KR102227351B1 - Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same - Google Patents

Abstract

In the present invention, a novel transition metal compound that exhibits high copolymerization, particularly 1-butene copolymerization, and can easily control properties such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of the synthesized olefin polymer, including A catalyst composition and a method for producing an olefin polymer using the catalyst composition are provided.

Description

A transition metal compound, a catalyst composition containing the same, and a method for producing an olefin polymer using the same TECHNICAL FIELD {TRANSITION METAL COMPOUND, CATALYST COMPOSITION COMPRISING THE SAME, AND METHOD FOR PREPARING OLEFIN POLYMER USING THE SAME}

The present invention relates to a novel transition metal compound having high copolymerizability, a catalyst composition comprising the same, and a method for producing an olefin polymer using the catalyst composition.

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 catalysts have been widely applied to conventional commercial processes since their invention in the 50s, but since they are multisite catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers, and the composition of comonomers. There is a problem in that there is a limit to securing desired physical properties because the distribution is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. It has a characteristic of obtaining a polymer having a narrow molecular weight distribution and a uniform composition distribution of a comonomer according to a single active point characteristic. In addition, it has properties that can change the stereoregularity, copolymerization properties, molecular weight, crystallinity, and the like 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 of 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 producing high molecular weight and a zirconium (Zr)-based metallocene catalyst producing low molecular weight on one support. As a result, 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 a disadvantage in that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle to support each of the metallocene catalysts used on the carrier.

Therefore, in order to solve the above-described disadvantages, there is a continuing need for a method of preparing an olefin-based polymer having a desired physical property by simply preparing a mixed supported metallocene catalyst having excellent activity.

U.S. Patent No. 5,032,562 U.S. Patent No. 5,525,678 U.S. Patent No. 5,914,289

The present invention is to provide a novel transition metal compound having high copolymerizability and a method for producing the same.

Another object of the present invention is to provide a catalyst composition containing the transition metal compound and a method for producing an olefin polymer using the same.

According to an embodiment of the present invention, there is provided a transition metal compound represented by the following formula (1):

[Formula 1]

In Formula 1,

Cp is any one of the ligands represented by the following formulas 2a to 2e,

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , R ₃₁ to R ₃₆ , R ₄₁ to R ₄₄ , and R ₅₁ to R ₅₄ are the same as or different from each other, and each independently, hydrogen, a hydrocar having 1 to 30 carbon atoms A bil group, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyloxy hydrocarbyl group having 2 to 30 carbon atoms;

M is a Group 4 transition metal;

X ₁ and X ₂ 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 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;

R ₁ to R ₅ are the same as or different from each other, and each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyloxy hydrocarbyl group having 2 to 30 carbon atoms Or is connected to each other to form an aliphatic or aromatic ring;

또는

이고,T is

or

ego,

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ to Y ₄ are the same as or different from each other, and each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxy hydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a C1-C30 hydrocarbyl (oxy)silyl group, a halogen-substituted C1-C30 hydrocarbyl group, and any one of _{-NR 61} R _62,

R ₆₁ And R ₆₂ are the same as or different from each other, and each independently hydrogen and one of a hydrocarbyl group having 1 to 30 carbon atoms, or are linked to each other to form an aliphatic or aromatic ring.

Specifically, the transition metal compound is R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , R ₃₁ to R ₃₆ , R ₄₁ to R ₄₄ , and R ₅₁ to R ₅₄ in Formulas 2a to 2e are the same as or different from each other, , Each independently, 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, an alkylaryl group having 7 to 20 carbon atoms, and any one of an arylalkyl group having 7 to 20 carbon atoms It may be a phosphorus compound.

In addition, in the transition metal compound, M is Ti, Zr or Hf in Formula 1, X ₁ and X ₂ are the same as or different from each other, and each independently, halogen, an alkyl group having 1 to 20 carbon atoms, and an alkoxy having 1 to 20 carbon atoms. It may be a compound that is any one of the groups.

In addition, in the transition metal compound, R ₁ and R ₅ in Formula 1 are the same or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms It may be a compound of any one of a group, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms.

이고, T₁이 C 또는 Si이며, Y₁ 및 Y₂가 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 및 탄소수 7 내지 20의 아릴알킬기, 탄소수 1 내지 20의 알콕시기, 및 탄소수 2 내지 20의 알콕시알킬기 중 어느 하나인 화합물일 수 있다.In addition, the transition metal compound is T in Formula 1

And, T ₁ is C or Si, Y ₁ and Y ₂ are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms It may be a compound of any one of a group, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxyalkyl group having 2 to 20 carbon atoms.

More specifically, the transition metal compound may be a compound represented by the following Formula 3a or 3b:

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b,

R ₁₁ to R ₁₄ , and R ₂₁ to R ₂₆ are the same as or different from each other, and each independently 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 It is any one of an alkylaryl group of to 20 and an arylalkyl group of 7 to 20 carbon atoms,

M is Ti or Zr,

X ₁ and X ₂ are the same as or different from each other, and each independently a halogen or an alkyl group having 1 to 20 carbon atoms,

R ₁ and R ₅ are the same as or different from each other, and each independently 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, an alkylaryl group having 7 to 20 carbon atoms, and Any one of arylalkyl groups having 7 to 20 carbon atoms,

Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ are the same as or different from each other, and each independently hydrogen, halogen, 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 any one of an alkylaryl group of to 20, an arylalkyl group of 7 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, and an alkoxyalkyl group of 2 to 20 carbon atoms.

More specifically, the transition metal compound may be any one of compounds represented by the following structural formula.

According to another embodiment of the present invention, there is provided a catalyst composition comprising the above-described transition metal compound.

