KR20180099269A - Catalyst composition for polymerizing olefin copolymer and preparation method of olefin copolymer - Google Patents

Abstract

The present invention relates to a catalyst composition for synthesizing an olefin co-polymer and a manufacturing method of the olefin co-polymer by using the catalyst composition, wherein the catalyst composition includes two-type metallocene catalysts, represented by a certain structure of chemical formula 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst composition for synthesizing an olefin copolymer, and a process for producing the olefin copolymer. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a catalyst composition for synthesizing an olefin copolymer and a process for producing the olefin copolymer.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad, The composition distribution is not uniform and there is a limit in securing desired physical properties.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Accordingly, there is a continuing need for a process for preparing an olefin polymer of desired properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

On the other hand, the linear low density polyethylene is a resin which is produced by copolymerizing ethylene and an alpha olefin at a low pressure using a polymerization catalyst, has a short molecular weight distribution and a short chain length and has no long chain branch. Linear low density polyethylene film has high tensile strength and elongation as well as general polyethylene characteristics, and has excellent tear strength and falling impact strength. Therefore, it is used for stretch film and overlap film which are difficult to apply low density polyethylene or high density polyethylene .

However, linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mostly prepared in a single gas phase reactor or a single loop slurry reactor, and productivity is high compared to the process using 1-octene comonomer. Due to limitations of catalyst technology and process technology, there is a problem that the physical properties are considerably weaker than when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability. Much effort has been made to improve these problems,

U.S. Patent No. 4,935,474 discloses a process for preparing polyethylene having a broad molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 discloses a process for producing polyethylene which is excellent in processability using a mixture of a monomer having good comonomer binding property and a monomer having no comonomer binding property and is particularly suitable for a film. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose that a polyethylene having at least two kinds of metal compounds is used as a metallocene-based catalyst and has a molecular weight distribution of at least two, and is used for films, blow molding, It is reported that it is applicable. However, these products have improved processability, but the dispersed state of the unit particles in molecular weight is not uniform, so that the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

Against this backdrop, there is a continuing need to produce better products with a balance between physical and processability, and further improvements are needed.

U.S. Patent No. 5914289 Korean Patent Application No. 2003-12308 US Patent No. 4935474 United States Patent No. 6828394 U.S. Patent No. 6841631 United States Patent No. 6894128

The present invention relates to a catalyst composition for olefin copolymer synthesis which can provide an olefin copolymer having high stiffness and crack resistance, which is excellent in environmental stress cracking resistance and processability, has high dimensional stability, and is required for a polymer injection product such as a bottle cap .

The present invention also relates to a process for preparing an olefin copolymer using the catalyst composition for synthesizing the olefin copolymer.

In the present specification, a first metallocene catalyst comprising a transition metal compound represented by the following general formula (1); And a second metallocene catalyst comprising a transition metal compound represented by the following formula (2): < EMI ID = 2.0 >

[Chemical Formula 1]

In Formula 1,

R ₁ is a straight or branched alkylene group having 1 to 10 carbon atoms, Ar ₁ is an aryl group having 6 to 20 carbon atoms,

Q1 is carbon, silicon or germanium;

A represents a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

L is a straight or branched alkylene group of C1 to C10;

R ₁₈ is hydrogen, halogen or a straight or branched alkyl group having 1 to 10 carbon atoms,

R ₂ to R ₁₇ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;

Two or more adjacent groups in one of the benzene rings of R ₂ to R ₁₇ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;

M ₁ is a Group 4 transition metal,

Y ₁ and Y ₂ are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group.

(2)

In Formula 2,

A ₁ represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, To C20 alkoxyalkyl groups, C3 to C20 heterocycloalkyl groups, or C5 to C20 heteroaryl groups;

D ₁ is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C1 C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

L ₁ is a straight or branched alkylene group of C1 to C10;

Wherein R ₂₁ to R ₂₉ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;

Two or more adjacent groups in the benzene ring of R ₂₁ to R ₂₉ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;

M ₂ is a Group 4 transition metal,

Y ₁₁ and Y ₁₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group.

The present inventors have found that when a catalyst composition comprising a first metallocene catalyst containing a transition metal compound represented by the general formula (1) and a second metallocene catalyst comprising the transition metal compound represented by the general formula (2) It is possible to provide an olefin copolymer having high stiffness and crack resistance, which is excellent in environmental stress cracking property and processability, has high dimensional stability, and is required for a polymer injection product such as a bottle cap, Respectively.

