KR102395103B1 - Method for preparing ethylene-alphaolefin copolymer - Google Patents

Abstract

The present invention relates to a method for preparing a copolymer of ethylene-alpha olefin having excellent physical properties, while reducing the generation of wax in the polymerization process to improve process stability, and SCB (short chain branch) content And through BOCD (Broad Orthogonal Co-monomer Distribution) structure control, melt index and melt flow rate ratio (MFRR, Melt Flow Rate Ratio), such as ethylene-alpha olefin copolymer that can implement excellent melt properties it's about how to

Description

Ethylene-alpha olefin copolymer manufacturing method {METHOD FOR PREPARING ETHYLENE-ALPHAOLEFIN COPOLYMER}

The present invention relates to a method for preparing a copolymer of ethylene-alpha olefin having excellent physical properties.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s. There is a problem in that there is a limit in securing desired properties because the distribution is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing an organometallic compound containing aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. , and has a narrow molecular weight distribution according to the single active point characteristic, and a polymer with a uniform composition distribution of comonomers is obtained. In addition, it has a characteristic that can change the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer according to the modification of the ligand structure of the catalyst and the change of polymerization conditions.

Specifically, U.S. Patent No. 5,032,562 describes a method for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is a method of producing a bimodal distribution polymer by supporting a titanium (Ti)-based Ziegler-Natta catalyst for generating a high molecular weight and a zirconium (Zr)-based metallocene catalyst for generating a low molecular weight on one support. Accordingly, there are disadvantages in that the supporting process is complicated and the morphology of the polymer is deteriorated due to the cocatalyst.

U.S. Patent No. 5,525,678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a non-metallocene compound on a carrier. This has disadvantages in that the metallocene compound and the non-metallocene compound must be supported separately, and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 discloses a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used in preparing the supported catalyst and preparation time are long, and , the inconvenience of having to support each of the metallocene catalysts to be used on a carrier followed.

Therefore, in order to solve the above disadvantages, there is a continuing demand for a method for preparing an olefin-based polymer having desired properties by simply preparing a hybrid supported metallocene catalyst having excellent activity.

The present invention, while reducing the generation of wax in the polymerization process, can improve process stability, while controlling the SCB (short chain branch) content and BOCD (Broad Orthogonal Co-monomer Distribution) structure, the melt index (Melt Index) and melt flow rate ratio (MFRR, Melt Flow Rate Ratio), etc., to provide a method for preparing an ethylene-alpha olefin copolymer that can implement excellent melt properties.

The present invention;

Step A) of supplying a compound represented by the following Chemical Formula 3 to the reaction system;

at least one first transition metal compound represented by the following Chemical Formula 1 by increasing the temperature of the reaction system to a polymerization temperature; at least one second transition metal compound represented by the following formula (2); and a step B) of supplying a supported hybrid catalyst including a carrier supporting the first and second transition metal compounds to the reaction system; and

In the reaction system, under the supply of hydrogen gas, comprising the step C) of copolymerizing ethylene and alpha olefin;

A method for preparing an ethylene-alpha olefin copolymer is provided.

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal,

R ₁₀ to R ₁₉ are the same as or different from each other, and each independently represents a hydrogen, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, and a C 2 to C 30 hydrocarbyloxy hydrocarbyl group. with the proviso that at least one of R ₁₀ to R ₁₉ is -(CH ₂ ) _n -OR (in this case, R is a linear or branched chain alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 10) ;

X ₁₁ and X ₁₂ are the same as or different from each other and are each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, —SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms;

[Formula 2]

In Formula 2,

M ₂ is a Group 4 transition metal,

Z is -O-, -S-, -NR ₂₁ - or -PR ₂₂ -, R ₂₁ and R ₂₂ are the same or different from each other, and each independently hydrogen, a C 1 to C 20 hydrocarbyl group, 1 to C 1 to Any one of a 20 hydrocarbyl (oxy) silyl group and a silyl hydrocarbyl group having 1 to 20 carbon atoms,

X ₂₁ and X ₂₂ are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,

또는

이고,T ₁ is

or

ego,

T is C, Si, Ge, Sn or Pb,

Y ₁₁ and Y ₂₁ are the same as or different from each other, and each independently represents hydrogen, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, a C 2 to C 30 hydrocarbyloxy hydrocarbyl group, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR ₂₃ R ₂₄ , and R ₂₃ and R ₂₄ are the same as or different from each other, and each independently any one of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or may be connected to each other to form an aliphatic or aromatic ring,

Y ₁₂ and Y ₂₂ is the same as or different from each other, and each independently represents any one of a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

C ₁₁ is any one of ligands represented by Formulas 2a to 2d;

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

R _2a to R _2r are the same as or different from each other, and each independently represent any one of hydrogen, a C 1 to C 30 hydrocarbyl group, and a C 1 to C 30 hydrocarbyloxy group;

[Formula 3]

D(R ₅₀ ) ₃

In Formula 3,

D is aluminum or boron,

R ₅₀ is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.

According to the method for producing an ethylene-alpha olefin copolymer of the present invention, even when a relatively small amount of hydrogen is added, high activity is maintained, the low molecular fraction is reduced, and the generation of wax in the polymerization process is reduced, so that the process is stable. In particular, through control of SCB (short chain branch) content and BOCD (Broad Orthogonal Co-monomer Distribution) structure, melt index and melt flow rate ratio (MFRR, Melt Flow Rate Ratio), etc., are excellent. An ethylene-alpha olefin copolymer capable of implementing melt properties may be provided.

1 is a molecular weight distribution curve of an ethylene-1-butene copolymer obtained in Examples and Comparative Examples of the present invention.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, the terminology used herein is used only to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "have" are intended to designate the existence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that the existence or addition of numbers, steps, elements, or combinations thereof, is not precluded in advance.

Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the invention,

Step A) of supplying a compound represented by the following Chemical Formula 3 to the reaction system;

at least one first transition metal compound represented by the following Chemical Formula 1 by increasing the temperature of the reaction system to a polymerization temperature; at least one second transition metal compound represented by the following formula (2); and a step B) of supplying a supported hybrid catalyst including a carrier supporting the first and second transition metal compounds to the reaction system; and

In the reaction system, under the supply of hydrogen gas, comprising the step C) of copolymerizing ethylene and alpha olefin;

A method for preparing an ethylene-alphaolefin copolymer is provided.