The catalyst composition may further include a second transition metal compound represented by Formula 4:

[Formula 4]

(Cp3R ₇₁ ) _n (Cp4R ₇₂ ) M'Z' _3-n

In Chemical Formula 4,

M'is a Group 4 transition metal;

Cp3 and Cp4 are the same as or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. , They may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ₇₁ and R ₇₂ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 To 20 aryloxy group, C2 to C20 alkenyl group, C7 to C20 alkylaryl group, C7 to C40 arylalkyl group, C8 to C40 arylalkenyl group, or C2 to C20 alkynyl group ;

Z'is a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An alkylidene having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, an alkylalkoxy having 2 to 20 carbon atoms, or an arylalkoxy having 7 to 40 carbon atoms;

n is 0 or 1.

More specifically, in the second transition metal compound, in Chemical Formula 4, Cp3 and Cp4 may each be a cyclopentadienyl group, _{and at least one of R 71} and R ₇₂ may be an alkoxyalkyl group having 2 to 20 carbon atoms.

In addition, the catalyst composition may further include one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 5 to 7:

[Formula 5]

R ₈₂ -[Al(R ₈₁ )-O] _m -R ₈₃

In Chemical Formula 5,

R ₈₁ , R ₈₂ and R ₈₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,

m is an integer greater than or equal to 2,

[Formula 6]

D(R ₈₄ ) ₃

In Chemical Formula 6,

D is aluminum or boron,

R ₈₄ is each independently any one of halogen, a C1-C20 hydrocarbyl group, and a halogen-substituted C1-C20 hydrocarbyl group,

[Formula 7]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In Chemical Formula 7,

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

Z is a Group 13 element, and A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And at least one hydrogen atom of these substituents is any one of a substituent substituted with at least one of halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbylsilyl group.

In addition, the catalyst composition further includes a carrier, and the transition metal compound may be supported on the carrier.

According to another embodiment of the present invention, there is provided a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the above-described catalyst composition.

In the above production method, the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, novonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4- It may include one or more selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

In addition, in the manufacturing method, the olefin polymer may be an ethylene-1-butene copolymer.

The transition metal compound according to the present invention exhibits high copolymerization, particularly 1-butene copolymerization, and can easily control properties such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of the synthesized olefin polymer.

Hereinafter, a supported catalyst according to a specific embodiment of the present invention and a method of preparing an olefin polymer using the supported catalyst will be described.

According to one embodiment of the invention, there is provided a transition metal compound represented by the following formula (1):

[Formula 1]

In Formula 1,

Cp is any one of the ligands represented by the following formulas 2a to 2e,

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , R ₃₁ to R ₃₆ , R ₄₁ to R ₄₄ , and R ₅₁ to R ₅₄ are the same as or different from each other, and each independently, hydrogen, a hydrocar having 1 to 30 carbon atoms A bil group, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyloxy hydrocarbyl group having 2 to 30 carbon atoms;

M is a Group 4 transition metal;

X ₁ and X ₂ 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 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;

R ₁ to R ₅ are the same as or different from each other, and each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyloxy hydrocarbyl group having 2 to 30 carbon atoms Or is connected to each other to form an aliphatic or aromatic ring;

또는

이고,T is

or

ego,

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ to Y ₄ are the same as or different from each other, and each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxy hydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a C1-C30 hydrocarbyl (oxy)silyl group, a halogen-substituted C1-C30 hydrocarbyl group, and any one of _{-NR 61} R _62,

R ₆₁ And R ₆₂ are the same as or different from each other, and each independently hydrogen and one of a hydrocarbyl group having 1 to 30 carbon atoms, or are linked to each other to form an aliphatic or aromatic ring.

In the present specification, the following terms may be defined as follows unless there is a specific limitation.

Hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from a hydrocarbon, and is an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, aralkenyl group, aralkynyl group, alkylaryl group, alkenylaryl group, and alkyi. It may include a nilaryl group and the like. In addition, 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, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group , n-heptyl group, cyclohexyl group, (cyclohexyl) methyl group, such as a linear or branched chain having 1 to 20 carbon atoms, or a cyclic alkyl group having 3 to 30 carbon atoms; Or it may be an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.

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 linear, branched or cyclic alkoxy group such as an n-hectoxy group, an n-heptoxy group, and a cyclohectoxy group; Or, it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.

Hydrocarbyloxy Hydrocarbyl group is a functional group in which at least one hydrogen of the hydrocarbyl group is substituted with at least one hydrocarbyloxy group. 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, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-moiety 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 -SiH 3} 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 dimethylmethylsilyl group, and a dimethylpropylsilyl group. Silyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, and dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups 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 -SiH 3} 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 -CH _{2 -SiH 3} , 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-SO 2} -R a, and R _a 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 _{-R b '} -SO ₂ -R _{b " , wherein R b '} and R _{b "} are the same as or different from each other, and each independently is any one of a hydrocarbyl group having 1 to 30 carbon atoms I can. 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 is a straight chain or branched chain having 1 to 20 carbon atoms, or includes a cyclic alkyl group having 3 to 20 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclohexyl group, cyclohexylmethyl group, methylcyclohexyl group, and the like, but are 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, and the like, but are 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, and the like, but are not limited thereto.

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

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 valence (atoms) to which the two substituents are bonded are connected to each other to form a ring. do.

The above-described substituents are optionally a hydroxy 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 hetero atoms of groups 14 to 16; -SiH ₃ ; 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.

Usually, high-density polyethylene is prepared by using 1-butene as a comonomer in a hexane slurry (Hx slurry) process. At this time, 1-butene copolymerization exhibits higher copolymerization compared to 1-hexene or 1-octene copolymerization due to the molecular size of 1-butene itself. However, since 1-butene copolymerization also increases the copolymerization of the conventional low-molecular low-copolymerization region, the overall copolymerization ratio of the polymer is different from the 1-hexene and 1-octene copolymerization tendency, and as a result, a flat comonomer. It causes problems such as comomoner distribution.