The transition metal compound of Formula 1 has a structure in which R1 and AR1 are linked to nitrogen of an indenoindole derivative. This structure is a novel one not previously known. Due to the structure in which R1 and AR1 are connected to each other, And relatively low hydrogen reactivity with higher activity for alpha olefins. Accordingly, the transition metal compound of Formula 1 in the catalyst composition may be a factor controlling the molecular weight and physical properties of the olefin copolymer to be produced.

Meanwhile, as described above, the first metallocene catalyst containing the transition metal compound of Formula 1 contributes mainly to the formation of a high molecular weight copolymer, and the first metallocene catalyst of Formula 2, which is used together with the first metallocene catalyst, A second metallocene catalyst comprising a transition metal compound can contribute primarily to making low molecular weight copolymers.

Particularly, the transition metal compound of the above formula (2) is a compound in which the functional group of A ₁ -D ₁ -L ₁ is bonded to the indenyl group in the cyclopentadienyl group and the indenyl group bonded around the transition metal, The cyclopentadienyl group and the indenyl group bonded together with the transition metal as a center can be used to synthesize the low molecular weight olefin copolymer at higher efficiency , High hydrogen reactivity and high C2 reactivity.

Thus, by using the catalyst composition including the first metallocene catalyst and the second metallocene catalyst, it is possible to produce both high molecular weight and low molecular weight copolymers, and by controlling the process conditions or the monomers to be used The molecular weight and physical properties of the olefin-based copolymer to be synthesized can be more easily controlled.

Specific examples of the transition metal compound represented by the above formula (1) are not limited to the above-described ranges of the above-mentioned chemical formula, but more preferred examples are as follows:

Wherein R ₁ is a straight or branched alkylene group having 1 to 5 carbon atoms, Ar ₁ is benzene,

R ₃ is a straight or branched alkyl group having 1 to 10 carbon atoms,

R < ₁₈ > is an alkyl group having 1 to 3 carbon atoms,

A ₁ is a linear or branched alkyl group having 3 to 8 carbon atoms,

D ₁ is oxygen or sulfur,

L &_lt; ₁ > is a straight chain alkyl group having 3 to 8 carbon atoms,

Wherein R ₂ to R ₁₇ are hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,

M ₁ is titanium, zirconium or hafnium, and Y ₁ and Y ₂ are halogen.

Specific examples of the transition metal compound of the above-mentioned formula (2) are not limited to the above-mentioned ranges of the above-mentioned formulas, but more preferred examples are as follows:

In Formula 2,

A is a linear or branched alkyl group having 3 to 8 carbon atoms,

D is oxygen or sulfur,

L is a straight chain alkyl group having 3 to 8 carbon atoms,

R ₂₁ to R ₂₉ are hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,

M ₁ is titanium, zirconium or hafnium, and Y ₁ and Y ₂ are halogen.

On the other hand, in the catalyst composition for synthesizing an olefin copolymer, the molar ratio of the first metallocene catalyst containing the transition metal compound of Formula 1 to the second metallocene catalyst of Formula 2 is very limited However, in order to maximize the effects of the above-mentioned effects, for example, high environmental stress cracking resistance and excellent processability, and high rigidity and crack resistance required for polymer injection products such as bottle caps, The molar ratio of the second metallocene catalyst comprising the transition metal compound of Formula 2 to the first metallocene catalyst comprising the metal compound may be 1.5-4.

If the molar ratio of the first metallocene catalyst comprising the transition metal compound of Formula 1 to the second metallocene catalyst comprising the transition metal compound of Formula 2 is too low compared to the first metallocene catalyst comprising the transition metal compound of Formula 1, The difference in the activity becomes excessive, so that the low molecular weight portion of the olefin copolymer produced from the catalyst composition becomes insufficient and thus the workability and the like may be lowered.

If the molar ratio of the first metallocene catalyst containing the transition metal compound of Formula 1 to the second metallocene catalyst of Formula 2 is too high, the first and second metallocene catalysts The activity difference between the olefin copolymer and the olefin copolymer produced from the catalyst composition becomes insufficient and the high-molecular-weight portion thereof becomes insufficient, thereby degrading the environmental stress cracking property and the like.

The catalyst composition for synthesizing an olefin copolymer may further contain a cocatalyst or a carrier.

The cocatalyst is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used when olefins are polymerized under a general metallocene catalyst.

Specifically, the promoter compound may include at least one of an aluminum-containing primary catalyst of the following general formula (6) and a boron-containing secondary catalyst of the general formula (7).

[Chemical Formula 6]

- [Al (X) -O-] _k-

In Formula 6, X is independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

 (7)

T ⁺ [BG ₄ ] ^-

In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.

By using such first and second co-catalysts, the molecular weight distribution of the finally produced polyolefin becomes more uniform, and the polymerization activity can be improved.

