KR20110073079A - NOVEL TRANSITION METAL COMPLEXES AND CATALYSTS COMPOSITIONS FOR PREPARING ELASTOMERIC COPOLYMERS OF ETHYLENE AND α-OLEFINS - Google Patents

Abstract

PURPOSE: A method for preparing elastomeric copolymers of ethylene and α-olefins is provided to produce a polymer with narrow molecular weight distribution using a single site catalyst with excellent high catalyst activity and good copolymerization reactivity with higher alpha-olefins. CONSTITUTION: A method for preparing elastomeric copolymers of ethylene and α-olefins comprises a step of copolymerizing ethylene and C3-C18 α-olefin comonomer in the presence of a transition metal catalyst of chemical formula 1 in a single reactor or serial or parallel secondary continuous reactor to prepare copolymers of ethylene and α-olefins with density of 0.850~0.900 g/cc.

Description

{Novel transition metal complexes and catalysts compositions for preparing elastomeric copolymers of ethylene and α-olefins}

The present invention relates to a method for producing an elastic copolymer of ethylene and α-olefin using a transition metal catalyst composition, and more particularly, to a cyclopentadiene derivative and a heterocyclic aryl at an ortho ( ortho ) position around a Group 4 transition metal. A transition metal catalyst composition comprising a Group 4 transition metal compound comprising at least one aryl oxide ligand substituted with a derivative and not crosslinked with each other, and at least one promoter selected from an aluminum compound and a boron compound. It relates to a method for producing an elastic copolymer of ethylene and α-olefin used.

In the past, so-called Ziegler-Natta catalyst systems composed of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkylaluminum compound have been generally used for preparing ethylene, α-olefin and copolymer. However, the Ziegler-Natta catalyst system exhibits high activity against ethylene homopolymerization, but due to its inhomogeneous catalytic activity, copolymerization with higher α-olefins is not good, and ethylene and α-olefins generally exhibit an elasticity of 0.900 or less. In order to prepare a copolymer of a large amount of α-olefin comonomers must be used, under these conditions there is a disadvantage that the activity of the catalyst is lowered. In addition, the copolymer produced using such a catalyst is very difficult to have suitable physical properties as an elastomer because the composition distribution is very uneven and the molecular weight distribution is wide.

Recently, a so-called metallocene catalyst system has been developed, which is composed of a metallocene compound of a periodic table Group 4 transition metal such as titanium, zirconium, and hafnium and methylaluminoxane as a promoter. Since the metallocene catalyst system is a homogeneous catalyst having a single catalytic activity point, it is possible to prepare a copolymer of ethylene and α-olefin having a narrower molecular weight distribution and a uniform composition distribution than the conventional Ziegler-Natta catalyst system. Have. For example, European Patent Nos. 320,762, 3,726,325 or JP 63-092621, JP 02-84405, or JP 03-2347 disclose Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp ₂ ZrMeCl, Cp ₂ ZrMe ₂ , Ethylene (IndH ₄ ) ₂ Activated metallocene compound with cocatalyst methylaluminoxane in ZrCl _2, etc. to copolymerize ethylene and α-olefin with high activity and have a molecular weight distribution (Mw / Mn) of 1.5 It has been reported that copolymers in the range of -2.0 can be prepared. However, as the catalyst system, when applied to a solution polymerization method performed at a high temperature of 80 ° C. or higher, a large amount of advanced α, like a Ziegler-Natta catalyst, is used to prepare an elastomer having a density of 0.900 or less due to the steric hindrance effect of the catalyst itself. The use of -olefins has disadvantages, and in this case, the β-hydrogen derivatization reaction predominates, so that the weight average molecular weight (Mw) is not suitable for producing a high molecular weight polymer of 30,000 or more.

On the other hand, as a catalyst capable of producing a high catalytic activity and a high molecular weight polymer in copolymerization of ethylene and α-olefin under solution polymerization conditions, so-called geometric non-metallocene catalysts in which transition metals are linked in a ring form are known. . In European Patent No. 0416815 and Patent No. 0420436, an example in which an amide group is linked to one cyclopentadiene ligand in a cyclic form is disclosed. In Patent No. 0842939, a phenol-based ligand is used as an electron donor compound and a cyclopentadiene ligand. An example of a catalyst connected in a cyclic form is shown. However, in the case of these geometric catalysts, the reactivity with higher α-olefins is remarkably improved due to the reduced steric hindrance of the catalyst itself. However, due to the complexity of the catalyst preparation step and the low yield of the ring formation reaction between the ligand and the transition metal compound, it is difficult to realize an economical manufacturing process suitable for preparing a copolymer of ethylene and α-olefin having a density of 0.900 or less. .

On the other hand, examples of non-metallic non-metallocene catalysts include US Patent No. 6,329,478 and Korean Patent Publication No. 2001-0074722. In this patent, a single-site catalyst using at least one phosphineimine compound as a ligand shows high ethylene conversion when copolymerizing ethylene and α-olefin under high temperature solution polymerization conditions of 140 ° C or higher. However, these catalysts, like metallocene catalysts, are not as reactive as higher α-olefins, making them suitable for preparing elastomers of ethylene and higher α-olefins, especially elastomers of ethylene and higher α-olefins with a density of 0.900 or less. Not.

In order to overcome the problems of the prior art, the present inventors have conducted extensive research, and as a result, a non-crosslinked transition metal catalyst system including a cyclopentadiene derivative and an aryloxide ligand in which a heterocyclic aryl derivative is substituted at an ortho- position is obtained. It has been found suitable for the production of elastic copolymers of ethylene and α-olefins having a density of 0.900 or less having a narrow molecular weight distribution and uniform density distribution, and the present invention has been completed based on this.