On the other hand, the transition metal compound according to an embodiment of the present invention is a ligand (Cp) of an aromatic ring group (Cp2) including a thiophene such as cyclopentadiene (Cp1) or benzocyclopentathiophene, and an indole ligand is a bridge It is asymmetrically crosslinked by (T), and M(X ₁ )(X ₂ ) exists between the two ligands, and the two ligands and the bridge and the metal (M) form a stable five-membered ring. Due to the unique structure, the bonding structure between metal ligands changes from cyclobutane to cyclopentane structure, and has a more stable metal ligand structure. In addition, as the space between the metal ligands becomes wider, the comonomer is easily introduced. In addition, since the nitrogen component of the conventional CGC catalyst can be used to maintain high copolymerizability, excellent catalytic activity and high copolymerizability can be exhibited. As a result, it is possible to control the copolymerization ratio of the entire polymer during 1-butene copolymerization.

Specifically, the ligand of Cp in the structure of the transition metal compound represented by Formula 1 may be any one of cyclopentadiene (Cp1) or benzocyclopentathiophene (Cp2) represented by Formulas 2a to 2e, and As described above, the Cp ligand may exhibit high polymerization activity by having an unshared electron pair capable of functioning as a Lewis base. In particular, when the Cp ligand is a cyclopentadiene (Cp1) ligand represented by Chemical Formula 2a having relatively little steric hindrance, it exhibits high copolymerization activity and low hydrogen reactivity, and thus a high molecular weight olefin polymer can be polymerized with high activity. In addition, when the Cp ligand is an aromatic cyclic group including thiophene represented by Formulas 2b to 2e, it may exhibit a highly active polymer polymerization form that maintains high copolymerization.

In addition, the Cp ligand can easily control properties such as the chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of the olefin polymer produced by adjusting the degree of steric hindrance according to the type of substituted functional group. I can. Specifically, the functional group in the ligand represented by Formulas 2a to 2e, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , R ₃₁ to R ₃₆ , R ₄₁ to R ₄₄ , and R ₅₁ to R ₅₄ are the same as each other or Different, and each independently, among 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, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms It can be either. More specifically, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , R ₃₁ to R ₃₆ , R ₄₁ to R ₄₄ , and R ₅₁ to R ₅₄ are the same as or different from each other, and each independently hydrogen or 1 to 10 carbon atoms It may be an alkyl group of, and more specifically, it may be a hydrogen or a methyl group. In this case, the transition metal compound may exhibit excellent catalytic activity and high comonomer conversion in the olefin polymerization process.

In addition, within the structure of the transition metal compound represented by Chemical Formula 1, the electronically-rich indole ligand stabilizes beta-hydrogen in the polymer chain in which nitrogen atoms grow by hydrogen bonds to inhibit beta-hydrogen elimination, thereby reducing high molecular weight polyolefins. It can be polymerized.

The indole ligand can also easily control properties such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of the olefin polymer produced by adjusting the degree of steric hindrance according to the type of substituted functional group. Specifically, in Formula 1, R ₁ and R ₅ are the same as or different from each other, and each independently 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 It may be any one of an alkylaryl group having 7 to 20 and an arylalkyl group having 7 to 20 carbon atoms, and more specifically, hydrogen. In this case, the transition metal compound may exhibit high activity, and mechanical properties, transparency, and processability may be improved by easily controlling the chemical structure, molecular weight, and molecular weight distribution of the olefin polymer to be produced.

일 수 있으며, 이때 Y₁ 및 Y₂가 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 1 내지 20의 알콕시기 및 탄소수 2 내지 20의 알콕시알킬기 중 어느 하나일 수 있고, 보다 구체적으로는 Y₁ 및 Y₂가 서로 동일하며 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. 구체적으로, 상기 Y₁ 및 Y₂는 각각 독립적으로 메틸기 또는 tert-부톡시헥실기인 것이 개선 효과의 현저함을 고려할 때 보다 바람직할 수 있으나, 이에만 한정되는 것은 아니다. 그리고, 상기 T₁은 C, Si, Ge, Sn 또는 Pb이거나; C 또는 Si이거나; 혹은 Si일 수 있다. In addition, within the structure of the transition metal compound represented by Chemical Formula 1, the two ligands can be crosslinked by a bridge -T- to exhibit excellent stability and polymerization activity, and when used as a supported catalyst supported on a support, excellent It can show loading stability. In order to secure this effect more effectively, T

In this case, Y ₁ and Y ₂ may each independently be any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxyalkyl group having 2 to 20 carbon atoms, and more specifically Y ₁ and Y ₂ are identical to each other and are methyl group, ethyl group, n-propyl group, n-butyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group , tert-butoxymethyl group, tert-butoxyethyl group, tert-butoxyhexyl group, and may be any one of phenoxyhexyl group. Specifically, Y ₁ and Y ₂ are each independently a methyl group or a tert-butoxyhexyl group may be more preferable considering the remarkable improvement effect, but is not limited thereto. And, the T ₁ is C, Si, Ge, Sn or Pb; Is C or Si; Or it may be Si.

_{Meanwhile, M(X 1} )(X ₂ ) exists between the crosslinked Cp ligand and the indole ligand, and M(X ₁ )(X ₂ ) may affect the storage stability of the metal complex. In order to more effectively secure this effect, X ₁ and X ₂ may each independently be any one of halogen, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more specifically, X ₁ and X ₂ are Each independently may be F, Cl, Br or I. And M is Ti, Zr or Hf; Is Zr or Hf; Or it could be Zr.

As an example, as the compound of Formula 1, which has excellent activity and can improve copolymerization, particularly, copolymerization of 1-butene, compounds represented by the following Formulas 3a and 3b may be exemplified.

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, M, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , R ₁ and R ₅ , X ₁ and X ₂ , Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ are as previously defined. .