The first cocatalyst of formula (6) may be an alkylaluminoxane compound having a linear, circular or network-like repeating unit bonded thereto. Specific examples of the first catalyst include methylaluminoxane (MAO), ethylaluminium Isobutylaluminoxane, butylaluminoxane, and the like.

Also, the second cocatalyst of formula (7) may be a tri-substituted ammonium salt, or a dialkylammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetradecyclooctadecylammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium (Tetrafluoroborate) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyl dioctadecylammonium tetrakis (Pentafluorophenyl) borate, triphenyl ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium (Pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6- Boronate in the form of a tri-substituted ammonium salt such as N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) compound; A borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) compound; (Pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylphosphonium tetrakis ) Borate and the like, and the like.

The mass ratio of the carrier to the total weight of the transition metal contained in the first metallocene compound and the second metallocene compound may be 10 to 10,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape.

In addition, the mass ratio of the cocatalyst compound to the carrier may be from 1: 1 to 1: 100. The mass ratio of the first metallocene compound represented by Formula 1 to the second metallocene compound represented by Formulas 3 to 5 is 10: 1 to 1:10, preferably 5: 1 to 1: 5 Lt; / RTI > When the cocatalyst and the metallocene compound are contained in the mass ratio, the activity and the polymer microstructure can be optimized.

On the other hand, the carrier may be a carrier containing a hydroxy group on its surface, preferably a carrier having a hydroxyl group and a siloxane group, which are dried and removed moisture from the surface, and have high reactivity.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

On the other hand, the catalyst composition for synthesizing an olefin copolymer includes a step of supporting a promoter compound on a support, supporting the first metallocene compound represented by the formula 1 on the support, And a second metallocene compound selected from the group consisting of compounds represented by the following general formula (1).

The order of the step of supporting the first metallocene compound and the step of supporting the second metallocene compound may be changed as necessary. That is, the first metallocene compound is first supported on the carrier, and then the second metallocene compound is further supported to prepare a hybrid supported metallocene catalyst. Alternatively, the second metallocene compound is supported on the carrier The first metallocene compound may be further supported on the support to prepare a hybrid supported metallocene catalyst.

In the preparation of the catalyst composition for synthesizing an olefin copolymer, a hydrocarbon solvent such as pentane, hexane or heptane, or an aromatic solvent such as benzene or toluene may be used as a reaction solvent. In addition, the metallocene compound and the co-catalyst compound may be used in the form supported on silica or alumina.

The catalyst composition for synthesizing an olefin copolymer may itself be used for polymerization of an olefin-based monomer. The catalyst composition for synthesizing an olefin copolymer may be prepared by reacting with an olefin monomer to prepare a prepolymerized catalyst. For example, the catalyst may be used separately as ethylene, propylene, 1-butene, 1-hexene, It may be prepared by contacting with an olefin-based monomer to prepare a prepolymerized catalyst.

On the other hand, in the present specification, a method for producing an olefin copolymer, which comprises copolymerizing ethylene and an alpha-olefin in the presence of the catalyst composition for synthesizing an olefin copolymer as described above, may be provided.

The olefin monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin having 2 or more double bonds or triene olefin, and more specific examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, Norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, Divinylbenzene, 3-chloromethylstyrene, and the like, and two or more of these monomers may be mixed and copolymerized.

The olefin-based polymer is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.

In the case where the olefin-based polymer is an ethylene / alpha olefin copolymer, the content of the alpha-olefin as the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose and the like of the olefin-based polymer. More specifically, it may be more than 0 and 99 mol% or less.

The copolymerization or polymerization reaction can be homopolymerized with one olefin monomer or copolymerized with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The copolymerization temperature may be about 25 to about 500 캜, preferably about 25 to about 200 캜, more preferably about 50 to about 150 캜. The polymerization pressure may be from about 1 to about 100 Kgf / cm ^2, preferably about 1 to about 50 Kgf / cm ^2, more preferably from about 5 to about 30 Kgf / cm ^2.

The catalyst composition for synthesizing an olefin copolymer may be prepared by reacting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and an aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane, Or a hydrocarbon solvent substituted with a chlorine atom, for example. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The characteristics of the olefin copolymer provided in the process for producing an olefin copolymer using the catalyst composition for synthesizing an olefin copolymer are as follows.

As described above, the olefin copolymer is excellent in processability due to its wide melt flow index and melt flow rate ratio, and has high molecular weight, broad molecular weight distribution and excellent short chain branching (SCB) per 100 high carbon Rigidity and crack resistance.