Accordingly, an object of the present invention is a transition metal compound useful as a catalyst for preparing a copolymer of ethylene and α-olefin having a density of 0.900 or less that can be variously applied as a film, a soft packaging material, a molded product, an electric wire, an impact reinforcement material, a hot melt adhesive, or the like. It is to provide a method for producing a copolymer of ethylene and α-olefin exhibiting elasticity at a density of 0.900 or less using a catalyst composition comprising a, high activity in high-density α-olefin copolymerization of ethylene and α-olefin with a density of 0.900 or less It provides a single point catalyst having excellent reactivity and a polymerization method for producing a narrow molecular weight distribution and composition distribution and a copolymer of ethylene and α-olefin having a weight average molecular weight of 30,000 or more from a commercial point of view. have.

One aspect of the present invention for achieving the above object relates to a cyclopentadiene derivative and ortho (ortho -) around the Group 4 transition metal, as shown in formula (1) where RE for interrogating a substituted aryl oxide ligand cyclic aryl derivative Α- of ethylene and at least one of C3-C18 in the presence of a catalyst composition comprising at least one transition metal catalyst comprising at least one and not cross-linking between ligands and at least one promoter selected from aluminum compounds and boron compounds Provided is a method of copolymerizing olefin comonomers to produce ethylene and α-olefin copolymers having a density of 0.850 to 0.900 g / cc.

 [Formula 1]

 Wherein M is a transition metal of Group 4 on the periodic table;

Cp is a fused ring comprising a cyclopentadienyl ring or a cyclopentadienyl ring capable of bonding a central metal M with a η ⁵ -bond, wherein the cyclopentadienyl ring or cyclopentadienyl fused ring is (C1-C20) Alkyl group, (C6-C30) aryl group, (C2-C20) alkenyl group, (C6-C30) aryl (C1-C20) alkyl group can be further substituted;

또는

이고; R¹, R², R³, R⁴, R⁵, R⁶, R⁷ 및 R⁸ 은 서로 독립적으로 수소 원자, (C1-C20)알킬기, (C3-C20)시클 로알킬기, (C1-C20)알킬 치환 또는 (C6-C30)아릴 치환 실릴기, (C6-C30)아릴기, (C6-C30)아릴(C1-C10)알킬기, (C1-C20)알콕시기, (C1-C20)알킬 치환 또는 (C6-C20)아릴 치환 실록시기, (C1-C20)알킬 치환 또는 (C6-C30)아릴 치환 아미노기, (C1-C20) 알킬 치환 또는 (C6-C30)아릴 치환 포스핀기, (C1-C20)알킬 치환 머캡토기 또는 니트로기이며, 상기 R¹ 내지 R⁸ 의 알킬기, 아릴 또는 알콕시기는 할로겐으로 더 치환되거나 인접한 치환체와 함께 융합고리를 형성할 수 있으며; A is a substituent of the following structure

or

ego; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a (C1-C20) alkyl group, a (C3-C20) cycloalkyl group, (C1-C20 ) Alkyl substituted or (C6-C30) aryl substituted silyl group, (C6-C30) aryl group, (C6-C30) aryl (C1-C10) alkyl group, (C1-C20) alkoxy group, (C1-C20) alkyl substituted Or (C6-C20) aryl substituted siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group, (C1-C20 An alkyl substituted mercapto group or a nitro group, wherein the alkyl group, aryl or alkoxy group of R ¹ to R ⁸ may be further substituted with halogen or may form a fused ring with adjacent substituents;

D is NR ⁹ , oxygen or sulfur atom; R ⁹ is a linear or nonlinear (C 1 -C 20) alkyl group, (C 6 -C 30) aryl group, (C 1 -C 20) alkyl substituted or (C 6 -C 30) aryl substituted silyl group;

n is an integer of 1 or 2;

X independently of one another is a halogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C30) aryl (C1-C20) alkyl group, (C1-C20) alkoxy group, (C3-C20) alkyl Group consisting of a siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group and (C1-C20) alkyl substituted mercapto group Is selected from.

Hereinafter, the present invention will be described in more detail.

In the transition metal compound of Formula 1, M, which is a central metal, is preferably titanium, zirconium or hafnium. In addition, Cp includes a cyclopentadiene anion or a cyclopentadienyl ring capable of bonding η ⁵ -to the central metal, and specific examples of the substituted or unsubstituted fused ring derivatives include cyclopentadienyl, methylcyclopentadienyl, Dimethyl cyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopentadienyl, tert -butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, Indenyl, methyl indenyl, dimethyl indenyl, ethyl indenyl, isopropyl indenyl, florenyl, methyl fluorenyl, dimethyl fluorenyl, ethyl fluorenyl or isopropyl fluorenyl and the like.

또는

로서, 하기 화학식 2 또는 화학식 3의 화합물로서 표시된다.The transition metal compound of the present invention is specifically a substituent of A

or

As a compound of the following formula (2) or (3).