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal,

R ₁₀ to R ₁₉ are the same as or different from each other, and each independently represents a hydrogen, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, and a C 2 to C 30 hydrocarbyloxy hydrocarbyl group. with the proviso that at least one of R ₁₀ to R ₁₉ is -(CH ₂ ) _n -OR (in this case, R is a linear or branched chain alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 10) ;

X ₁₁ and X ₁₂ are the same as or different from each other and are each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, —SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms;

[Formula 2]

In Formula 2,

M ₂ is a Group 4 transition metal,

Z is -O-, -S-, -NR ₂₁ - or -PR ₂₂ -, R ₂₁ and R ₂₂ are the same or different from each other, and each independently hydrogen, a C 1 to C 20 hydrocarbyl group, 1 to C 1 to Any one of a 20 hydrocarbyl (oxy) silyl group and a silyl hydrocarbyl group having 1 to 20 carbon atoms,

X ₂₁ and X ₂₂ are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,

또는

이고,T ₁ is

or

ego,

T is C, Si, Ge, Sn or Pb,

Y ₁₁ and Y ₂₁ are the same as or different from each other, and each independently represents hydrogen, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, a C 2 to C 30 hydrocarbyloxy hydrocarbyl group, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR ₂₃ R ₂₄ , and R ₂₃ and R ₂₄ are the same as or different from each other, and each independently any one of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or may be connected to each other to form an aliphatic or aromatic ring,

Y ₁₂ and Y ₂₂ is the same as or different from each other, and each independently represents any one of a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

C ₁₁ is any one of ligands represented by Formulas 2a to 2d;

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

R _2a to R _2r are the same as or different from each other, and each independently represent any one of hydrogen, a C 1 to C 30 hydrocarbyl group, and a C 1 to C 30 hydrocarbyloxy group;

[Formula 3]

D(R ₅₀ ) ₃

In Formula 3,

D is aluminum or boron,

R ₅₀ is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.

Unless otherwise limited herein, the following terms may be defined as follows.

The hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from hydrocarbon, and is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkyl group. It may include a nylaryl group and the like. The hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, and a n-hexyl group. , a straight-chain, branched-chain or cyclic alkyl group such as n-heptyl group and cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.

The hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms may be a hydrocarbyloxy group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group , a straight-chain, branched-chain or cyclic alkoxy group such as n-hexoxy group, n-heptoxy group, cyclohexoxy group; Alternatively, it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.

A hydrocarbyloxyhydrocarbyl group is a functional group in which one or more hydrogens of a hydrocarbyl group are substituted with one or more hydrocarbyloxy groups. Specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms may be a hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms or 2 to 15 carbon atoms. More specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert- part It may be a oxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group, or a phenoxyhexyl group.

The hydrocarbyl(oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH3 are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. Specifically, the hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms may be a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, the hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms is an alkyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, and a dimethylpropylsilyl group. silyl group; alkoxysilyl groups such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group and a dimethoxyethoxysilyl group; It may be an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, and a dimethoxypropylsilyl group.

The silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which at least one hydrogen of the hydrocarbyl group is substituted with a silyl group. The silyl group may be -SiH3 or a hydrocarbyl(oxy)silyl group. Specifically, the silylhydrocarbyl group having 1 to 20 carbon atoms may be a silylhydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the silylhydrocarbyl group having 1 to 20 carbon atoms may be -CH2-SiH3, a methylsilylmethyl group, or a dimethylethoxysilylpropyl group.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The sulfonate group has a structure of -O-SO2-Ra, and Ra may be a hydrocarbyl group having 1 to 30 carbon atoms. Specifically, the sulfonate group having 1 to 30 carbon atoms may be a methanesulfonate group or a phenylsulfonate group.

The sulfone group having 1 to 30 carbon atoms has a structure of -Rb'-SO2-Rb", wherein Rb' and Rb" are the same as or different from each other, and may each independently be any one of a hydrocarbyl group having 1 to 30 carbon atoms. Specifically, the sulfone group having 1 to 30 carbon atoms may be a methylsulfonylmethyl group, a methylsulfonylpropyl group, a methylsulfonylbutyl group, or a phenylsulfonylpropyl group.

The alkyl group having 1 to 20 carbon atoms includes a straight-chain or branched alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and a jade group. til group, and the like, but is not limited thereto.

In addition, the alkenyl group having 2 to 20 carbon atoms includes a linear or branched alkenyl group, and specifically, an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc., but is not limited thereto.

In addition, the aryl group having 6 to 20 carbon atoms includes a monocyclic or condensed aryl group, and specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, etc. may be mentioned, but is not limited thereto.

In addition, the alkoxy group having 1 to 20 carbon atoms may include, but is not limited to, a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, and the like.

In addition, the alkylene group is a divalent functional group in the form of removing two hydrogen atoms from an alkane. Specifically, the alkylene group having 1 to 5 carbon atoms may be a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group.

In the present specification, that two substituents adjacent to each other are connected to each other to form an aliphatic or aromatic ring means that the atom(s) of the two substituents and the valences (atoms) to which the two substituents are bonded are connected to each other to form a ring do. Specifically, examples in which R23 and R24 of -NR23R24 are connected to each other to form an aliphatic ring include a piperidinyl group, and examples in which R23 and R24 of -NR23R24 are connected to each other to form an aromatic ring A pyrrolyl group and the like can be exemplified.

The above-mentioned substituents are optionally a hydroxyl group within the range of exhibiting the same or similar effect as the desired effect; halogen; hydrocarbyl group; hydrocarbyloxy group; a hydrocarbyl group or a hydrocarbyloxy group containing at least one hetero atom among the heteroatoms of Groups 14 to 16; -SiH3; hydrocarbyl (oxy) silyl group; phosphine group; phosphide group; sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.

First, a hybrid supported catalyst used in an embodiment of the present invention will be described.

In the hybrid supported catalyst, the first transition metal compound may mainly contribute to making a low molecular weight copolymer having a low SCB (short chain branch) content. In addition, the second transition metal compound may mainly contribute to making a copolymer of medium molecular weight having a high SCB content.

Accordingly, in the supported hybrid catalyst according to an embodiment of the present invention, the content of side branches can be controlled by using the high-copolymerizable transition metal compound and the low-copolymerizable transition metal compound together as a hybrid catalyst. , which is very advantageous for copolymerizing ethylene-alpha olefins having a BOCD (broad orthogonal co-monomer distribution) structure in which the comonomer content is concentrated in medium-molecular-weight heavy chains. In addition, this ethylene-alpha olefin is a medium molecular weight olefinic copolymer having a high SCB (Short Chain Branch) content, specifically, an SCB content of about 7 or more, or about 7.1 or more, and at the same time has a narrow molecular weight distribution, and has better physical properties. can indicate

Specifically, the first transition metal compound represented by Formula 1 has a structure in which an indene group and cyclopentadiene (Cp) are not connected by a cross-linking, and the electronic/stereoscopic environment around the transition metal can be easily controlled. , as a result, properties such as chemical structure, molecular weight distribution, and mechanical properties of the synthesized ethylene-alpha olefin can be easily controlled.