Specifically, the olefin copolymer has a weight average molecular weight of 100,000 to 300,000 g / mol, a molecular weight distribution (Mw / Mn) of 5 to 30, a density of 0.930 to 0.960 g /

(Log M) of the molecular weight (M) with respect to the olefin copolymer is represented by the x-axis and the branch content of 2 to 7 carbon atoms per 1,000 carbon atoms is represented by the y-axis, the logarithm of the molecular weight (M) The difference between the average slope value in the range of the value of log M (M) to 3 to Mp and the average slope value in the range of the log value (log M) of the molecular weight (M) in the range of Mp to 5.5 may be 2 or more. Wherein Mp is a maximum value in a GPC curve graph plotting the logarithm (log M) of the molecular weight (M) of the olefin copolymer along the x axis and the molecular weight distribution (dw / dlog M) Denotes the numerical value of the x-axis (log M) appearing, and w denotes the weight fraction.

More specifically, in a graph in which the logarithm (log M) of the molecular weight (M) relative to the olefin copolymer is represented by the x-axis and the branch content of 2 to 7 carbon atoms per 1,000 carbon atoms is represented by the y-axis, The average slope value in the range of logarithm (log M) of 3 to Mp may be larger than the average slope value of logarithm (log M) of molecular weight M in the range of Mp to 5.5.

(Log M) of the molecular weight (M) with respect to the olefin copolymer is represented by the x-axis and the branch content of 2 to 7 carbon atoms per 1,000 carbon atoms is represented by the y-axis, the molecular weight The average slope value (slope 1) in the range of the log value (log M) of 3 to Mp may be related to the stiffness and crack resistance of the olefin copolymer, and the log value (log M) of the molecular weight The average slope value (slope 2) in the range of Mp to 5.5 can be related to the stiffness of the olefin copolymer and the dimensional stability of the polymer.

Wherein Mp is a maximum value in a GPC curve graph plotting the logarithm (log M) of the molecular weight (M) of the olefin copolymer along the x axis and the molecular weight distribution (dw / dlog M) It means the value of x axis (log M) appearing. Based on this value, the left side can be classified into the low molecular weight region and the right side can be classified into the high molecular weight region.

Accordingly, as the difference between the slope 1 and the slope 2 is 2 or more, particularly, the slope 1 has a larger value than the slope 2, the SCB increases as the molecular weight increases before the Mp value, and Mp The olefin copolymer may have a polymer structure having SCB of a certain level or more after the value, and thus the olefin copolymer may have high workability and high rigidity and crack resistance

More specifically, the logarithm of the molecular weight (M) in the graph of the logarithm (log M) of the molecular weight (M) as the x axis and the branching content of 2 to 7 carbon atoms per 1,000 carbon atoms as the y axis (log 1 M) in the range of 3 to Mp may be 2 to 15 and the logarithm M of the molecular weight M may be the average slope value in the range of Mp to 5.5 Slope 2) may be -3 to 3 (in this case, the slope 1 is larger than the slope 2).

In the graph in which the logarithm (log M) of the molecular weight (M) relative to the olefin copolymer is represented by the x-axis and the branch content of 2 to 7 carbon atoms per 1,000 carbon atoms is represented by the y-axis, the value of the slope 1 2 to 15, the olefin copolymer can have a high rigidity required for a polymer injection product and can not be easily broken. Thus, a highly rigid container requiring high pressure resistance and chemical resistance and a high rigidity Bottle caps and the like.

Further, in a graph in which the logarithm (log M) of the molecular weight (M) relative to the olefin copolymer is represented by the x-axis and the branch content of 2 to 7 carbon atoms per 1,000 carbon atoms is represented by the y-axis, Depending on whether the value is between -3 and 3, the olefin copolymer can have improved crack resistance with higher dimensional stability.

In the above, Mw denotes a weight-average molecular weight, and w denotes a weight fraction. In addition, a GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw can be defined based on the molecular weight measured through GPC or the like.

Meanwhile, more specific characteristics of the olefin copolymer of one embodiment are as follows.

The weight average molecular weight (Mw) of the olefin copolymer may be 100,000 to 300,000 g / mol. More preferably, the weight average molecular weight may be at least 120,000 g / mol, at least 130,000 g / mol, or at least 140,000 g / mol, at most 250,000 g / mol, or at most 220,000 g / mol, or at most 200,000 g / mol .

In the olefin copolymer, the olefin polymer according to the present invention may have a molecular weight distribution (Mw / Mn) of 5 to 30, or 7 to 20. The olefin-based polymer having such a broad molecular weight distribution can exhibit better processability.