[Formula 2]

(3)

With respect to R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ on the heterocyclic aryl group substituted aryloxide ligand of Formula 1 to Formula 3, examples of the fluorine atom include fluorine , Chlorine, bromine or iodine atoms;

Examples of linear or nonlinear (C1-C20) alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec -butyl, tert -butyl, n-pentyl, neopentyl, A wheat group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group or n-eicosyl group, of which methyl, ethyl, isopropyl or tert -butyl group are preferred. Is;

The (C3-C20) cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cychlorohexyl group, a cychlorohaptyl group, or an adamantyl group, of which a cyclopentyl group or cyclohexyl group is preferable. ego;

Examples of the (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group are methylsilyl group, ethylsilyl group, phenylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group, diphenylmethylsilyl group, trimethyl Silyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri- sec -butylsilyl group, tri- tert -butylsilyl group, tri-isobutyl Silyl group, tert -butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, or triphenylsilyl group, Among these, trimethylsilyl group, tert- Butyldimethylsilyl group or triphenylsilyl group;

The (C6-C30) aryl group or the (C1-C20) alkyl (C6-C30) aryl group is, for example, a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2 , 3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3 , 4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec -butylphenyl group, tert -butyl Phenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, biphenyl (biphenyl), florenyl, triphenyl, Naphthyl group or anthracenyl group, of which preferred is phenyl group, naphthyl group, biphenyl, biisopropylphenyl, 3,5-xylyl group It is 2,4,6, and;

Examples of the (C6-C30) aryl (C1-C10) alkyl group are benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, ( 2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, ( 2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl-phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2 , 4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) Methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl ) Methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylpe ) Methyl group, (n- tetradecyl-phenyl) methyl, triphenylmethyl group, naphthyl can be mentioned a methyl group or an anthracenyl group, of which preferred is a benzyl group, a triphenylmethyl group, and;

Examples of the (C1-C20) alkoxy group are methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec -butoxy group, tert -butoxy group, n-pentoxy group and neopentoxy group , n-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadexyl group or n-ecosoxy group, and among these, methoxy group, ethoxy group, isopropoxy group or tert- Butoxy group;

Examples of the (C1-C20) alkyl substituted or (C6-C20) aryl substituted siloxy group include trimethylsiloxy group, triethylsiloxy group, tri-n-propylsiloxy group, triisopropylsiloxy group, and tri-n-butylsiloxy group , Tri- sec -butylsiloxy group, tri- tert -butylsiloxy group, tri-isobutylsiloxy group, tert -butyldimethylsiloxy group, tri-n-pentylsiloxy group, tri-n-hexylsiloxy group or tricyclohexyl Siloxy groups; preferred are trimethylsiloxy groups or tert -butyldimethylsiloxy groups;

Examples of the (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di- sec -butyl Amino group, di- tert -butylamino group, diisobutylamino group, tert - butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, dibenzylamino group, Methylethylamino group, methylphenylamino group, benzylhexylamino group, bistrimethylsilylamino group or bis-tert-butyldimethylsilylamino group, or the same alkyl substituted phosphine group, of which dimethylamino group, diethylamino group or diphenylamino group are preferable;

Examples of the (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group include dimethylphosphine group, diethylphosphine group, di-n-propylphosphine group, diisopropylphosphine group, di-n-butylphosphine group , Di- sec -butylphosphine group, di- tert -butylphosphine group, diisobutylphosphine group, tert -butylisopropylphosphine group, di-n-hexylphosphine group, di-n-octylphosphine group, di-n -Decyl phosphine group, diphenyl phosphine group, dibenzyl phosphine group, methyl ethyl phosphine group, methyl phenyl phosphine group, benzyl hexyl phosphine group, bistrimethylsilyl phosphine group or bis-tert- butyl dimethyl silyl phosphine group, Preferred among them are a dimethylphosphine group, diethylphosphine group or diphenylphosphine group;

Examples of (C1-C20) alkyl-substituted mercapto groups are methylmercaptan, ethylmercaptan, propylmercaptan, isopropylmercaptan, 1-butylmercaptan, isopentylmercaptan, preferably ethylmercaptan, or iso Propylmercaptan;

The alkyl, aryl or alkoxy group of R ¹ to R ⁸ may be further substituted with halogen or may form a fused ring with adjacent substituents.

R ⁹ is a linear or non-linear (C1-C20) alkyl group which is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec -butyl, tert -butyl, n-pentyl or neopentyl , Amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, or n-eicosyl group, and among these, methyl group, ethyl group and isopropyl group are preferable. , tert -butyl group, amyl group;

Examples of the (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group include methylsilyl group, ethylsilyl group, phenylsilyl group, dimethylsilyl group, diethylsilyl group or diphenylsilyl group, trimethylsilyl group, Triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri- sec -butylsilyl group, tri- tert -butylsilyl group, tri-isobutylsilyl group, and tert -butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group or triphenylsilyl group, and among these, trimethylsilyl group and tert -butyldimethylsilyl Group or triphenylsilyl group.

X is an example of a halogen atom, and a fluorine, chlorine, bromine or iodine atom;

Examples of (C1-20) alkyl groups other than Cp derivatives include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec -butyl, tert -butyl, n-pentyl and neopentyl, Amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group or n-eicosyl group, of which methyl, ethyl, isopropyl and tert -butyl are preferred. Group or amyl group;

The (C3-C20) cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cychlorohaptyl group or an adamantyl group, of which a cyclopentyl group or a cychlorohexyl group is preferable. ; Examples of (C6-C30) aryl (C1-C20) alkyl group are benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, ( 2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, ( 2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl-phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2 , 4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) Methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl ) Methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylpe ) Methyl group, (n- tetradecyl phenyl) methyl group, can be mentioned a naphthyl group or an anthracenyl group, of which preferred is a benzyl group;