More specifically, specific examples of the 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 transition metal compound represented by Formula 1 is specifically prepared by connecting a Cp derivative and an indole derivative with a bridge compound to prepare a ligand compound, and then adding a metal precursor compound to perform metallation. However, it is not limited thereto.

More specifically, first, a lithium salt obtained by reacting a Cp derivative with an organolithium compound such as n-BuLi is prepared, and then the organic lithium salt of Cp and a halogenated compound of the bridge compound are mixed and reacted, and then the indole derivative is mixed with an organolithium compound such as n-BuLi. By reacting with a lithium salt obtained by reacting with an organolithium compound, a ligand compound is prepared. The ligand compound or its lithium salt and a metal precursor compound are mixed, reacted for about 12 hours to about 24 hours until the reaction is completed, and then the reaction product is filtered and dried under reduced pressure to form a transition metal compound represented by Formula 1 above. Can be manufactured. The method for preparing the transition metal compound of Formula 1 will be described in detail in Examples to be described later.

Meanwhile, according to another embodiment of the present invention, there is provided a catalyst composition comprising a transition metal compound represented by Formula 1 (hereinafter, referred to as “first transition metal compound”).

In addition, the catalyst composition may further include a second transition metal compound represented by Formula 4 below to improve copolymerization:

[Formula 4]

(Cp3R ₇₁ ) _n (Cp4R ₇₂ ) M'Z' _3-n

In Formula 4, M'is a Group 4 transition metal;

Cp3 and Cp4 are the same as or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. , They may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ₇₁ and R ₇₂ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 To 20 aryloxy group, C2 to C20 alkenyl group, C7 to C20 alkylaryl group, C7 to C40 arylalkyl group, C8 to C40 arylalkenyl group, or C2 to C20 alkynyl group ;

Z'is a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An alkylidene having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, an alkylalkoxy having 2 to 20 carbon atoms, or an arylalkoxy having 7 to 40 carbon atoms;

n is 0 or 1.

The second transition metal compound represented by Formula 4 may be included in a mixture with the first transition metal compound, or may be included in a state supported on a carrier together with the first transition metal compound.

The second transition metal compound mainly contributes to making a low molecular weight copolymer having a low SCB (short chain branch) content, and when used with the first transition metal compound, a high molecular weight olefin-based copolymer having a high SCB content At the same time, it is possible to manufacture an olefin polymer having excellent physical properties and excellent processability due to its wide molecular weight distribution.

Specific examples of the second transition metal compound represented by Formula 4 may include compounds represented by the following structural formulas, but the present invention is not limited thereto.

In addition, among the second transition metal compounds, Cp3 and Cp4 in Formula 4 are each a cyclopentadienyl group, and as a substituent, _{at least one of R 71} and R ₇₂ has 2 to 20 carbon atoms, or 2 to carbon atoms. By introducing an alkoxyalkyl group of 10, more specifically a t-butoxyhexyl group, when preparing a polyolefin using a comonomer, it exhibits a lower conversion rate to the comonomer compared to other Cp-based catalysts that do not contain the substituent. It is possible to prepare a low-medium molecular weight polyolefin having a controlled monomer distribution. Accordingly, when used as a hybrid catalyst together with the first transition metal compound, the polyolefin in the high molecular weight region by the second transition metal compound exhibits high copolymerizability and low molecular weight due to the action of the first transition metal compound. Polyolefins in the domain may exhibit low copolymerizability. Accordingly, it is very advantageous to polymerize a polyolefin having a broad orthogonal co-monomer distribution (BOCD) structure in which the content of comonomer is concentrated in the high molecular weight main chain, that is, the side branch content increases toward the high molecular weight. .

Specifically, as an example, the second transition metal compound that has excellent activity and can further improve the copolymerization, particularly the copolymerization of 1-butene when used with the first transition metal compound described above, is a compound represented by the following structural formula Can be

In addition, the catalyst composition may further include a cocatalyst to activate the transition metal compound.

The cocatalyst is an organometallic compound containing a group 13 metal, and is not particularly limited as long as it can be used when polymerizing olefins under a general metallocene catalyst. Specifically, the cocatalyst may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 5 to 7.

[Formula 5]

R ₈₂ -[Al(R ₈₁ )-O] _m -R ₈₃

In Chemical Formula 5,

R ₈₁ , R ₈₂ and R ₈₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,

m is an integer of 2 or more.

[Formula 6]

D(R ₈₄ ) ₃

In Chemical Formula 6,

D is aluminum or boron,

Each of the three R ₈₄ is independently a halogen, a C 1 to C 20 hydrocarbyl group, a C 1 to C 20 hydrocarbyloxy group, and a halogen substituted C 1 to C 20 hydrocarbyl group.

[Formula 7]

^{[LH] + [W (A} ) 4] - or ^{[L] + [W (A} ) 4] -

In Chemical Formula 6,

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 at least one hydrogen atom of these substituents is any one of substituents substituted with at least one substituent among halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms.

Non-limiting examples of the compound represented by Formula 5 above include methylaluminoxane, ethylaluminoxane, iso-butylaluminoxane or tert-butylaluminoxane. And, non-limiting examples of the compound represented by Formula 6 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-sec-butyl aluminum , Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide or dimethyl aluminum Ethoxide, etc. are mentioned. Finally, non-limiting examples of the compound represented by Formula 7 include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and N,N-dimethylanilinium tetrakis. (Pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N,N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N,N-dimethylanil Linium 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 Tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis (2,3,4,6-tetra) Fluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis ( Pentafluorophenyl) borate, and the like.

The catalyst composition may further include a carrier, and the first transition metal compound and optionally a second transition metal compound represented by Formula 1 may be provided in a form supported on the carrier.

As the carrier, a carrier containing a hydroxy group or a siloxane group on the surface may be used. Specifically, as the carrier, a carrier containing a highly reactive hydroxyl group or a siloxane group may be used by drying at a high temperature to remove moisture from the surface. More specifically, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used. The carrier may be dried at high temperature, and these may include oxides, carbonates, sulfates, and nitrate components 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°C, there is too much moisture so that the moisture on the surface and the cocatalyst react, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.