In addition, in at least one of the substituents of the indene group and the cyclopentadiene group is -(CH ₂ )n-OR ₂₀ (in this case, R 20 is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 4). ), low molecular weight ethylene with a controlled degree of copolymerization or comonomer distribution by introducing a substituent of -Can produce alpha olefins.

When the first transition metal compound having the above structure is supported on a carrier, the -(CH ₂ )n-OR20 group among the substituents can form a covalent bond through close interaction with the silanol group on the surface of the silica used as the support. Stable supported polymerization is possible.

In Formula 1, M1 is a Group 4 transition metal, and may be specifically Ti, Zr, or Hf, and more preferably, Ti or Zr.

In addition, in Formula 1, R10 and R19 are specifically the same as or different from each other, and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms. It is selected from the group consisting of an alkylaryl group of to 20 and an arylalkyl group having 7 to 20 carbon atoms, with the proviso that at least one of R10 and R19 may be -(CH ₂ )n-OR ₂₀ . The -(CH ₂ )n-OR ₂₀ functional group may affect the copolymerizability of an alpha olefin comonomer such as 1-butene or 1-hexene, where n is 4 or less In the case of having a short alkyl chain of Accordingly, in Formula 1, any one or more substituents of R10 and R11, or any one or more substituents of R16 to R19 of the cyclopentadiene (Cp) may be -(CH ₂ )n-OR ₂₀ , and more Specifically, one or more substituents of R10 and R11 may be -(CH ₂ )n-OR ₂₀ .

In addition, in Formula 1, X11 and X12 may be the same as or different from each other and each independently represent a halogen or an alkyl group having 1 to 20 carbon atoms.

Specific examples of the first transition metal compound represented by Formula 1 may include compounds represented by the following structural formulas, but the present invention is not limited thereto.

The first transition metal compound represented by Chemical Formula 1 may be synthesized by applying known reactions, and for more detailed synthesis methods, refer to the Examples of the present specification.

Meanwhile, in the second transition metal compound, the transition metal compound represented by Chemical Formula 2 includes an aromatic ring compound containing thiophene as different ligands and a base compound containing a Group 14 or 15 atom. and different ligands are crosslinked by T ¹ , and have a structure in which M ² (X ²¹ )(X ²² ) exists between different ligands. The supported catalyst on which a transition metal compound having such a specific structure is supported can be applied to a polymerization reaction of an olefin polymer to exhibit high activity and provide an olefin polymer having a high molecular weight.

Specifically, the ligand of C ¹¹ in the structure of the transition metal compound represented by Formula 2 may affect, for example, olefin polymerization activity and copolymerization properties of olefins.

As a C ¹¹ ligand, in Formulas 2a to 2d described above;

R ^2a to R ^2d , R ^2g to R ^2j , R ^2m , R ²ⁿ , R ^2q and R ^2r are the same or different from each other, and each independently represent any one of hydrogen and a C 1 to C 10 hydrocarbyl group, and more specifically is hydrogen or an alkyl group having 1 to 10 carbon atoms;

R ^2e , R ^2f , R ^2k , R ^2l , R ^2o , R ^2p , R ^2s and R ^2t are the same as or different from each other, and each independently any one of a C 1 to C 10 hydrocarbyl group, more specifically C When including a ligand which is any one of 1 to 10 alkyl groups;

It is possible to provide a catalyst exhibiting a high comonomer conversion with good catalytic activity in the olefin polymerization process.

In addition, in the structure of the transition metal compound represented by Formula 2, the Z ligand may also affect the polymerization activity of the olefin. In particular, when Z in Formula 2 is -NR ²¹ -, wherein R ²¹ is a hydrocarbyl group having 1 to 10 carbon atoms, more specifically an alkyl group having 1 to 10 carbon atoms, a catalyst exhibiting very high activity in the olefin polymerization process is provided. can do.

의 구조를 가질 수 있으며, 여기서 T는 C 또는 Si이고, Y¹¹ 및 Y¹²는 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 2 내지 20의 알콕시알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기, 및 탄소수 7 내지 20의 아릴옥시알킬기 중 어느 하나 일 수 있으며, 보다 더 구체적으로, Y¹¹ 및 Y¹²는 서로 동일하거나 상이하고, 각각 독립적으로 메틸기, 에틸기, n-프로필기, n-부틸기, 메톡시메틸기, 메톡시에틸기, 에톡시메틸기, iso-프로폭시메틸기, iso-프로폭시에틸기, iso-프로폭시헥실기, tert-부톡시메틸기, tert-부톡시에틸기, tert-부톡시헥실기 및 페녹시헥실기 중 어느 하나일 수 있다. The C ¹¹ ligand and the Z ligand may be crosslinked by -T ¹ - to exhibit excellent loading stability and polymerization activity. For this effect, the T ¹ is

wherein T is C or Si, Y ¹¹ and Y ¹² are the same as or different from each other, and each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 2 to 20 carbon atoms It may be any one of an alkoxyalkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an aryloxyalkyl group having 7 to 20 carbon atoms, and more specifically, Y ¹¹ and Y ¹² are the same as or different from each other, and each independently a methyl group, an ethyl group, n-propyl group, n-butyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxy It may be any one of an ethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group, and a phenoxyhexyl group.

Specifically, it may be more preferable that Y ¹¹ and Y ¹² are each independently a methyl group or a tert-butoxyhexyl group in consideration of the remarkable improvement effect, but is not limited thereto.

Meanwhile, M ² (X ²¹ )(X ²² ) exists between the cross-linked C ¹¹ ligand and the Z ligand, and M ² (X ²¹ )(X ²² ) may affect the storage stability of the metal complex. . In order to ensure this effect more effectively, a transition metal compound in which X ²¹ and X ²² are each independently any one of halogen may be used.

As an example, compounds represented by the following Chemical Formulas 21 to 24 may be exemplified as the compound of Chemical Formula 2, which has superior activity, can improve copolymerization of ethylene, and can express ultra-high molecular weight.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In Formulas 4 to 7, the M, R ^2a to R ^2t , T, X ¹¹ , X ¹² , Y ¹¹ and Y ¹² is as defined above.

Specific examples of the second transition metal compound represented by Formula 2 may include compounds represented by the following structural formulas, but the present invention is not limited thereto.