(C1-C20) Alkoxy group methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec -butoxy group, tert -butoxy group, n-pentoxy group, neopentoxy group, n -Hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadexyl group or n-ecosoxy group, and among these, a methoxy group, an ethoxy group, an isopropoxy group or a tert -butoxy group is preferable. Is; Examples of the (C3-C20) alkylsiloxy group include trimethylsiloxy group, triethylsiloxy group, tri-n-propylsiloxy group, triisopropylsiloxy group, tri-n-butylsiloxy group, tri- sec -butylsiloxy group, Tri- tert -butylsiloxy group, tri-isobutylsiloxy group, tert -butyldimethylsiloxy group, tri-n-pentylsiloxy group, tri-n-hexylsiloxy group or tricyclohexylsiloxy group, among which Preferred are trimethylsiloxy groups, or tert -butyldimethylsiloxy groups;

Examples of (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino groups, or (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine groups, include dimethylamino groups, diethylamino groups, di-n-propyl Amino group, diisopropylamino group, di-n-butylamino group, di- sec -butylamino group, di- tert -butylamino group, diisobutylamino group, tert - butylisopropylamino group, di-n-hexylamino group, di-n -Octylamino group, di-n-decylamino group, diphenylamino group, dibenzylamino group, methylethylamino group, methylphenylamino group, benzylhexylamino group, bistrimethylsilylamino group or bis-tert-butyldimethylsilylamino group, or the same alkyl substituted phosphine group Among these, preferred are dimethylamino group, diethylamino group or diphenylamino group;

Examples of the (C1-C20) alkyl substituted mercapto group are methylmercaptan, ethylmercaptan, propylmercaptan, isopropylmercaptan, 1-butylmercaptan or isopentylmercaptan.

On the other hand, the transition metal compound of Formula 1 according to the present invention, in order to become an active catalyst component used in the polymerization of olefins, preferably weak binding force while extracting the X ligand in the transition metal compound according to the present invention to cation the central metal A counterion having an ion, ie a boron compound or an aluminum compound, or a mixture thereof, capable of acting as an anion, is used as promoter. In this case, the aluminum compound used is to remove traces of polar substances such as water, which act as catalyst poisons. However, when the X ligand is halogen, it may also act as an alkylating agent.

The boron compound which may be used as a promoter in the present invention may be selected from compounds represented by the following Chemical Formulas 4 to 6 as shown in US Patent No. 5,198,401.

[Formula 4]

B (R ¹⁰ ) ₃

[Chemical Formula 5]

[R ¹¹ ] ⁺ [B (R ¹⁰ ) ₄ ] ^-

[Formula 6]

[(R ¹² ) _q ZH] ⁺ [B (R ¹⁰ ) ₄ ] ^-

In Chemical Formulas 4 to 6, B is a boron atom; R ¹⁰ is a phenyl group, wherein the phenyl group is 3 to 5 selected from a fluorine atom or a (C1-C20) alkyl group unsubstituted or substituted by a fluorine atom, or a (C1-C20) alkoxy group unsubstituted or substituted by a fluorine atom May be further substituted with 4 substituents;

R ¹¹ is a (C5-C7) aromatic radical (C1-C20) alkyl (C6-C20) aryl radical or a (C6-C30) aryl (C1-C20) alkyl radical such as a triphenylmethyl radical;

Z is nitrogen or phosphorus atom;

R ¹² is a (C1-C20) alkyl radical, or an annilium radical substituted with two (C1-C10) alkyl groups with a nitrogen atom; q is an integer of 2 or 3.

Preferred examples of the boron-based cocatalysts include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro Phenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4 , 5-tetrafluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate or tetrakis (3,5-bistrifluoromethylphenyl) borate Can be mentioned. Specific examples of these compounds include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Phenylmethyl tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (penta) Fluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium Tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium Tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorofe Borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl ) Borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate And most preferred of these are N, N-dimethylanilinium tetrakispentafluorophenylborate, triphenylmethyllinium tetrakispentafluorophenylborate or trispentafluoroborate.

As the aluminum compound used in the present invention, an aluminoxane compound of Formula 7 or Formula 8, an organoaluminum compound of Formula 9, or an organoaluminum hydrocarbyl oxide compound of Formula 10 or Formula 11 may be used.

[Formula 7]

(-Al (R ¹³ ) -O-) _m

[Formula 8]

(R ¹³ ) ₂ Al-(-O (R ¹³ )-) _p- (R ¹³ ) ₂

[Formula 9]

(R ¹⁴ ) _r Al (E) _3-r

[Formula 10]

(R ¹⁵ ) ₂ AlOR ¹⁶

[Formula 11]

R ¹⁵ Al (OR ¹⁶ ) ₂

In Formulas 7 to 11, R ¹³ is a (C1-C20) alkyl group, preferably a methyl group or an isobutyl group, m and p are integers between 5 and 20; R ¹⁴ and R ¹⁵ are each independently of the (C1-C20) alkyl group; E is a hydrogen atom or a halogen atom; r is an integer of 1 to 3; R ¹⁶ may be selected from a (C1-C20) alkyl group or a (C6-C30) aryl group.

As a specific example that can be used as the aluminum compound,

Aluminoxane compounds include methylaluminoxane, improved methylaluminoxane or tetraisobutylaluminoxane;

Examples of organoaluminum compounds include trialkylaluminums including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum or trihexylaluminum; Dialkylaluminum chlorides including dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride or dihexylaluminum chloride; Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride or hexylaluminum dichloride; And dialkylaluminum hydrides including dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride or dihexylaluminum hydride, preferably trialkylaluminum, More preferably, it is triethyl aluminum or triisobutyl aluminum.

In this case, the molar ratio of the transition metal atom (M): boron atom: aluminum atom, which is the central metal, is preferably 1: 0.1 to 100: 10 to 1,000, and more preferably 1: 0.5 to 5: 25 to 500.