The olefin copolymer may have a density of 0.930 to 0.960 g / cm < ³ > but is not limited thereto.

Further, the olefin copolymer may be a _.16 MFR ₂ of 0.01 to 1.0 g / 10min (the melt flow index measured at 190 ℃, 2.16 kg load in accordance with ASTM D1238). The MFR _{2 .16} and more preferably is, 0.05 g / 10min or higher, or 0.1 g / 10min or higher, 0.15 g / 10min and not more than, 0.9 g / 10min or less, or 0.8 g / 10min or less, or 0.6 g / 10min may be below have.

The olefin copolymer preferably has an MFRR of _{5 / 2.16} (a melt flow index measured at 190 占 폚 under a load of 5 kg according to ASTM D1238 _divided by a melt flow index measured at 190 占 폚 under a load of 2.16 kg) of 4 to 20 Value. More preferably, the MFRR _{5 /2.16} may be 4 or more, or 4.2 or more, or 4.3 or more, 10 or less, or 9.5 or less, or 9 or less.

The spiral flow length (190 DEG C, 90 bar) shows the workability of the ethylene / alpha-olefin copolymer. The larger the value, the better the processability. For example, for the olefin copolymer, an ENGEL 150 ton injector is used and the spiral flow length (SF) measured with a mold thickness of 1.5 mm, an injection temperature of 190 DEG C, a mold temperature of 50 DEG C and an injection pressure of 90 bar The spiral flow length may be more than 13 cm or 15 cm, and the upper limit thereof is not limited, but may be 30, for example.

In addition to the above mechanical properties and processability, the olefin copolymer is also characterized by excellent environmental stress crack resistance (ESCR).

In general, the processability and the environmental stress cracking property are conflicting physical properties. When the melt index is increased in order to improve processability, the environmental stress cracking property is lowered. However, the olefin copolymer satisfies both good processability and environmental stress cracking resistance.

The olefin copolymer may have an environmental stress cracking resistance (ESCR) of 200 hours or more, or 240 hours or more, or 300 hours or more as measured according to ASTM D 1693. When the environmental stress cracking resistance (ESCR) is 200 hours or more, the performance can be stably maintained in the state of use for the bottle cap. Therefore, the upper limit value is not substantially significant, but may be 1,000 hours or less, or 800 hours or less, . Since it exhibits a high performance environmental stress cracking property as described above, it can be molded into a food container product such as a bottle cap and can maintain its continuous performance even when it is used under high temperature and high pressure conditions.

According to the present invention, there is provided a catalyst for synthesizing an olefin copolymer capable of providing an olefin copolymer having high stiffness and crack resistance, which is excellent in environmental stress cracking resistance and processability, has high dimensional stability, and is required for a polymer injection product such as a bottle cap A composition and a process for preparing an olefin copolymer can be provided.

1 is a graph showing the logarithmic value (log M) of the molecular weight (M) relative to the olefin copolymer obtained in Example 3 as the x axis and the branch content of 2 to 7 carbon atoms per 1,000 carbon atoms as the y axis And a GPC curve graph in which the logarithm (log M) of the molecular weight (M) is represented by the x-axis and the molecular weight distribution (dw / dlog M) relative to the logarithm is represented by the y-axis.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[Preparation Example: Preparation of metallocene compound]

Production Example 1

Preparation of 1-1 ligand compounds

(Reaction scheme 1-1)

3.0 g (9.7 mmol) of the starting material in Reaction Scheme 1-1 was dissolved in 4.6 mL of MTBE (38.8 mmol) and hexane (100 mL) and 4.3 mL (10.7 mmol) of 2.5 M n-BuLi hexane solution was added to the solution in dry ice / acetone bath And the mixture was stirred at room temperature overnight. (2.6 g) of 6- (tert-butoxy) hexyl dichloro (methyl) silane was dissolved in 50 mL of hexane, and the Li slurry was dropwise added dropwise via a cannula under a dry ice / acetone bath. After completion of the dropwise addition, the temperature of the reaction was slowly raised to room temperature and then stirred overnight at room temperature. At the same time, 1.6 g (9.7 mmol) of Fluolene was dissolved in THF and 4.3 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. The synthesized intermediate was continuously used in the reaction without NMR confirmation.

The lithiated solution of Fluolene was slowly added dropwise to the silicon solution in a dry ice / acetone bath and stirred overnight at room temperature. After the reaction, the residue was extracted with ether / water, and the residual moisture of the organic layer was removed with MgSO ₄ to obtain 7.4 g of a ligand compound (Mw: 834.11, 11 mmol).