The transition metal compound represented by the above formula (2) may be synthesized by applying known reactions, and more detailed synthesis methods may refer to Examples.

Meanwhile, the first and second transition metal compounds may be stably supported on a carrier due to the above-described structural characteristics.

As the carrier, a carrier containing a hydroxyl group or a siloxane group on the surface may be used. Specifically, as the carrier, by drying at a high temperature to remove moisture from the surface, a carrier containing a highly reactive hydroxyl group or siloxane group may be used.

More specifically, silica, alumina, magnesia, or a mixture thereof may be used as the carrier. The carrier may be dried at a high temperature, and they typically include oxides, carbonates, sulfates, and nitrates such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg(NO ₃ ) ₂ .

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. When the drying temperature of the carrier is less than 200 ℃, there is too much moisture and the surface moisture and the cocatalyst react. It is undesirable because it disappears and only the siloxane remains, reducing the reaction site with the co-catalyst.

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

If the amount of the hydroxyl group is less than 0.1 mmol/g, there are few reaction sites with the co-catalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be caused by moisture other than the hydroxyl group present on the surface of the carrier particle. not.

In addition, the supported hybrid catalyst according to an embodiment of the present invention may further include a co-catalyst to activate the transition metal compound, which is a catalyst precursor. The cocatalyst is not particularly limited as long as it is an organometallic compound containing a Group 13 metal, and can be used when polymerizing olefins under a general metallocene catalyst. Specifically, the cocatalyst may be at least one compound selected from the group consisting of compounds represented by the following formula (4).

[Formula 4]

R ₄₁ -[Al(R ₄₂ )-O]nR ₄₃

In Formula 4,

R ₄₁ , R ₄₂ and R ₄₃ are

each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

n is an integer greater than or equal to 2;

[Formula 5]

[LH]+[W(A) ₄ ]- or [L]+[W(A) ₄ ]-

In Formula 5,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

W is a group 13 element, and four A are a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and one or more of the substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents of halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl(oxy)silyl group.

Non-limiting examples of the compound represented by Formula 4 may include methylaluminoxane, ethylaluminoxane, iso-butylaluminoxane, or tert-butylaluminoxane.

And, non-limiting examples of the compound represented by Formula 6 include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis( Pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium Tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3 ,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetra Kis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluoro Rophenyl)borate, hexadecyldimethylammonium tetrakis(pentafluorophenyl)borate, N-methyl-N-dodecylanilinium tetrakis(pentafluorophenyl)borate or methyldi(dodecyl)ammonium tetrakis(penta fluorophenyl) borate and the like.

Such a hybrid supported catalyst may be prepared by, for example, supporting a promoter on a support and loading the first and second transition metal compounds, which are catalyst precursors, on a support on which the promoter is supported.

Specifically, in the step of supporting the cocatalyst on the carrier, the cocatalyst may be added to the carrier dried at a high temperature and stirred at a temperature of about 20 to 120° C. to prepare the cocatalyst supported carrier.

And, in the step of supporting the catalyst precursor on the support supporting the promoter, a transition metal compound is added to the support supporting the promoter obtained in the step of supporting the promoter on the support, and the transition metal compound is added by stirring at a temperature of about 20 to 120 ° C. A catalyst can be prepared.

In the step of supporting the catalyst precursor on the support on which the promoter is supported, a supported catalyst may be prepared by adding a transition metal compound to the support on which the promoter is supported and stirring, and then adding the promoter to the support.

The content of the carrier, the promoter, and the transition metal compound used in the hybrid supported catalyst according to an embodiment of the present invention may be appropriately adjusted according to the desired physical properties or effects of the supported catalyst.

Specifically, in the supported hybrid catalyst according to an embodiment of the present invention, a mixing molar ratio of the first transition metal compound and the second transition metal compound is 2:1 to 1:5, more specifically 1.5:1 to 1 : can be 1.5. By including the first and second transition metal compounds in the above-described mixing molar ratio, excellent physical properties are obtained through improvement of short chain branch (SCB) content, reduction of molecular weight distribution, and broad orthogonal co-monomer distribution (BOCD) structure formation. It is easier to produce an olefin polymer having

In addition, in the hybrid supported catalyst according to an embodiment of the invention, the weight ratio of the total transition metal compound including the first and second transition metal compounds to the carrier is 1:10 to 1:1,000, more specifically 1: It may be 10 to 1:500. When the carrier and the transition metal compound are included in a mid-ratio ratio within the above range, an optimal shape may be exhibited.

In addition, when the hybrid supported catalyst further includes a promoter, the weight ratio of the promoter to the support is 1:1 to 1:100, more specifically 1:1 to 1; It can be 50. When the cocatalyst and the carrier are included in the above weight ratio, the activity and the microstructure of the polymer can be optimized.

In preparing the hybrid supported catalyst, as the reaction solvent, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used.

For a specific method of preparing the supported catalyst, reference may be made to Examples to be described later. However, the preparation method of the supported catalyst is not limited to the content described herein, and the preparation method may additionally employ a step commonly employed in the technical field to which the present invention belongs, and the step of the preparation method ( ) can be modified by means of a routinely changeable step(s).

Next, an embodiment of the present invention for preparing an ethylene-alpha olefin copolymer using the above-described hybrid supported catalyst will be described.

First, a compound represented by the following Chemical Formula 3 is supplied to the reaction system.

[Formula 3]

D(R ₅₀ ) ₃

In Formula 3,

D is aluminum or boron,

R ₅₀ is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.

Non-limiting examples of the compound represented by Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-sec-butylaluminum , tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaaluminum, dimethylaluminum methoxide or dimethylaluminum Ethoxide etc. are mentioned.

The compound represented by Chemical Formula 3 acts as a chain transfer agent in the polymerization reaction system, and depending on the time of input, it affects the metallocene compound supported on the carrier, that is, the first and second transition metal compounds. influence will be different. In the case of the present invention, the content of side branches in the polymerization reaction can be adjusted by adding the compound represented by Chemical Formula 3 to the reaction system first, and then separately adding the metallocene-supported catalyst and the like described above. It is very advantageous for copolymerizing ethylene-alpha olefins having a characteristic molecular weight distribution structure in which the monomer is concentrated in a medium chain of medium to high molecular weight.

The step of supplying the compound represented by Formula 3 to the reaction system may be carried out at about 0 to about 40° C., preferably, at room temperature.

Thereafter, the temperature of the reaction system may be increased to a polymerization temperature, for example, from about 60 to about 100°C, preferably from about 70 to about 90°C.