The method for preparing a copolymer of ethylene and an α-olefin having a density of 0.900 or less using the transition metal catalyst composition of the present invention is carried out using the transition metal catalyst, a promoter, and an ethylene and α-olefin comonomer in the presence of a suitable organic solvent. In contact with the solution. In addition, one or more continuous stirring or pipe types may be used in the reactor, and when two or more are used in series or in parallel, copolymers having different molecular weights and densities according to reaction fractions may be different depending on the reaction conditions of each reactor. It is also possible to prepare a copolymer in a mixed form.

Preferred organic solvents that can be used in the preparation method are C3-C20 hydrocarbons, specific examples of which are butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane , Benzene, toluene or xylene, and the like, and in some cases, a mixture of two or more of the above organic solvents may be used.

As the comonomer, C3-C18 α-olefins may be used, and preferably propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1- At least one can be selected from the group consisting of dodecene, 1-hexadecene, and 1-octadecene. More preferably, 1-butene, 1-hexene, 1-octene or 1-decene can be copolymerized with ethylene.

The polymerization reaction is carried out at a pressure and at a temperature where the reactants in the reactor can be in solution. In this case, the preferable polymerization reactor pressure is 10 to 200 atm, preferably 20 to 150 atm, and the polymerization temperature is 60 to 250 ° C, preferably 80 to 170 ° C.

Copolymers prepared according to the process of the invention usually contain 40 to 90% by weight of ethylene, preferably 50 to 85% by weight of ethylene, more preferably in the range of 55 to 80% by weight. The density range is between 0.850 and 0.900 g / cc, preferably between 0.855 and 0.899 g / cc, more preferably between 0.860 and 0.890 g / cc.

Hydrogen may be used as a molecular weight regulator to control the molecular weight when preparing the copolymer, and usually has a weight average molecular weight (Mw) in the range of 30,000 to 500,000, and has a molecular weight distribution in the range of 1.5 to 3.0.

The copolymer of ethylene and α-olefin prepared as described above is different from the copolymer prepared from the existing Ziegler-Natta catalyst, which has a small branch due to α-olefin in the high molecular weight portion and most branches are concentrated in the low molecular weight portion. Even in the molecular weight part, the α-olefin branch is uniformly distributed, and there is almost no low molecular weight component containing a large amount of α-olefin branch that can be extracted from hexane, etc., thereby providing important physical properties as an elastomer and greatly improving hygiene of the final product. Can be. Therefore, the copolymer of ethylene and α-olefin prepared in this way can be variously applied, such as impact resistance reinforcement of the crystalline polymer, film, soft packaging material, molding product, wire coating, hot melt adhesive.

Since the catalyst composition presented in the present invention is present in a uniform form in the polymerization reactor, it is preferable to apply to the solution polymerization process carried out at a temperature above the melting point of the polymer. However, as disclosed in US Pat. No. 4,752,597, the transition metal catalyst and the promoter may be supported on a porous metal oxide support, and may be used in slurry polymerization or gas phase polymerization as a non-uniform catalyst composition.

The transition metal catalyst composition according to the present invention and a method for preparing a copolymer of ethylene and an α-olefin using the same have a high catalytic activity and have excellent copolymerization reactivity with higher α-olefins and produce a high molecular weight polymer in high yield. As a result, commercial practicality is high in preparing a copolymer having an elasticity of 0.850 to 0.900 g / cc compared to metallocene and non-metallocene-based single site catalysts. In addition, since it is a non-crosslinked single-site catalyst, the production process of the catalyst is simple and the production yield is high. Thus, the catalyst production cost is low, and the amount of the α-olefin comonomer is used is low.

Therefore, the transition metal catalyst composition and preparation method according to the present invention can be usefully used for the preparation of copolymers of ethylene and α-olefins having various physical properties and elasticity.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited by the following Examples.

Except where noted, all ligand and catalyst manufacturing processes were carried out using standard Schlenk or glovebox techniques under nitrogen atmosphere and the organic solvent used for the reaction was refluxed under sodium metal and benzophenone to remove moisture Distilled immediately before use. ¹ H-NMR analysis of the prepared ligand and catalyst was carried out using Varian Oxford 300 MHz at room temperature.

Cyclohexane, a polymerization solvent, was used after passing through a tube filled with a Q-5 catalyst (manufactured by BASF), silica gel and activated alumina and bubbling with high purity nitrogen to sufficiently remove moisture, oxygen and other catalyst poisons.

The polymerized polymer was analyzed by the method described below.

1. Melt Flow Index (MI)

It measured according to ASTM D 2839.

2. Density

According to ASTM D 1505, it was measured using a density gradient tube.

3. Melting Point (Tm) Analysis

Dupont DSC2910 was used in a 2 ^nd heating conditions at a rate of 10 ℃ / min under a nitrogen atmosphere.

4. Molecular Weight and Molecular Weight Distribution

PL210 GPC equipped with PL Mixed-BX2 + preCol was used to measure 1.0 mL / min at 135C in 1,2,3-trichlorobenzene solvent and molecular weight was corrected using PL polystyrene standards.