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

If the amount of the hydroxy group is less than 0.1 mmol/g, the reaction site with the cocatalyst is small, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.

As described above, when the catalyst composition further includes a carrier and a cocatalyst together with the second transition metal compound, such a catalyst composition may include, for example, supporting the cocatalyst on the carrier and the catalyst precursor on the cocatalyst supporting carrier. It may be prepared by supporting one first transition metal compound and a second transition metal compound.

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

And, in the step of supporting the catalyst precursor on the cocatalyst-supporting carrier, the first transition metal compound and the second transition metal compound are added to the cocatalyst-carrying carrier obtained in the step of supporting the cocatalyst on the support, and then It can be stirred at a temperature of 20 to 120 ℃ to prepare a supported catalyst.

In the step of supporting the catalyst precursor on the cocatalyst-carrying support, the first and second transition metal compounds are added to the co-catalyst-carrying support, respectively, and stirred, and then a co-catalyst is additionally added to prepare a supported catalyst. can do.

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

Specifically, in the catalyst composition according to an embodiment of the present invention, when a second transition metal compound is further included, the mixing molar ratio of the first transition metal compound and the second transition metal compound is 1:1 to 1:5, More specifically, it may be 1:1 to 1:3. By including each of the transition metal compounds in the mixing molar ratio described above, it is possible to exhibit more excellent copolymerization.

In addition, when the catalyst composition further includes a carrier, the weight ratio of the total transition metal compound and the carrier contained in the catalyst composition may be 1:10 to 1:1,000, more specifically 1:10 to 1:500. When the carrier and the transition metal compound are included in the weight ratio within the above range, the optimum shape may be exhibited.

In addition, the weight ratio of the cocatalyst to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50. When the cocatalyst and the carrier are included in the weight ratio, the activity and the microstructure of the polymer can be optimized.

In addition, the catalyst composition may further include a hydrocarbon solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene or toluene as the reaction solvent.

On the other hand, according to another embodiment of the present invention, in the presence of the catalyst composition, there is provided a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer.

Examples of olefin monomers applicable to the above production method include ethylene, alpha-olefins, cyclic olefins, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, 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. When the olefin polymer is a copolymer of ethylene and other comonomers, the comonomer is at least one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, More specifically, it is preferable that it is a comonomer of 1-butene.

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

Specifically, the polymerization reaction may be performed under a temperature of about 50 to 110°C or about 60 to 100°C and a ^{pressure of about 1 to 100 kgf/cm 2} or about 1 to 50 kgf/cm ^2.

In addition, in the polymerization reaction, the catalyst composition 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. At this time, by treating the solvent with a small amount of alkyl aluminum, etc., a small amount of water or air that may adversely affect the catalyst may be removed in advance.

As the olefin polymer prepared by the above method is prepared using the above-described transition metal compound, it has high copolymerizability, and as a result, can exhibit improved physical properties.

Specifically, the olefin polymer has a weight average molecular weight of 100,000 to 3,000,000 g/mol, a molecular weight distribution of 2 to 10, and more specifically, a weight average molecular weight of 100,000 to 1,500,000 g/mol, and a molecular weight distribution of 2 to It can be 3.5.

In addition, when the olefin polymer has a log value (log M) of the weight average molecular weight (M) as the x-axis, and the molecular weight distribution (dwt/dlog M) with respect to the log value as the y-axis, a molecular weight distribution curve is drawn, It may have a BOCD structure in which the content of branches of 2 to 7 carbon atoms per 1,000 carbons increases toward higher molecular weight.

In addition, when the olefin polymer is an ethylene/1-butene copolymer, the content of 1-butene introduced into the polymer by using the transition metal compound and the catalyst composition containing the same is 3 to 7 per 1000 carbon atoms in the polymer, More specifically, it may be 3.3 to 6.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention, and the scope of the invention is not limited to any meaning by this.

Synthesis example 1: Preparation of transition metal compound (A)

(A)

(A)

In a 250 ml round bottom flask, 2.44 g of tetramethylcyclopentadiene (TMCP) was added, and 60 ml of tertiary butyl methyl ether (TBME) was added. At -78°C, 8ml of n-BuLi (2.5M) was added and stirred at room temperature for 4 hours. After adding 2.6 g of dichlorodimethylsilane at -78°C and stirring at room temperature for 4 hours, LiCl was removed through a filter to obtain an intermediate. It was used for the subsequent reaction without a separate purification process.

2.35 g of indole was added to a 250 ml round bottom flask, and 60 ml of TBME was added. At -78°C, 8ml of n-BuLi(2.5M) was added and stirred at room temperature for 4 hours. _{CO 2} gas bubbling in the flask solution was performed at -78°C for 5 minutes, stirred at room temperature for 30 minutes, and then the solvent was distilled under reduced pressure to remove _{CO 2 gas in the flask.} Thereafter, after adding 60 ml of TBME, 12 ml of t-BuLi (1.7M) was added again at -78°C and stirred at room temperature for 4 hours. After lowering the temperature to -78°C, the intermediate prepared above was added to the flask, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. The _{reaction was stopped using H 2} O, and the resulting reaction product was extracted with ether, _{dried over MgSO 4} , and the remaining solvent was distilled under reduced pressure. The resulting product was heated at 120° C. for 3 hours to proceed with a dicarbonylation reaction, and recrystallized using normal hexane to obtain reactant 1 (1.9 g, yield 32%).