And, after the temperature rise, the supported hybrid catalyst may be supplied to the reaction system, and the copolymerization of ethylene and alpha olefin may proceed under the supply of hydrogen gas in the reaction system under the polymerization temperature conditions described above.

The polymerization reaction may be performed under the above-described temperature conditions and pressure of about 1 to about 100 kgf/cm ² or about 1 to about 50 kgf/cm ² .

According to an embodiment of the present invention, when hydrogen is supplied, the hydrogen gas may be preferably supplied in an amount of about 0.1 to about 0.4 parts by weight, or about 0.3 to about 0.4 parts by weight, based on 100 parts by weight of the ethylene. As such, according to the manufacturing method of the present invention, a relatively small amount of hydrogen may be introduced to proceed a polymerization reaction, and thus, the generation of a wax component, which is a reaction by-product, may be reduced. In addition, the low molecular weight fraction in the copolymer is relatively reduced, so that it is possible to prepare an olefin copolymer having a medium molecular weight and a narrow molecular weight distribution, in particular, having a unique BOCD structure.

In addition, the hybrid supported catalyst may have a high SCB (short chain branch) content compared to ethylene-alpha olefin polymerized using a conventional transition metal compound catalyst due to a specific structure, and a medium molecular weight and narrow molecular weight distribution. It is possible to provide a copolymer, particularly an ethylene-alpha olefin copolymer having a BOCD structure, and in this ethylene-alpha olefin copolymer, a melt index and a melt flow rate ratio (MFRR, Melt Flow Rate Ratio), etc. , the flow-related properties can be improved.

In addition, the process of supplying the compound represented by Chemical Formula 3 to the reaction system, increasing the temperature, supplying the hybrid supported catalyst, and performing the copolymerization may be performed as a continuous process.

For the polymerization reaction of the olefin monomer, various polymerization processes known as polymerization reaction of the olefin monomer, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process, may be employed, preferably continuous It may be food solution polymerization.

In addition, in the polymerization reaction, the supported hybrid catalyst may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. In this case, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that may adversely affect the catalyst may be removed in advance.

The alpha olefin comonomer participating in the copolymerization with ethylene is specifically, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, It may include at least one selected from the group consisting of 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, and most preferably 1- Butenes may be used. Accordingly, the ethylene-alpha olefin copolymer described above may be, preferably, an ethylene-1-butene copolymer.

Specifically, when the ethylene-alpha olefin copolymer is an ethylene-1-butene copolymer, the weight average molecular weight may be about 100,000 g/mol or less, preferably about 50,000 to about 100,000 g/mol, and molecular weight distribution is less than about 10, preferably less than about 8, or from about 5 to about 8, which may exhibit a narrow molecular weight distribution.

In addition, when a molecular weight distribution curve is drawn with the log value (log M) of the weight average molecular weight (M) as the x-axis and the molecular weight distribution (dwt/dlog M) for the log value as the y-axis, It may have a BOCD structure in which a branch content having 2 to 7 carbon atoms increases toward a higher molecular weight.

In addition, in the ethylene-1-butene copolymer prepared according to an embodiment of the present invention, in the molecular weight distribution curve described above, there is one point at which the increase value of the slope, that is, the second degree differential value is smaller than 0, It may be a monomodal curve, and in this case, the point at which the above-mentioned second degree differential value becomes smaller than 0 appears in a region where the log value (log M) is about 4.5 to about 5.5. It is possible to have a molecular weight distribution form.

Hereinafter, through specific examples of the invention, the operation and effect of the invention will be described in more detail. However, these embodiments are merely presented as an example of the invention, and the scope of the invention is not defined thereby.

<Example>

production example One: first transition Preparation of metal compound (A)

(A)

(A)

1-1 Preparation of Ligand Compounds

After adding 10.8 g (100 mmol) of chlorohexanol to a dried 250 mL Schlenk flask, 10 g of molecular sieve and 100 mL of MTBE (methyl tert-butyl ether) were added, and 20 g of sulfuric acid was slowly added over 30 minutes. did The reaction mixture slowly turned pink over time, and after 16 h it was poured into ice-cold saturated sodium bicarbonate solution. The mixture was extracted 4 times using 100 mL of ether each, and the collected organic layer was dried over MgSO ₄ , filtered, and the solvent was removed under vacuum under reduced pressure to remove 10 g of 1-(tert butoxy)-6-chlorohexane ( 60% yield) was obtained.

¹ H NMR (500 MHz, CDCl ₃ ): 3.53 (2H, t), 3.33 (2H, t), 1.79 (2H, m), 1.54 (2H, m), 1.45 (2H, m), 1.38 (2H, m) ), 1.21 (9H, s)

4.5 g (25 mmol) of the above-synthesized 1-(tert butoxy)-6-chlorohexane was added to a dried 250 mL Schlenk flask and dissolved in 40 mL of THF. 20 mL of sodium indenide THF solution was slowly added thereto and stirred for one day. The reaction mixture was quenched by adding 50 mL of water, extracted with ether (50 mL x 3), and then the collected organic layer was sufficiently washed with brine. The remaining moisture was dried over MgSO ₄ , filtered, and the solvent was removed under vacuum to obtain 3-(6-tert-butoxy hexyl)-1H-indene, a dark brown viscous product, in quantitative yield.

Mw = 272.21 g/mol

¹ H NMR (500 MHz, CDCl ₃ ): 7.47 (1H, d), 7.38 (1H, d), 7.31 (1H, t), 7.21 (1H, t), 6.21 (1H, s), 3.36 (2H, m) ), 2.57 (2H, m), 1.73 (2H, m), 1.57 (2H, m), 1.44 (6H, m), 1.21 (9H, s)

1-2 Preparation of transition metal compounds

In a dried 250 mL Schlenk flask, 5.44 g (20 mmol) of 3-(6-tert-butoxy hexyl)-1H-indene prepared above was added and dissolved in 60 mL of ether. 13 mL of n-BuLi 2.0M hexane solution was added thereto, stirred for one day, and then a toluene solution of n-butyl cyclopentadiene ZrCl ₃ (concentration 0.378 mmol/g) was slowly added at -78°C. When the reaction mixture was raised to room temperature, it changed from a clear brown solution to a white suspension in which a yellow solid floated. After 12 hours, 100 mL of hexane was added to the reaction mixture to form an additional precipitate. Then, it is filtered under argon to obtain a yellow filtrate, which is dried to obtain the desired compound 3-(6-(tert-butoxy)hexyl)-1H-inden-1-yl)(3-butylcylcopenta-2,4-dien- It was confirmed that 1-yl) zirconium (IV) chloride was produced.