^{1 H NMR (500 MHz, CDCl} 3): 7.90 ~ 6.98 (20H, m), 5.67 (2H, s), 4.31 ~ 3.89 (2H, m), 3.18 (2H, m), 2.37 (3H, d), 1.33-1.25 (6H, m), 1.15 (9H, s), 0.91 (4H, m)

Preparation of 1-2 metallocene compounds

(Reaction scheme 1-2)

7.4 g (Mw: 834.11, 11 mmol) of the ligand compound synthesized in 1-1 above was dissolved in 80 mL of toluene and 5.2 mL (44 mmol) of MTBE and 9.7 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath And stirred at room temperature overnight.

ZrCl ₄ (THF) ₂ was prepared and 80 mL of toluene was added to prepare a slurry. An 80 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice / acetone bath. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and then hexane was added thereto for sonication for 1 hour. The slurry was filtered to obtain 5.9 g of a filtered solid metallocene compound (yield 70.1 mol%, purity 92.8 wt%).

^{1 H NMR (500 MHz, CDCl} 3): 7.92 ~ 6.69 (20H, m), 5.49 (2H, m), 3.36 (2H, m), 2.55 (3H, s), 2.55 (3H, s), 2.08 ( (2H, m), 1.81 (2H, m), 1.60 (4H, m), 1.24

[Production example of second metallocene compound]

Production Example 2

(CH ₂ ) ₆ -Cl was prepared by the method described in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol and reacted with Indene to give t-Butyl-O- _{t-Butyl-O- (CH 2} ) to give the ₆ -Indene.

Further, t-Butyl-O- (CH ₂ ) ₆ -Indene was dissolved in THF at -78 ° C, and then normal butyl lithium (n-BuLi) was added slowly, and the temperature was raised to room temperature, followed by reaction for 8 hours. The solution was again at -78 ℃ ZrCl ₄ (THF) ₂ (1 equivalent) / THF (30 ml) was added slowly and the mixture was further reacted at room temperature for 6 hours.

Cyclopentadiene (1 eq.) Was dissolved in THF and n-butyllithium (n-BuLi) was added slowly. The temperature was raised to room temperature and the reaction was carried out for 8 hours. The solution _{t-Butyl-O- (CH 2} ) was added slowly to a solution of ₆ -Indene mixture was allowed to react at room temperature for 6 hours.

Then, all volatile substances were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to be filtered. The filtered solution was vacuum dried.

¹ H NMR (500 MHz, CDCl ₃ ): 7.92-6.69 (4H, m), 6.69-5.49 (6H, m), 1.80-1.22 (10H, m), 1.11 )

[Example: Preparation of hybrid supported catalyst]

Example 1

100 mL of toluene solution was added to a 250 mL glass high pressure reactor and the reactor temperature was maintained at 40 ° C. 1,000 g of silica (SYLOPOL 948, manufactured by Grace Davison), which was dehydrated by applying a vacuum at a temperature of 600 캜 for 12 hours, was charged into the reactor and the silica was sufficiently dispersed. Then, the metallocene compound of Preparation Example 2 was dissolved in 0.29 mmol / ₂ in toluene, and the mixture was reacted at 40 ° C for 2 hours with stirring. Then, 50 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added to the reactor, and the mixture was stirred at 40 ° C and 200 rpm for 12 hours.

After completion of the stirring, the metallocene compound of Preparation Example 1 was added to the reactor at a rate of 0.11 mmol / g SiO ₂ , and the mixture was reacted at 40 ° C with stirring at 200 rpm for 12 hours.

The reactor was charged with 3.0 kg of hexane, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. Followed by drying under reduced pressure at 40 DEG C for 4 hours to prepare 8 g of hybrid supported catalyst.

Example 2

In the same manner as in Example 1 except that the metallocene compound of Preparation Example ₂ was changed to 0.25 mmol / g SiO ₂ and the metallocene compound of Production Example 1 was added to 0.10 mmol / g SiO ₂ in Example 1, Catalyst.

Example 3

A supported catalyst was prepared in the same manner as in Example 2, except that a 20 L SUS reactor was used as a carrier in a unit of 1 Kg and the amount of the used material was changed accordingly.

Comparative Example 1

The olefin copolymer (ME1000, manufactured by LG Chemical), which was prepared with a Ziegler-Natta catalyst, was used as Comparative Example 1.

<Experimental Example>

Evaluation of physical properties of polymer

1) Density: ASTM 1505

2) Melt Index (MFR, 2.16 kg / 21.6 kg): Measuring temperature 190 占 폚, ASTM 1238

3) MFRR _(0.6 MFR ₂₁ / MFR _{2 .16):} MFR is _0.6 to _21, a melt index (MI, 21.6kg load) divided by the rate MFR _{2 .16} (MI, 2.16kg load).