5. α-olefin content (% by weight) in the copolymer

The Bruker DRX500 nuclear magnetic resonance spectrometer was used to measure ¹³ C-NMR mode at 120 C using a 1,2,4 trichlorobenzene / C ₆ D ₆ (7/3 weight fraction) mixed solvent at 125 MHz. (Reference: Randal, JC JMS - Rev . Macromol. Chem . Phys . 1980, C29 , 201)

Preparation Example 1 Preparation of ( dichloro ) ( pentamethylcyclopentadienyl ) (2-thiophen-2'-yl) phenoxy ) titanium ( IV )

2- (2'- Methoxyphenyl Preparation of thiophene

2-bromo thiophene (7.2 g, 43.9 mmol), 2-methoxyphenylboronic acid (6.7 g, 43.9 mmol), palladium acetate (0.14 g, 0.62 mmol), triphenylphosphine (0.6 mg, 2.3 mmol) ) And 10 ml of water and 40 ml of dimethoxyethane mixed solution were added to a flask on which potassium phosphate (9.40 g, 44.3 mmol) was added and refluxed for 6 hours. After cooling to room temperature, an aqueous ammonium chloride solution (50 mL) and 100 mL of diethyl ether were added, the organic layer was separated, the residue was extracted with diethyl ether, the collected organic layer was dried over magnesium sulfate, and volatiles were removed. Then purified by hexane using a silica gel chromatography tube to give 7.9 g (yield 95%) of 2- (2'-methoxyphenyl) thiophene as a colorless liquid.

¹ H-NMR (C ₆ D ₆ ) δ = 3.26 (s, 3H), 6.49-6.53 (d, 1H), 6.77-7.03 (m, 4H), 7.47-7.49 (d, 1H), 7.60-7.64 ( d, 1H) ppm

Preparation of 2- (thiophen-2'-yl) phenol

2- (2'-methoxyphenyl) thiophene (7 g, 36.8 mmol) prepared above was dissolved in 100 mL of methylene chloride, and 40 mL of borontribromide (1M-methylene chloride solution) was added dropwise at -78 ° C. The temperature was gradually raised to room temperature and reacted for 3 hours. After the reaction, a mixed solution of ice (50 g) and diethyl ether (100 mL) were added, the organic layer was separated, the aqueous layer was extracted with diethyl ether, the collected organic layer was dried over magnesium sulfate, and the volatiles were removed. Purified with a mixed solution of hexane and methylene chloride to give 2.9g (yield 40%) of 2- (thiophen-2'-yl) phenol as a colorless liquid.

¹ H-NMR (C ₆ D ₆ ) δ = 6.54-6.58 (d, 1H), 6.59-6.95 (m, 4H), 7.12-7.15 (d, 1H), 7.36-7.41 (d, 1H) ppm

( Dichloro ) ( Pentamethylcyclopentadienyl ) (2-thiophene-2'-yl) Phenoxy )titanium( IV Manufacture of

2- (thiophene-2'-yl) phenol (2.07 g, 11.76 mmol, Aldrich) was added to the dried flask, dissolved in diethyl ether, and stirred well. N-butyllithium (8.08 ml, 1.6 M in hexane, Aldrich) was slowly added dropwise to the mixture. After dropping, the temperature is maintained for 1 hour and then raised to room temperature and stirred for 12 hours. After removing the solvent layer, the precipitate was washed with hexane, and the volatiles of the obtained precipitate were removed and dissolved in toluene. After the temperature of this mixture was lowered to 0 ° C., pentamethylcyclopentadienyl titanium chloride (1.70 g, 5.88 mmol) was dissolved in toluene and slowly added dropwise thereto. After dropping, it is maintained for 1 hour, then raised to room temperature and stirred for another 24 hours. After the reaction was completed, the solids were filtered out, the volatiles were removed from the solution, and then dissolved in toluene to recrystallize to obtain 1.64 g (yield 65%) of orange crystals.

¹ H-NMR (C ₆ D ₆ ) δ = 1.73 (s, 15H), 6.75-6.79 (d, 1H), 6.85-6.94 (m, 3H), 7.14-7.18 (d, 1H), 7.41-7.45 ( d, 1H)), 7.57-7.59 (d, 1H) ppmMass (APCI mode, m / z): 429

Preparation Example 2 Preparation of ( dichloro ) ( pentamethylcyclopentadienyl ) (2- (pyridin-2'-yl) phenoxy ) titanium ( IV )

2- (2'- Methoxyphenyl Preparation of Pyridine

2-bromo pyridine (4.28 ml, 43.9 mmol), 2-methoxyphenylboronic acid (6.7 g, 43.9 mmol), palladium acetate (0.14 g, 0.62 mmol), triphenylphosphine (0.6 mg, 2.3 mmol) 10 ml of water and 40 ml of dimethoxyethane mixed solution were added to a flask to which potassium phosphate (9.40 g, 44.3 mmol) was added and refluxed for 6 hours. After cooling to room temperature, an aqueous ammonium chloride solution (50 mL) and 100 mL of diethyl ether were introduced, the organic layer was separated, the residue was extracted with diethyl ether, the collected organic layer was dried over magnesium sulfate, and volatiles were removed. Purification with normal hexane using a silica gel chromatography tube yielded 7.7 g (yield 95%) of a colorless liquid, 2- (2'-methoxyphenyl) pyridine.

¹ H-NMR (C ₆ D ₆ ) δ = 3.22 (s, 3H), 6.55-8.67 (m, 8H) ppm

Preparation of 2- (pyridin-2'-yl) phenol

40 ml of 35% hydrochloric acid was added and 40 ml of pyridine was stirred at 200 ° C. for 30 minutes, followed by distillation of water at 220 ° C. to remove 2- (2'-methoxyphenyl) pyridine (6.8 g, 36.8 mmol), followed by 12 at 200 ° C. The reaction was time. The temperature was lowered to room temperature, and distilled water was added, followed by titration with an aqueous sodium hydroxide solution. Extract the organic layer with methylene chloride, dry with magnesium sulfate, remove volatiles and purify with a mixture of hexane and ethyl acetate using a silica gel chromatography tube. 3.5g of yellow solid 2- (pyridin-2'-yl) phenol (Yield 52%) was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 6.30-7.72 (m, 7H), 8.43-8.67 (m, 2H) ppm