Mw = 554.75 g/mol

¹ H NMR (500 MHz, CDCl ₃ ): 7.62 (2H, m), 7.24 (2H, m), 6.65 (1H, s), 6.39 (1H, s), 6.02 (1H, s), 5.83 (1H, s) ), 5.75 (1H, s), 3.29 (2H, m), 2.99 (1H, m), 2.89 (1H, m), 2.53 (1H, m), 1.68 (2H, m), 1.39-1.64 (10H, m), 1.14 (9H, s), 0.93 (4H, m)

production example 2: second transition Preparation of metal compound (B)

(1) Preparation of Ligand A

1-benzothiophene 4.0 g (30 mmol) was dissolved in THF to prepare a 1-benzothiophene solution. Then, 14 mL (36 mmol, 2.5 M in hexane) of an n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution.

Then, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80°C, and the resulting solution was stirred at room temperature for about 10 hours.

Thereafter, 10% HCl was poured into the solution to quench the reaction, and the organic layer was separated with dichloromethane to form a beige solid (2E)-1-(1-benzothien-2-yl)-2- Methyl-2-buten-1-one was obtained.

¹ H NMR (CDCl ₃ ): 7.85-7.82 (m, 2H), 7.75 (m, 1H), 7.44-7.34 (m, 2H), 6.68 (m, 1H), 1.99 (m, 3H), 1.92 (m , 3H)

A solution of 5.0 g (22 mmol) of (2E)-1-(1-benzothien-2-yl)-2-methyl-2-buten-1-one prepared above in 5 mL of chlorobenzene was stirred vigorously. 34 mL of sulfuric acid was slowly added to the solution. Then, the solution was stirred at room temperature for about 1 hour. Then, ice water was poured into the solution, the organic layer was separated with an ether solvent, and 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopenta[d]thiophen-3-one as a yellow solid 4.5 g (91% yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 (m, 1H), 2.63 (m, 1H), 1.59 (d, 3H), 1.39 (d , 3H)

A solution of 2.0 g (9.2 mmol) of 1,2-dimethyl-1,2-dihydro-3H-benzo [b] cyclopenta [d] thiophen-3-one in a mixed solvent of 20 mL of THF and 10 mL of methanol 570 mg (15 mmol) of NaBH ₄ was added at 0°C. Then, the solution was stirred at room temperature for about 2 hours. Then, HCl was added to the solution to adjust the pH to 1, and the organic layer was separated with an ether solvent to obtain an alcohol intermediate.

A solution was prepared by dissolving the alcohol intermediate in toluene. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution, and the mixture was refluxed for about 10 minutes. The obtained reaction mixture was separated by column chromatography to give an orange-brown color, and 1.8 g (9.0 mmol, 98) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene (ligand A) in liquid form. % yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s, 1H), 3.35 (q, 1H), 2.14 (s, 3H), 1.14 (d, 3H)

(2) Preparation of Ligand B

Put 13 mL (120 mmol) of t-butylamine and 20 mL of an ether solvent in a 250 mL schlenk flask, and transfer 16 g (6-tert-butoxyhexyl)dichloro(methyl)silane (6-tert-butoxyhexyl)dichloro(methyl)silane to another 250 mL schlenk flask ( 60 mmol) and 40 mL of an ether solvent were added to prepare a t-butylamine solution and a (6-tert-butoxyhexyl)dichloro(methyl)silane solution, respectively. Then, the t-butylamine solution was cooled to -78 °C, and a (6-tert-butoxyhexyl)dichloro(methyl)silane solution was slowly injected into the cooled solution, and the solution was stirred at room temperature for about 2 hours. did The resulting white suspension was filtered to give an ivory color, and liquid 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilaneamine (ligand B) was obtained.

¹ H NMR (CDCl ₃ ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0.40 (s, 3H)

(3) crosslinking of ligands A and B

1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (ligand A) was added to a 250 mL schlenk flask, and 30 mL of THF was added to prepare a ligand A solution. . After the ligand A solution was cooled to -78 °C, 3.6 mL (9.1 mmol, 2.5M in hexane) of an n-BuLi solution was added to the ligand A solution, which was stirred at room temperature overnight to obtain a purple-brown solution. got it The solvent of the purple-brown solution was replaced with toluene, and a solution in which 39 mg (0.43 mmol) of CuCN was dispersed in 2 mL of THF was injected into this solution to prepare a solution A.

Meanwhile, solution B prepared by injecting 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilaneamine (ligand B) and toluene into a 250 mL schlenk flask was cooled to -78 °C. Solution A prepared above was slowly injected into the cooled solution B. And the mixture of solutions A and B was stirred at room temperature overnight. Then, by filtration and removing the resulting solid, 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl) brown color and viscous liquid 4.2 g (>99% yield) of -3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1-methylsilaneamine (cross-linked product of ligands A and B) was obtained.

After lithiation of the cross-linked product at room temperature to confirm the structure of the cross-linked product of ligands A and B, H-NMR spectra were obtained using a sample dissolved in a small amount of pyridine-D5 and CDCl ₃ .

¹ H NMR (pyridine-D5 and CDCl ₃ ): 7.81 (d, 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t, 2H), 3.15 (s, 6H), 2.23 -1.73 (m, 10H), 2.15 (s, 9H), 1.91 (s, 9H), 1.68 (s, 3H)

(4) Preparation of transition metal compounds

1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene in a 250 mL schlenk flask 4.2 g (8.6 mmol) of -3-yl)-1-methylsilanamine (cross-linked product of ligands A and B) was added, and 14 mL of toluene and 1.7 mL of n-hexane were added to the flask to dissolve the cross-linked product. After the solution was cooled to -78 °C, 7.3 mL (18 mmol, 2.5M in hexane) of an n-BuLi solution was injected into the cooled solution. Then, the solution was stirred at room temperature for about 12 hours. Then, 5.3 mL (38 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40° C. for about 3 hours to prepare solution C.

Meanwhile, 2.3 g (8.6 mmol) of TiCl ₄ (THF) ₂ and 10 mL of toluene were added to a separately prepared 250 mL schlenk flask to prepare a solution D in which TiCl ₄ (THF) ₂ was dispersed in toluene. Solution C prepared before solution D was slowly injected at -78°C, and the mixture of solutions C and D was stirred at room temperature for about 12 hours. Thereafter, the solution was depressurized to remove the solvent, and the resulting solute was dissolved in toluene. Then, the solid not dissolved in toluene was removed by filtration, and the solvent was removed from the filtered solution to obtain 4.2 g (83% yield) of a transition metal compound in the form of a brown solid.