CDCl ₃ : 0.101 (6H, s), 0.323 (3H, s), 1.797 (6H, s), 1.948 (3H, s), 1.961 (3H, s), 3.105 (1H, s), 6.497 (1H, ddd ), 7.162 (1H, ddd), 7.159 (1H, dddd), 7.298 (1H, dddd), 7.471 (1H, dddd)

1.9 g of the reaction product 1 prepared above was added to a 250 ml round bottom flask, and 25 ml of TBME was added. At -78°C, 5.2ml of n-BuLi (2.5M) was added and stirred at room temperature for 4 hours. _{Thereafter, 2.15 g of TiCl 4} (THF) ₂ was added at -78°C, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. After removing LiCl using a filter, distillation under reduced pressure was performed, and transition metal compound A having the above structure was obtained through recrystallization of hexane (1.3 g, yield 49%).

¹ H NMR (300 MHz, CDCl ₃ ): 0.699 (6H, s), 1.797 (6H, s), 2.123 (6H, s), 6.66 (1H, dd), 6.87 (1H, ddd), 7.35 (1H, dddd), 7.93 (1H, dddd), 7.95 (1H, dddd)

Synthesis example 2: Preparation of transition metal compound (B)

(B)

(B)

In a 250 ml round bottom flask, 6 g of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene was added, and 90 ml of TBME was added. At -78°C, 12ml of n-BuLi (2.5M) was added and stirred at room temperature for 4 hours. After adding 3.9 g of dichlorodimethylsilane at -78°C and stirring at room temperature for 4 hours, LiCl was removed through a filter to obtain an intermediate. It was used for the subsequent reaction without a separate purification process.

3.51 g of indole was added to a 250 ml round bottom flask, and 90 ml of TBME was added. Into -78 ℃ n-BuLi (2.5M) 12ml was stirred at room temperature for 4 hours. _{CO 2} gas bubbling in the flask solution was performed at -78°C for 5 minutes, stirred at room temperature for 30 minutes, and then the solvent was distilled under reduced pressure to remove _{CO 2 gas in the flask.} Thereafter, after 90ml of TBME was added, 18ml of t-BuLi (1.7M) was added again at -78°C, followed by stirring at room temperature for 4 hours. After lowering the temperature to -78°C, the intermediate prepared above was added to the flask, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. The _{reaction was stopped using H 2} O, and the resulting reaction product was extracted with ether, _{dried over MgSO 4} , and the remaining solvent was distilled under reduced pressure. The resulting product was heated at 120° C. for 3 hours to proceed with a dicarbonylation reaction, and recrystallized using normal hexane to obtain reactant 2 (2.6 g, yield 23%).

CDCl ₃ : 0.227 (6H), 1.647 (3H, s), 2.092 (3H, s), 4.470 (1H, s), 6.499 (1H, ddd), 7.160 (1H, dddd), 7.164 (1H, ddd), 7.299 (1H, dddd), 7.362 (1H, ddd), 7.471 (1H, dddd), 7.508 (1H, ddd), 7.924 (1H, ddd), 8.087 (1H, ddd)

2.6 g of the reaction product 2 prepared above was added to a 250 ml round bottom flask, and 30 ml of TBME was added. At -78°C, 5.6ml of n-BuLi (2.5M) was added and stirred at room temperature for 4 hours. _{Thereafter, 2.32 g of TiCl 4} (THF) ₂ was added at -78°C, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. After removing LiCl using a filter, distillation under reduced pressure was performed, and a transition metal compound B having the above structure was obtained through recrystallization of hexane (1.4 g, yield 41%).

¹ H NMR (300 MHz, CDCl ₃ ): 0.799 (6H, s), 2.250 (6H, s), 2.718 (6H, s), 6.658 (1H, ddd), 6.871 (1H, dddd), 7.352 (1H, ddd), 7.424 (1H, dddd), 7.493 (1H, ddd), 7.932 (2H, m), 7.944 (1H, ddd), 8.056 (1H, ddd)

Synthesis Example 3: Preparation of transition metal compound A supported catalyst

(1) Preparation of cocatalyst-supporting carrier

100 mL of toluene was added to a 300 mL glass reactor, and 10 g of silica (SP2410 from Grace Davison) was added, followed by stirring while raising the temperature of the reactor to about 40°C. After sufficiently dispersing silica, 60 mL of a methylaluminoxane (MAO) solution (10 wt% in toluene) (Albemarle) was added to the reactor, and the temperature of the reactor was raised to about 60°C, and then at about 200 rpm for about 12 hours. Stirred. Thereafter, the temperature of the reactor was lowered to about 40° C., the stirring was stopped, and after setting for about 10 minutes, the reaction solution was decanted. 100 ml of toluene was added to the resulting reaction product, stirred for about 10 minutes, stopped stirring, and allowed to stand for 10 minutes, followed by decantation of toluene. As a result, a cocatalyst carrying carrier (MAO/SiO ₂ ) was obtained.

(2) Preparation of supported catalyst

50 mL of toluene was added to the reactor containing the cocatalyst-carrying carrier (MAO/SiO ₂ ), 0.70 g of the transition metal compound (A) prepared in Synthesis Example 1 and 10 ml of toluene were added to the reactor, followed by stirring at 200 rpm for 60 minutes. . After stopping the stirring, the mixture 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 transferred to a 200 ml schlenk flask, and the hexane solution was decanted. Then, it was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported catalyst.

Synthesis Example 4: Preparation of transition metal compound B supported catalyst

In Synthesis Example 3, a supported catalyst was prepared in the same manner as in Synthesis Example 3, except that 0.490 g of the transition metal compound (B) prepared in Synthesis Example 2 was used as the transition metal compound.