( Dichloro ) ( Pentamethylcyclopentadienyl ) (2- (pyridin-2'-yl) Phenoxy )titanium( IV Manufacturing

2- (pyridin-2'-yl) phenol (2.64 g, 15.42 mmol, Aldrich) was added to the dried flask, dissolved in toluene, stirred well and the temperature was lowered to 0 ° C. N-butyllithium (5.86 ml, 2.5 M in hexane Aldrich) was slowly added dropwise to the mixture. After dropping, the temperature is maintained for 1 hour and then raised to room temperature and stirred for 12 hours. After removing the solvent layer, the precipitate is washed with purified normal hexane, the obtained volatiles of the precipitate are removed and dissolved in toluene. After the temperature of this mixture was lowered to 0 ° C., pentamethylcyclopentadienyl titanium chloride (2.23 g, 12.59 mmol) was dissolved in toluene and slowly added dropwise thereto. After dropping, it is maintained for 1 hour, then raised to room temperature and stirred for another 24 hours. After the reaction was completed, the solids were filtered out, the volatiles were removed from the solution, and then dissolved in toluene to recrystallize to obtain 2.1 g (yield 49%) of orange crystals.

¹ H-NMR (C ₆ D ₆ ) δ = 1.66 (s, 15H), 6.617.35 (m, 5H), 7.80 (m, 1H), 8.08 (m, 1H), 8.62 (m, 1H) ppm

Mass (APCI mode, m / z): 424

Example  One

Copolymerization of ethylene and 1-octene was carried out using a batch polymerization apparatus as follows.

After sufficiently drying, 1140 mL of cyclohexane and 150 ml of 1-octene were added to a 2000 mL stainless steel reactor substituted with nitrogen, and then modified methylaluminoxane-7 (Akzo Nobel, modified MAO-7, 7 wt% Al Isopar solution). ) 54.2 mM, 11.1 mL of toluene solution was added to the reactor. The reactor was then heated to 140 ° C., followed by (dichloro) (pentamethylcyclopentadienyl) (2-thiophen-2′-yl) phenoxy) titanium (IV) (5 mM toluene solution prepared in Preparation Example 1). ) 0.4 mL and 0.6 mL of triphenylmethyllinium tetrakispentafluorophenylborate (99%, Boulder Scientific) 10 mM toluene solution were added sequentially, followed by filling the reactor with ethylene pressure up to 30 kg / cm ² and continuously It was supplied to the polymerization to be. Within 1 minute of the reaction, the maximum temperature was reached to 162.5 ° C. After 1 minute, 100 mL of 10 vol% aqueous hydrochloric acid solution was added to terminate the polymerization. After stirring for 1 hour with 1.5 L of ethanol, the reaction product was filtered and separated. It was. The recovered reaction product was dried in a vacuum oven at 60 ° C. for 8 hours to give 37.5 g of polymer. The melt index of the polymer was 10.5, the density was 0.8835 g / cc, the weight average molecular weight (Mw) was 48,000 g / mol, the molecular weight distribution (Mw / Mn) was 2.25, and 1-octene content was analyzed by gel chromatography. 25.1 wt%.

Example  2

The copolymerization of ethylene and 1-octene was performed in the same manner as in Example 1 except that 230 mL of 1-octene was used.

The maximum temperature reached 164.5 ° C. and finally 40.0 g of polymer was obtained. The melt index of the polymer was 14.2, the density was 0.8710 g / cc, the weight average molecular weight (Mw) was 36,000 g / mol, the molecular weight distribution (Mw / Mn) was 2.20, and the 1-octene content was analyzed by gel chromatography. 31.3 wt%.

Example  3

Copolymerization of ethylene and 1-decene was carried out in the same manner as in Example 1 except that 150 mL of 1-decene was used instead of 1-octene.

The maximum temperature reached 165 ° C. and finally 41.0 g of polymer was obtained. The melt index of the polymer was 12.0 and the density was 0.8897 g / cc. The weight average molecular weight (Mw) was 42,000 g / mol and the molecular weight distribution (Mw / Mn) was 2.60 when analyzed by gel chromatography.

Example  4

The copolymerization of ethylene and 1-octene was performed in the same manner as in Example 1 except that the reaction temperature was heated to 80 ° C. and 150 mL of 1-decene was added before the catalyst was added.

The maximum temperature of 154.0 ° C was reached and finally 95.0 g of polymer was obtained. The melt index of the polymer was 8.5 and the density was 0.8840 g / cc, and the weight average molecular weight (Mw) was 61,000 g / mol when analyzed by gel chromatography. The molecular weight distribution (Mw / Mn) was 2.30.

Example  5

Ethylene was the same as in Example 1 except for using (dichloro) (pentamethylcyclopentadienyl) (2- (pyridin-2'-yl) phenoxy) titanium (IV) prepared in Preparation Example 2 as a catalyst. Copolymerization with 1-octene was carried out.

The maximum temperature of 168 ° C was reached and finally 47 g of polymer was obtained. The melt index of the polymer was 12.5, the density was 0.8795 g / cc, and the weight average molecular weight (Mw) was 41,000 g / mol when analyzed by gel chromatography. The molecular weight distribution (Mw / Mn) was 2.15 and the 1-octene content was 29.3 wt%.

Example  6

Copolymerization of ethylene and 1-octene was performed in the same manner as in Example 5 except that 60 mL of 1-octene was used.