(B)

(B)

¹ H NMR (CDCl ₃ ): 8.01 (d, 1H), 7.73 (d, 1H), 7.45-7.40 (m, 2H), 3.33 (t, 2H), 2.71 (s, 3H), 2.33 (d, 3H) ), 1.38 (s, 9H), 1.18 (s, 9H), 1.80-0.79 (m, 10H), 0.79 (d, 3H)

production example 3: Preparation of hybrid supported catalyst

(1) Co-catalyst loading

100 mL of toluene was put into a 300 ml glass reactor, 10 g of silica (SP2410 by Grace Davison) was added, and then the reactor was stirred while raising the temperature of the reactor to about 40°C. After dispersing the silica sufficiently, 60 mL of a methylaluminoxane (MAO) solution (10wt% in toluene) (Albemarle) was added to the reactor, the temperature of the reactor was raised to about 60°C, and then the temperature of the reactor was increased to about 200 rpm. stirred for hours. After that, after lowering the temperature of the reactor to about 40 °C, stirring was stopped, and after setting for about 10 minutes, the reaction solution was decantation. 100 ml of toluene was added to the resulting reactant, stirred for about 10 minutes, the stirring was stopped, and the toluene was decanted after standing for 10 minutes. As a result, a promoter supported carrier (MAO/SiO ₂ ) was obtained.

(2) Preparation of supported catalyst

50 mL of toluene was put into a reactor containing a promoter supporting carrier (MAO/SiO ₂ ), 2.1 g of the transition metal compound (A) prepared in Preparation Example 1 and 10 ml of toluene were put into the reactor, and stirred at 200 rpm for 60 minutes did

Here, 6.7 g of the transition metal compound (B) prepared in Preparation Example 2 and 10 ml of toluene were added to a reactor and stirred at 200 rpm for 12 hours. After stopping the stirring, it was allowed to stand for 10 minutes, and the reaction solution was decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was used as a 250 ml schlenk flask, followed by decantation of the hexane solution. Thereafter, it was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

Olefin-1- butene Copolymer preparation

Example One

In a 2L autoclave high-pressure reactor, 2ml of triethylaluminum (hereinafter, TEAL) and 0.8 kg of hexane were added, and the temperature was raised to 80°C while stirring at 500 rpm.

After introducing the supported catalyst and hexane prepared above into the reactor through the sample port, when the temperature inside the reactor reaches 78° C., 10 g of each of ethylene and 1-butene, hydrogen is supplied under a pressure of 9 bar, and stirred at 500 rpm, 1 hour reacted while After completion of the reaction, hexane was first removed through a filter, and dried in a vacuum oven at 80° C. for 4 hours to obtain an ethylene-1-butene copolymer.

Example 2

Triethylaluminum (hereinafter, TEAL) 1ml (1.0M hexane) and 0.8 kg of hexane were added to a 2L autoclave high-pressure reactor, and the temperature was raised to 80° C. while stirring at 500 rpm.

After introducing the supported catalyst and hexane prepared above into the reactor through the sample port, when the temperature inside the reactor reaches 78° C., 10 g of each of ethylene and 1-butene, hydrogen is supplied under a pressure of 9 bar, and stirred at 500 rpm, 1 hour reacted while After completion of the reaction, hexane was first removed through a filter, and dried in a vacuum oven at 80° C. for 4 hours to obtain an ethylene-1-butene copolymer.

comparative example One

In a 2L autoclave high-pressure reactor, 2ml of TEAL (1.0M hexane), a supported catalyst, and hexane were placed in a vial and put into the reactor, 0.8 kg of hexane was added, and the temperature was raised to 80°C while stirring at 500rpm.

Other than that, it proceeded in the same manner as in Example 1.

comparative example 2

In a 2L autoclave high-pressure reactor, 1ml of TEAL (1.0M hexane), a supported catalyst, and hexane were put in a vial, and put into the reactor, 0.8 kg of hexane was added, and the temperature was raised to 80° C. while stirring at 500rpm.

Other than that, it proceeded in the same manner as in Example 1.

The reaction conditions are summarized in Table 1 below.

first and second transition metal compound ratio
(molar ratio) Hydrogen
flow
(Compared to 100 parts by weight of ethylene) TEAL
input time TEAL
input amount\
(ml) Example 1 1:1 0.37 line input 2 Example 2 1:1 0.37 line input One Comparative Example 1 1:1 0.47 Simultaneous input with supported catalyst 2 Comparative Example 2 1:1 0.47 Simultaneous input with supported catalyst One

test example

activation:

The yield was calculated by measuring the mass of the copolymer prepared in Examples and Comparative Examples, and the unit mass of the catalyst used in the reaction and the mass of the polymer calculated per time were measured to determine the activity of the catalyst used in each Example and Comparative Examples (activity) was calculated and the results are shown in Table 1 below.

Molecular Weight and Molecular Structure:

A weight average molecular weight (Mw) and molecular weight distribution (PDI) were calculated through GPC analysis by taking 10 mg of the copolymer prepared in Examples and Comparative Examples as a sample.

In addition, the sample was pretreated by dissolving it in 1,2,4-Trichlorobenzene containing 0.0125% BHT at 160℃ for 10 hours using PL-SP260, and then PerkinElmer Spectrum 100 FT-IR connected to high temperature GPC (PL-GPC220). Measure the SCB (Short Chain Branch) content (branch content of 2 to 7 carbon atoms per 1,000 carbons, unit: ea/1,000C) at 160 ° C using When a molecular weight distribution curve is drawn with log M) as the x-axis and the molecular weight distribution (dwt/dlog M) for the log value as the y-axis, the left and right sides of 60% of the total area except for the left and right ends of 20% SCB (Short Chain Branch) content at the boundary (branch content of 2 to 7 carbon atoms per 1,000 carbons, unit: pcs/1,000C) was measured.

Determination of WAX content:

After the polymerization was completed, a hexane filter was performed to recover the polymer, and 100 ml of the filtered solvent (hexane) was settling for 2 hours, and then the volume of the obtained wax was measured.

Flow properties measurement:

Melting Index (MI) was measured at 190°C according to ASTM D1238 standard, and MI _21.6 and MI _2.16 values were measured, respectively, and expressed as a melt flow rate ratio (MFRR, Melt Flow Rate Ratio).

The measurement results are summarized in Table 2 below.