Synthesis Example 5: Preparation of hybrid supported catalyst (A/D)

(1) Preparation of cocatalyst-supporting carrier

100 mL of toluene was added to a 300 mL glass reactor, and 10 g of silica (SP2410 from Grace Davison) was added, followed by stirring while raising the temperature of the reactor to about 40°C. After sufficiently dispersing silica, 60 mL of a methylaluminoxane (MAO) solution (10 wt% in toluene) (Albemarle) was added to the reactor, and the temperature of the reactor was raised to about 60°C, and then at about 200 rpm for about 12 hours. Stirred. Thereafter, the temperature of the reactor was lowered to about 40° C., the stirring was stopped, and after setting for about 10 minutes, the reaction solution was decanted. 100 ml of toluene was added to the resulting reaction product, stirred for about 10 minutes, stopped stirring, and allowed to stand for 10 minutes, followed by decantation of toluene. As a result, a cocatalyst carrying carrier (MAO/SiO ₂ ) was obtained.

(2) Preparation of supported catalyst

50 mL of toluene was added to the reactor containing the cocatalyst-supporting carrier (MAO/SiO ₂ ), 0.618 g of the transition metal compound (A) prepared in Synthesis Example 1 and 10 mL of toluene were added to the reactor, followed by stirring at 200 rpm for 60 minutes. . Here, 0.320 g of a second transition metal compound (D) represented by the following structural formula and 10 ml of toluene were added to the reactor, followed by stirring at 200 rpm for 12 hours. After stopping the stirring, the mixture 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 transferred to a 200 ml schlenk flask, and the hexane solution was decanted. Then, it was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(D)

(D)

Synthesis example 6: Preparation of hybrid supported catalyst (B/D)

A hybrid supported catalyst was carried out in the same manner as in Synthesis Example 5, except that 0.735 g of the transition metal compound (B) prepared in Synthesis Example 2 was used instead of the transition metal compound (A) in Synthesis Example 5 Was prepared.

Synthesis example 7: Preparation of hybrid supported catalyst (E/D)

In Synthesis Example 6, a hybrid supported catalyst was prepared in the same manner as in Synthesis Example 6, except that 0.765 g of the transition metal compound (E) represented by the following chemical structural formula was used instead of the transition metal compound (B). Was prepared.

(E)

(E)

Synthesis Example 8: Preparation of hybrid supported catalyst (F/D)

In Synthesis Example 6, a hybrid supported catalyst was prepared in the same manner as in Synthesis Example 5, except that 0.883 g of the transition metal compound (F) represented by the following chemical structural formula was used instead of the transition metal compound (B). Was prepared.

(F)

(F)

Example 1: Preparation of Olefin Polymer

The transition metal compound A supported catalyst prepared in Synthesis Example 3 was quantified in a glove box, placed in a 50 mL glass bottle, sealed with a rubber septum, taken out from the glove box, and a catalyst to be injected into polymerization was prepared. The polymerization was carried out in a 600 mL metal alloy reactor equipped with a mechanical stirrer, adjustable temperature, and usable at high pressure. To this reactor, 400 mL of hexane containing 1.0 mmol of triethylaluminium and the supported catalyst prepared above were added to the reactor without air contact, and then 4 g of 1-butene was added at 80°C. Polymerization was carried out for 1 hour while continuously adding gaseous ethylene monomer to the reactor at ^{a pressure of 9 kgf/cm 2.} The polymerization was terminated by first stopping the reaction and then evacuating and removing unreacted ethylene.

The polymer product obtained therefrom was filtered to remove most of the solvent, and then dried in a vacuum oven at 80° C. for 4 hours.

Example 2: Preparation of Olefin Polymer

An olefin polymer was prepared in the same manner as in Example 1, except that the transition metal compound B supported catalyst prepared in Synthesis Example 4 was used instead of the supported catalyst of Synthesis Example 3 used in Example 1. .

Example 3: Preparation of Olefin Polymer

An olefin polymer was prepared in the same manner as in Example 1, except that the hybrid supported catalyst prepared in Synthesis Example 5 was used instead of the supported catalyst of Synthesis Example 3 used in Example 1.

Example 4: Preparation of Olefin Polymer

An olefin polymer was prepared in the same manner as in Example 1, except that the hybrid supported catalyst prepared in Synthesis Example 6 was used instead of the supported catalyst of Synthesis Example 3 used in Example 1.

Comparative Example 1: Preparation of olefin polymer

An olefin polymer was prepared in the same manner as in Example 1, except that the hybrid supported catalyst prepared in Synthesis Example 7 was used instead of the supported catalyst of Synthesis Example 3 used in Example 1.

Comparative Example 2: Preparation of olefin polymer

An olefin polymer was prepared in the same manner as in Example 1, except that the hybrid supported catalyst prepared in Synthesis Example 8 was used instead of the supported catalyst of Synthesis Example 3 used in Example 1.

Comparative example 3: Preparation of olefin polymer

In the preparation example of the supported catalyst of Synthesis Example 3, a supported catalyst was prepared by performing the same method except that the transition metal compound (E) represented by the following structural formula was used as the transition metal compound.

An olefin polymer was prepared in the same manner as in Example 1, except that the transition metal compound (E) supported catalyst prepared above was used instead of the supported catalyst of Synthesis Example 3 used in Example 1. .

(E)

(E)

Comparative example 4: Preparation of olefin polymer

In the Preparation Example of the supported catalyst of Synthesis Example 3, a supported catalyst was prepared by performing the same method as the transition metal compound (F) represented by the following structural formula as the transition metal compound.

An olefin polymer was prepared in the same manner as in Example 1, except that the transition metal compound (F) supported catalyst prepared above was used instead of the supported catalyst of Synthesis Example 3 used in Example 1. .

(F)

(F)

Test example

The yield was calculated by measuring the mass of the olefin polymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4, and the unit mass of the catalyst used in the reaction and the mass of the polymer calculated per hour were measured to compare with each example. The activity (activity) of the catalyst used in the examples was calculated and the results are shown in Table 1 below.

In addition, 10 mg of the polymer prepared in each of the Examples and Comparative Examples was taken as a sample, and the weight average molecular weight (Mw) and molecular weight distribution (MWD) were calculated through GPC analysis.