4) Molecular weight and molecular weight distribution: 1, 2, 4-Trichlorobenzene containing 0.0125% of BHT was dissolved in PL-SP260 at 160 ° C for 10 hours and PL-GPC220 was used. , And the weight average molecular weight was measured. The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

Using the measured GPC data, a GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw is derived.

5) ESCR: The time to F50 (50% destruction) was measured using a 10% Igepal CO-630 Solution according to ASTM D 1693 at a temperature of 50 ° C.

6) Spiral flow length (SF): An ENGEL 150-ton injection machine was used. The mold thickness was 1.5 mm, the injection temperature was 190 ° C, the mold temperature was 50 ° C, and the injection pressure was 90 bar.

7) Short chain branch (SCB) content (branch content of 2 to 7 carbon atoms per 1,000 carbon units, unit: 1,000C) was measured. Specifically, the sample was pre-treated with 1, 2, 4-Trichlorobenzene containing 0.0125% of BHT at 160 ° C. for 10 hours using PL-SP260VS and then subjected to PerkinElmer Spectrum 100 FT- IR at 160 &lt; 0 &gt; C.

8) Measurement of crack resistance

Specimens were prepared by injecting the olefin copolymer obtained in each of Examples and Comparative Examples in the form of a bottle cap (width 28 mm, thickness 1 mm). Then, the pieces were bonded to a PET preform holder, placed in a 42 ° C igepal 5% solution bath, and a water pressure of 5 bar was applied to the line connected to the inside of the PET preform from the outside. The initial point of occurrence of cracks in the specimen was monitored to determine the average point of time of 10 specimens.

Experimental Example 1: Ethylene-1-hexene copolymerization

Each of the hybrid supported metallocene catalysts prepared in Example 1 and Example 2 was charged into a 2 L CSTR reactor (continuous stirred tank reactor) to prepare an olefin polymer. 1-hexene was used as the comonomer, and the reactor pressure was maintained at 10 bar and the polymerization temperature was maintained at 90 ° C.

The polymerization conditions using the hybrid supported metallocene catalysts of Examples 1 and 2 and the physical properties of the synthesized ethylene-1-hexene copolymer are summarized in Table 1 below.

Catalyst (mmol / gSiO ₂₎ Polymerization conditions MW (Kg / mol) MWD MI MFRR SCB count
(mol%) Production Example 1 Production Example 2 Hydrogen
(Volume ratio to C2) 1-hexene (cc) Example 1 0.29 0.11 0.25 10 142,000 12.9 0.42 7.37 5.0 Example 2 0.25 0.10 0.25 10 190,000 15.1 0.25 7.45 5.4

Experimental Example 2 : Ethylene-1- Hexen  Copolymerization

Each of the hybrid supported metallocene catalysts prepared in Example 3 was charged into a 50 L CSTR reactor (continuous stirred tank reactor) to prepare an olefin polymer. 1-hexene was used as the comonomer, and the reactor pressure was maintained at 10 bar and the polymerization temperature was maintained at 90 ° C. In this case, as shown in Table 2 below, the polymerization conditions were changed from Example 3 to Example 4.

The polymerization conditions using the hybrid supported metallocene catalysts of Examples 3 and 4 and Comparative Example 1 are summarized in Table 2 below, and physical properties of the obtained polymers are shown in Table 3 below.

Catalyst (mmol / gSiO ₂₎ Polymerization conditions Production Example 1 Production Example 2 Hydrogen (g / hr) 1-butene (cc / min) Example 3 0.25 0.11 2 6 Example 4 0.25 0.11 2.5 6 Comparative Example 1 Ziegler Natta catalyst 6

division Comparative Example 1 Example 3 Example 4 MW (Kg / mol) 140,925 125,300 150,450 MWD 5.9 21.2 18.0 MI 2.2 1.20 0.51 MFRR 3.2 5.45 6.20 density
(g / cm3) 0.952 0.952 0.951 Mp 4.8 3.9 4.3 Slope 1 0.2 7.5 5.0 Tilt 2 0.1 1.4 -0.5 SCB count 3.1 5.8 6.0 Crack resistance (Hr) 8 95 90 ESCR (Hr) 25 350 340 Spiral (cm) 8 22 20

1) The Mp is a maximum value in a GPC curve graph showing a logarithm (log M) of the molecular weight (M) of the olefin copolymer as the x axis and a molecular weight distribution (dw / dlog M) Means the value of the x axis (log M) where the value appears.