MFRR Wax
(ml) activation
(kg-copolymer/g-Cat.) SCB
(%) Tm
(℃) Molecular Weight
(Mw/10 ⁴ ) Molecular Weight
distribution Example 1 30 25 3.7 7.2 126.3 14.7 7.6 Example 2 29 27 4.1 7.3 126.0 15.5 7.5 Comparative Example 1 47 40 5.2 6.9 128.5 12.6 12.2 Comparative Example 2 47 40 6.5 7.0 128.3 12.4 12.0

Referring to Table 2, it can be clearly seen that the hybrid supported catalyst of Examples can provide an ethylene-1-butene copolymer having a BOCD structure with a relatively narrow molecular weight distribution compared to Comparative Examples.

1 shows the log value (log M) of the weight average molecular weight (M) of the ethylene-1-butene copolymer obtained in the Examples and Comparative Examples as the x-axis, and the molecular weight distribution with respect to the log value ( The molecular weight distribution curve is shown with dwt/dlog M) as the y-axis.

Referring to FIG. 1 , in the ethylene-1-butene copolymer prepared according to an embodiment of the present invention, in the molecular weight distribution curve described above, the point at which the increase value of the slope, that is, the second degree differential value, becomes smaller than 0 is 1 It can be clearly confirmed that there is a monomodal curve, and at this time, the point where the above-described second degree differential value is smaller than 0 is that the log value (log M) is about 4.5 to about 5.5 It can be clearly seen that the region has a characteristic molecular weight distribution.

In addition, the supported hybrid catalyst of Examples showed a relatively small amount of wax content compared to Comparative Examples, and it was confirmed that a copolymer of excellent quality could be prepared.

Claims (10)

Step A) of supplying a compound represented by the following Chemical Formula 3 to the reaction system;
at least one first transition metal compound represented by the following Chemical Formula 1 by increasing the temperature of the reaction system to a polymerization temperature; at least one second transition metal compound represented by the following formula (2); and a step B) of supplying a supported hybrid catalyst including a carrier supporting the first and second transition metal compounds to the reaction system; and
In the reaction system, under the supply of hydrogen gas, comprising the step C) of copolymerizing ethylene and alpha olefin;
Method for preparing ethylene-alphaolefin copolymer:
[Formula 1]

In Formula 1,
M ₁ is a Group 4 transition metal,
R ₁₀ to R ₁₉ are the same as or different from each other, and each independently a group consisting of hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms. is selected from, provided that at least one of R ₁₀ to R ₁₉ is -(CH ₂ ) _n -OR (in this case, R is a linear or branched chain alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 10) ;
X ₁₁ and X ₁₂ are the same as or different from each other and are each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, —SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms;
[Formula 2]

In Formula 2,
M ₂ is a Group 4 transition metal,
Z is -O-, -S-, -NR ₂₁ - or -PR ₂₂ -, R ₂₁ and R ₂₂ are the same as or different from each other, and each independently hydrogen, a C 1 to C 20 hydrocarbyl group, 1 to C 1 to Any one of a 20 hydrocarbyl (oxy) silyl group and a silyl hydrocarbyl group having 1 to 20 carbon atoms,
X ₂₁ and X ₂₂ are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,
T ₁ is

or

ego,
T is C, Si, Ge, Sn or Pb,
Y ₁₁ and Y ₂₁ are the same as or different from each other, and are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR ₂₃ R ₂₄ , and R ₂₃ and R ₂₄ are the same as or different from each other, and each independently any one of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or may be connected to each other to form an aliphatic or aromatic ring,
Y ₁₂ and Y ₂₂ is the same as or different from each other, and each independently represents any one of a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,
C ₁₁ is any one of ligands represented by Formulas 2a to 2d;
[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

R _2a to R _2r are the same as or different from each other, and each independently represent any one of hydrogen, a C 1 to C 30 hydrocarbyl group, and a C 1 to C 30 hydrocarbyloxy group;
[Formula 3]
D(R ₅₀ ) ₃
In Formula 3,
D is aluminum or boron,
R ₅₀ is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.
According to claim 1,
M ₁ is Ti, Zr or Hf;
R ₁₀ and R ₁₉ are the same as or different from each other, and each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and 7 carbon atoms. to 20 is selected from the group consisting of an arylalkyl group, with the proviso that at least one of R ₁₀ and R ₁₉ is -(CH ₂ )n-OR ₂₀ , R ₂₀ is a linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer from 2 to 10;
X ₁₁ and X ₁₂ are the same as or different from each other, and each independently represent a compound that is a halogen or an alkyl group having 1 to 20 carbon atoms;
A method for producing an ethylene-alpha olefin copolymer.
According to claim 1,
The first transition metal compound is any one of the compounds represented by the following structural formula,
Method for preparing ethylene-alphaolefin copolymer:

According to claim 1,
The second transition metal compound is any one of the compounds represented by the following structural formula,
Method for preparing ethylene-alphaolefin copolymer:

According to claim 1, wherein the hydrogen gas is supplied in an amount of 0.1 to 0.4 parts by weight based on 100 parts by weight of the ethylene,
A method for producing an ethylene-alpha olefin copolymer.
According to claim 1,
The alpha olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 - containing at least one selected from the group consisting of tetradecene, 1-hexadecene, and 1-eicosene,
A method for producing an ethylene-alpha olefin copolymer.
According to claim 1,
The first transition metal compound and the second transition metal compound are included in a molar ratio of 2:1 to 1:5,
A method for producing an ethylene-alpha olefin copolymer.
According to claim 1,
The hybrid supported catalyst is
In addition to the first transition metal compound and the second transition metal compound, any one or more of a compound represented by the following formula (4) and a compound represented by the following formula (5) are further supported,
Method for preparing ethylene-alphaolefin copolymer:
[Formula 4]
R ₄₁ -[Al(R ₄₂ )-O]nR ₄₃
In Formula 4,
R ₄₁ , R ₄₂ and R ₄₃ are
each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen, n is an integer of 2 or more,
[Formula 5]
[LH]+[W(A) ₄ ]- or [L]+[W(A) ₄ ]-
In Formula 5,
L is a neutral or cationic Lewis base, H is a hydrogen atom,
W is a group 13 element, and four A are a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and one or more of the substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, a C1-20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl(oxy)silyl group.
According to claim 1,
The carrier is at least one selected from the group consisting of silica, alumina and magnesia,
A method for producing an ethylene-alpha olefin copolymer.
According to claim 1,
Steps A) to C) proceed as a continuous process,
Step A) is carried out at 0 to 40 °C,
Thereafter, the temperature of the reaction system is raised to 60 to 100 ℃,
Steps B) and C) are, at 60 to 100° C., an ethylene-method for producing an alpha olefin copolymer.

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