The maximum temperature of 171.0 ° C was reached and finally 49 g of polymer was obtained. The melt index of the polymer was 11.0 and the density was 0.8998 g / cc, and the weight average molecular weight (Mw) was 43,000 g / mol, The molecular weight distribution (Mw / Mn) was 2.10 and the 1-octene content was 16.5 wt%.

Example  7

The copolymerization of ethylene and 1-octene was performed in the same manner as in Example 5 except that 230 mL of 1-octene was used.

The maximum temperature reached 169 ° C and finally 48 g of polymer was obtained. The melt index of the polymer was 17.0 and the density was 0.8690 g / cc. The weight average molecular weight (Mw) was 31,000 g / mol when analyzed by gel chromatography. The molecular weight distribution (Mw / Mn) was 2.25 and the 1-octene content was 33.5 wt%.

Example  8

The copolymerization of ethylene and 1-octene was performed in the same manner as in Example 7, except that the reaction temperature was heated to 80 ° C. before the catalyst was added.

The maximum temperature reached 148 ° C and finally 92 g of polymer was obtained. The melt index of the polymer was 5.5 and the density was 0.8810 g / cc. The weight average molecular weight (Mw) was 79,000 g / mol when analyzed by gel chromatography. The molecular weight distribution (Mw / Mn) was 2.05 and the 1-octene content was 26.3 wt%.

As can be seen from the above examples, a copolymer of ethylene and α-olefin having a high molecular weight of 30,000 or more and a narrow molecular weight distribution of 3 or less at a density of 0.900 g / cc or less through the catalyst composition and the preparation method according to the present invention It can be seen that can be prepared successfully under the batch reaction conditions.

In addition, using the catalyst system of the present invention, a copolymer of ethylene and α-olefin having a density of 0.900 g / cc or less can be produced with high yield while introducing a small amount of α-olefin comonomer under high temperature solution polymerization conditions. Shows.

Although described in detail with respect to embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.

Claims (12)

Ethylene having a density of 0.850 to 0.900 g / cc by copolymerization of ethylene and an α-olefin comonomer of C3-C18 in a single reactor or a catalyst composition comprising a transition metal catalyst represented by the following formula (1) in a series or parallel secondary continuous reactor: And a copolymer of α-olefin. [Formula 1]

[In Formula 1, M is a transition metal of Group 4 on the periodic table; Cp is a fused ring comprising a cyclopentadienyl ring or a cyclopentadienyl ring capable of bonding a central metal M with a η ⁵ -bond, wherein the cyclopentadienyl ring or cyclopentadienyl fused ring is (C1-C20) Alkyl group, (C6-C30) aryl group, (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group; A is a substituent of the following structure

or

ego; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a (C1-C20) alkyl group, a (C3-C20) cycloalkyl group, (C1-C20) Alkyl substituted or (C6-C30) aryl substituted silyl, (C6-C30) aryl group, (C6-C30) aryl (C1-C10) alkyl group, (C1-C20) alkoxy group, (C1-C20) alkyl substituted or (C6-C20) aryl substituted siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino group or (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group, (C1-C20) An alkyl-substituted mercapto group or a nitro group, wherein the alkyl, aryl or alkoxy group of R ¹ to R ⁸ may be further substituted with halogen or form a fused ring with adjacent substituents; D is NR ⁹ , oxygen or sulfur atom; R ⁹ is a linear or nonlinear (C 1 -C 20) alkyl group, (C 6 -C 30) aryl group, (C 1 -C 20) alkyl substituted or (C 6 -C 30) aryl substituted silyl group; n is an integer of 1 or 2; X independently of one another is a halogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C30) aryl (C1-C20) alkyl group, (C1-C20) alkoxy group, (C3-C20) alkyl Group consisting of a siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group and (C1-C20) alkyl substituted mercapto group Is selected from.] The method of claim 1, M of the transition metal catalyst of Formula 1 is Ti, Zr or Hf, characterized in that the copolymer of ethylene and α-olefin. The method of claim 1, The catalyst composition is a transition metal catalyst of Formula 1; Cocatalysts of aluminoxane compounds or organoaluminum compounds; And a cocatalyst of the boron compound. The method of claim 3, wherein The ratio of the transition metal catalyst of Formula 1 to the cocatalyst is 1: 0.5 to 50: 1 to 1,000 based on the molar ratio of the transition metal atom (M): boron atom: aluminum atom. Incorporation method. The method of claim 3, wherein The cocatalyst of the boron compound is one or a mixture selected from N, N-dimethylanilinium tetrakispentafluorophenylborate and triphenylmethyllinium tetrakispentafluorophenylborate. Method of producing a copolymer. The method of claim 1, The α-olefin comonomer is at least one selected from propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene A method for producing a copolymer of ethylene and an α-olefin. The method of claim 1, Method of producing a copolymer of ethylene and α-olefins, characterized in that the content of α-olefin comonomer in the copolymer is 10% by weight to 60% by weight. The method of claim 1, The copolymer has a density of 0.850 to 0.899 g / cc ethylene and α-olefin copolymer production method. The method of claim 8, The copolymer has a density of 0.860 to 0.890 g / cc ethylene and α-olefin copolymer production method. The method of claim 1, The weight average molecular weight of the copolymer is 30,000 to 500,000, the molecular weight distribution (Mw / Mn) is 1.5 to 3.0, characterized in that the copolymer of ethylene and α-olefin. The method of claim 1, The pressure in the reactor for preparing the copolymer is 10 to 150 atm, the polymerization reaction temperature is 80 to 250 ℃ characterized in that the copolymer production method of ethylene and α-olefin. A copolymer of ethylene and an -olefin produced by the method of any one of claims 1 to 11.