2) slope 1 means the mean slope value in the range of the logarithm of the molecular weight (M) (log M) in the range of 3 to Mp and slope 2 means the logarithm of the molecular weight (M) in the range of Mp to 5.5 Means the mean slope value in the range.

1, the logarithm (log M) of the molecular weight (M) relative to the olefin copolymer prepared using the catalyst of Example 3 was plotted on the x-axis and the number of carbon atoms the logarithm of the slope 1 (the logarithm of the logarithm of the molecular weight (M) in the range of 3 to Mp) and the slope of the logarithm of the logarithm of the logarithm of the molecular weight (M) M)] is greater than or equal to 2, specifically, the slope 1 is within the range of 2 to 15 and the slope 2 is within the range of from -3 to 3. [

As shown in Table 2 above, the olefin copolymer obtained by using the mixed metallocene catalyst of the above-mentioned example has a spiral flow length of at least 300 hours and a relatively high spiral flow length and a SCB number of 4 or more , Bottle caps, and other polymer injection products, as well as high rigidity and crack resistance.

Claims (9)

A first metallocene catalyst comprising a transition metal compound of Formula 1; And
A second metallocene catalyst comprising a transition metal compound represented by the following formula (2): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
R ₁ is a straight or branched alkylene group having 1 to 10 carbon atoms, Ar ₁ is an aryl group having 6 to 20 carbon atoms,
Q1 is carbon, silicon or germanium;
A represents a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L is a straight or branched alkylene group of C1 to C10;
R ₁₈ is hydrogen, halogen or a straight or branched alkyl group having 1 to 10 carbon atoms,
R ₂ to R ₁₇ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;
Two or more adjacent groups in one of the benzene rings of R ₂ to R ₁₇ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
M ₁ is a Group 4 transition metal,
Y ₁ and Y ₂ are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group,
(2)

In Formula 2,
A ₁ represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, To C20 alkoxyalkyl groups, C3 to C20 heterocycloalkyl groups, or C5 to C20 heteroaryl groups;
D ₁ is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C1 C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L ₁ is a straight or branched alkylene group of C1 to C10;
Wherein R ₂₁ to R ₂₉ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;
Two or more adjacent groups in the benzene ring of R ₂₁ to R ₂₉ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
M ₂ is a Group 4 transition metal,
Y ₁₁ and Y ₁₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group.
The method according to claim 1,
Wherein R ₁ is a straight or branched alkylene group having 1 to 5 carbon atoms, Ar ₁ is benzene,
R ₃ is a straight or branched alkyl group having 1 to 10 carbon atoms,
R &lt; ₁₈ &gt; is an alkyl group having 1 to 3 carbon atoms,
A ₁ is a linear or branched alkyl group having 3 to 8 carbon atoms,
D ₁ is oxygen or sulfur,
L &_lt; ₁ &gt; is a straight chain alkyl group having 3 to 8 carbon atoms,
Wherein R ₂ to R ₁₇ are hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,
M ₁ is titanium, zirconium or hafnium, Y ₁ and Y ₂ are halogen,
A catalyst composition for synthesizing an olefin copolymer.
The method according to claim 1,
In Formula 2,
A is a linear or branched alkyl group having 3 to 8 carbon atoms,
D is oxygen or sulfur,
L is a straight chain alkyl group having 3 to 8 carbon atoms,
R ₂₁ to R ₂₉ are hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,
M ₁ is titanium, zirconium or hafnium, and Y ₁ and Y ₂ are halogen.
The method according to claim 1,
Wherein the molar ratio of the first metallocene catalyst comprising the transition metal compound of Formula 1 to the second metallocene catalyst comprising the transition metal compound of Formula 2 is from 1.5 to 4,
A catalyst composition for synthesizing an olefin copolymer.
The method according to claim 1,
Wherein the catalyst composition for synthesizing an olefin copolymer further comprises a cocatalyst or a carrier.
6. The method of claim 5,
Wherein the cocatalyst comprises at least one member selected from the group consisting of compounds represented by formulas (6) and (7):
[Chemical Formula 6]
- [Al (X) -O-] _k-
In Formula 6, X is independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
(7)
T ⁺ [BG ₄ ] ^-
In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.
6. The method of claim 5,
Wherein the mass ratio of the transition metal contained in the first metallocene compound and the second metallocene compound to the total weight of the transition metal is 10 to 10,000.
6. The method of claim 5,
Wherein the weight ratio of the cocatalyst to the support is in the range of 1 to 100.
A process for producing an olefin copolymer, comprising the step of copolymerizing ethylene and an alpha-olefin in the presence of the catalyst composition for the synthesis of an olefin copolymer of claim 1.

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