^{In addition, the content of 1} -butene contained in the polymers prepared in Examples and Comparative Examples was calculated through 1 H-NMR to evaluate the degree of acceleration of the copolymerization reaction of the catalyst. The number of 1-butene contained in the olefin polymer is shown in Table 1 below based on 1000 carbon atoms of the polymer.

In addition, the melting temperature (Tm) of the polymers prepared in Examples and Comparative Examples was measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the olefin polymer was heated to 220° C., maintained at the temperature for 5 minutes, cooled to 20° C., and heated again to 220° C. to obtain Tm. At this time, the rate of rise and fall of the temperature were each adjusted to 10°C/min.

catalyst Active [kg PE./g cat. h] Weight average molecular weight
(g/mol) Molecular weight distribution 1-C4 incoporated No. (NMR) Tm (℃) Example 1 A supported catalyst 2.7 650,000 2.3 5.7 123.9 Example 2 B supported catalyst 3.5 1,030,000 2.3 5.3 124.2 Example 3 A/D
Hybrid supported catalyst 12.3 167,000 3.0 3.9 126.6 Example 4 B/D
Hybrid supported catalyst 13.5 194,000 3.4 3.3 127.2 Comparative Example 1 E/D
Hybrid supported catalyst 11.2 183,000 3.2 2.0 127.3 Comparative Example 2 F/D
Hybrid supported catalyst 11.7 203,000 3.7 1.3 128.1 Comparative Example 3 E catalyst
(Support) 2.3 700,000 2.3 2.9 124.8 Comparative Example 4 F catalyst
(Support) 3.3 1,200,000 2.6 2.3 125.4

Referring to Table 1, the catalyst compositions of Examples 1 to 4 including at least one of transition metal compounds A and B prepared in Synthesis Examples 1 and 2 exhibit high copolymerizability compared to Comparative Examples 1 to 4. I got it.

Claims (15)

Transition metal compound represented by the following formula (1):
[Formula 1]

In Formula 1,
Cp is any one of the ligands represented by the following formulas 2a to 2c,
[Formula 2a]

[Formula 2b]

[Formula 2c]

In Formulas 2a to 2c, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₆ , and R ₃₁ to R ₃₆ are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 20 carbon atoms,
M is Ti, Zr, or Hf,
X ₁ and X ₂ are the same as or different from each other and are each independently halogen,
R ₁ to R ₅ are each hydrogen,
T is

Is,
T ₁ is Si,
Y ₁ and Y ₂ are the same as or different from each other, and are each independently an alkyl group having 1 to 20 carbon atoms.
delete delete delete delete The transition metal compound of claim 1, wherein the transition metal compound is a compound represented by the following Formula 3a or 3b.
[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b,
R ₁₁ to R ₁₄ , and R ₂₁ to R ₂₆ are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 20 carbon atoms,
M is Ti or Zr,
X ₁ and X ₂ are the same as or different from each other and are each independently halogen,
R ₁ to R ₅ are each hydrogen,
Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ are the same as or different from each other, and each independently a C 1 to C 20 alkyl group.
The transition metal compound of claim 1, wherein the transition metal compound is any one of compounds represented by the following structural formula.

A catalyst composition for producing an olefin polymer through a polymerization reaction, comprising the transition metal compound of claim 1.
The catalyst composition for preparing an olefin polymer according to claim 8, further comprising a second transition metal compound represented by Formula 4 below:
[Formula 4]
(Cp3R ₇₁ ) _n (Cp4R ₇₂ ) M'Z' _3-n
In Formula 4, M'is a Group 4 transition metal;
Cp3 and Cp4 are the same as or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. , They may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ₇₁ and R ₇₂ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms To 20 aryloxy group, C2 to C20 alkenyl group, C7 to C20 alkylaryl group, C7 to C40 arylalkyl group, C8 to C40 arylalkenyl group, or C2 to C20 alkynyl group ;
Z'is a halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C7-C40 alkylaryl group, a C7-C40 arylalkyl group, a C6-C20 aryl group, a substituted or unsubstituted An amino group, an alkylalkoxy having 2 to 20 carbon atoms, or an arylalkoxy having 7 to 40 carbon atoms;
n is 0 or 1.
The polymerization reaction of claim 9, wherein the second transition metal compound is a compound wherein Cp3 and Cp4 in Formula 4 are each a cyclopentadienyl group, _{and at least one of R 71} and R ₇₂ is an alkoxyalkyl group having 2 to 20 carbon atoms. Catalyst composition for producing an olefin polymer through.
According to claim 8, Compounds represented by the following formulas 5 and 6, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N,N-dimethylanilinium tetra Kiss (pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N,N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N,N-dimethyl Anilinium 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-trimethylaniline Linium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis (2,3,4,6- Tetrafluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate and methyldi (dodecyl) ammonium tetrakis (Pentafluorophenyl) a catalyst composition for producing an olefin polymer through a polymerization reaction, further comprising at least one cocatalyst selected from the group consisting of borate:
[Formula 5]
R ₈₂ -[Al(R ₈₁ )-O] _m -R ₈₃
In Chemical Formula 5,
R ₈₁ , R ₈₂ and R ₈₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,
m is an integer greater than or equal to 2,
[Formula 6]
D(R ₈₄ ) ₃
In Chemical Formula 6,
D is aluminum or boron,
Each of R ₈₄ is independently a halogen, a C 1 to C 20 hydrocarbyl group, and a halogen substituted C 1 to C 20 hydrocarbyl group.
The catalyst composition for preparing an olefin polymer according to claim 8, further comprising a carrier, wherein the transition metal compound is supported on the carrier.
A method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition of any one of claims 8 to 12.
The method of claim 13, wherein the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, novonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4- A method for producing an olefin polymer comprising at least one selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
14. The method of claim 13, wherein the olefin polymer is an ethylene-1-butene copolymer.