched alkyl group, C _3-20 cycloalkyl group or substituted cycloalkyl group; Or C _6-40 aryl group, alkylaryl group or arylalkyl group, r ³ is a hydrogen atom; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-20 aryl group, alkylaryl group or aryl Alkyl group). The method of claim 1, wherein the second step is carried out in the same reactor as the first step or by transferring to another reactor. The method of claim 1, wherein the α-olefin / cyclic olefin / diene copolymer is further supplied in the second step. The method of claim 1, wherein the metallocene catalyst and the cocatalyst injected in the second step are the same as or different from those injected in the first step. The method of claim 1, wherein the α-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, and 1-octene. The method of claim 1, wherein the cyclic olefin is cyclobutene, cyclopentene, cyclohexene, 3,4-dimethyl cyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexyl, styrene, α -Methylstyrene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, norbornene, 5-methyl norbornene, 5,6-dimethyl norbornene, 1-methyl norbornene, 5 -Ethyl norbornene, 5-n-butyl norbornene, 5-isobutyl norbornene, 7-methyl norbornene, 5-phenyl norbornene, 5-methyl-5-phenyl norbornene, 5-benzyl norbornene, 5- Tolyl Norbornene, 5-ethylphenyl norbornene, 5-isopropylphenyl norbornene, 5-biphenyl norbornene, tetracyclo-3-dodecene, 8-methyl tetracyclo-3-dodecene, 8-ethyl tetracyclo Preparation of α-olefin / cyclic olefin / diene copolymer, characterized in that it is selected from the group consisting of -3-dodecene, 8-propyl tetracyclo-3-dodecene, 8-butyl tetracyclo-3-dodecene and the like. room . The method of claim 1, wherein the diene is a compound capable of coordination polymerization, 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, dicyclopentadiene, norbornadiene, 4-vinyl-1 -Cyclohexene, 3-vinyl-1-cyclohexene, 2-vinyl-1-cyclohexene, 1-vinyl-1-cyclohexene, o-divinylbenzene, p-divinylbenzene and m-di Process for producing α-olefin / cyclic olefin / diene copolymer, characterized in that selected from the group consisting of vinylbenzene. delete The metallocene catalyst of claim 8, wherein the metallocene catalyst is (C ₅ H ₅ ) ₂ (ZrCl) -O- (C ₆ H ₄ ) ₂ C (CH ₃ ) ₂ -O- (ZrCl) (C ₅ H ₅ ) ₂ , (C ₅ H ₅ ) ₂ (TiCl) -O- (C ₆ H ₄ ) ₂ C (CH ₃ ) ₂ -O- (TiCl) (C ₅ H ₅ ) ₂ ; rac-ethylenebis (indenyl) zirconium dichloride [rac-Et (Ind) ₂ ZrCl ₂ ], I-flofilidene (cyclopentadienyl) (fluorenyl) zirconium dichloride [i-Pr (Cp) ( Flu) ZrCl ₂ ], (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (CGC), α-olefin / cyclic olefin Method for preparing / diene copolymer. The molar ratio of the Group 4 transition metal in the catalyst component (moles of two-stage transition metals / one-stage transition) in the ratio of using the metallocene catalyst of the first step and the metallocene catalyst of the two step Metal mole) is 1-20, The manufacturing method of the alpha olefin / cyclic olefin / diene copolymer characterized by the above-mentioned. The method of claim 1, wherein the promoter is an organometallic compound or a mixture of non-coordinated Lewis acid and alkylaluminum. The method for producing α-olefin / cyclic olefin / diene copolymer according to claim 11, wherein the organometallic compound is an alkylaluminum oxane or an organoaluminum compound. 13. The method of claim 12, wherein the alkyl aluminum oxane is methylaluminoxane or modified methylaluminoxane. The α-olefin / cyclic olefin / diene air according to claim 12, wherein the organoaluminum compound has a unit represented by the following formula (2) and is a chain or cyclic aluminum oxane represented by the following formulas (3) and (4). Process for the preparation of coalescing. [Formula 2] [Formula 3] [Formula 4] (In the formula 2, 3 and 4, R 'is an alkyl group of C _1~6, p is an integer from 0 to 100). The method of claim 11, wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, triisobutyl aluminum, diisobutyl aluminum chloride, tri (n-butyl) aluminum, tri (n-propyl) ) Aluminum and triisopropyl aluminum; The non-coordinating Lewis acids include N, N-dimethyl aniline tetrakis (pentafluorophenyl) borate, triphenyl carbenium tetrakis (pentafluorophenyl) borate, ferrocerium tetrakis (pentafluorophenyl) borate, tris (Pentafluorophenyl) A method for producing an α-olefin / cyclic olefin / diene copolymer, which is selected from the group consisting of borates. 12. The molar ratio of the transition metal in the component of the alkylaluminum: metallocene catalyst, which is the cocatalyst, is in the range of 1: 1 to 100,000: 1, and the non-coordinating Lewis acid: metallocene catalyst, A molar ratio of the transition metal in the component is in the range of 0.1: 1 to 20: 1, wherein the α-olefin / cyclic olefin / diene copolymer production method. The molar ratio of aluminum to the Group 4 transition metal in the metallocene-based catalyst sum component, that is, the molar ratio of aluminum to transition metal is 0.1: 1 to 100,000: 1. It is a range, The manufacturing method of the alpha olefin / cyclic olefin / diene copolymer. delete delete delete