KR101889980B1 - New Transition metal complex having Quinolin-1(2H)-yl group and catalyst composition containing the same for olefin polymerization, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transition metal catalyst composition having a high catalytic activity for the production of a transition metal compound and an ethylene homopolymer or a copolymer of ethylene and an a-olefin containing the same, and more particularly to a transition metal catalyst composition having a cyclopentadiene derivative And an aryl group and an alkyl group and has a fused structure at the same time, minimizing steric hindrance, facilitating the injection of comonomer, reducing the vibronic mode at high temperature, (2H) -based ligand and not cross-linking ligands to ethylene homopolymers or copolymers of ethylene and a-olefins. The present invention also relates to a process for producing a copolymer of ethylene homopolymer or ethylene and an? -Olefin using the transition metal catalyst composition and a process for producing an ethylene homopolymer or a copolymer of ethylene and? -Olefin prepared by using the transition metal compound or the transition metal catalyst composition, Olefin < / RTI >

Description

TECHNICAL FIELD The present invention relates to a novel transition metal compound having a quinoline-1 (2H) -yl group, a transition metal catalyst composition for olefin polymerization including the same, and a process for producing a copolymer of ethylene homopolymer or ethylene and an? -1 (2H) -yl group and catalyst composition containing the same olefin polymerization, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same}

The present invention relates to transition metal compounds and transition metal catalyst compositions for the preparation of ethylene homopolymers or copolymers of ethylene and alpha-olefins containing them. More specifically, a cyclopentadiene derivative is present around a Group 4 transition metal; And an aryl group and an alkyl group and has a fused structure at the same time, minimizing steric hindrance, facilitating the injection of comonomer, reducing the vibronic mode at high temperature, (2H) -based ligand and is not cross-linked between ligands, and a transition metal catalyst composition for the production of a copolymer of ethylene homopolymer or ethylene and alpha-olefin containing the same.

The present invention also relates to a process for producing an ethylene homopolymer or a copolymer of ethylene and an? -Olefin using a transition metal catalyst composition for the production of a copolymer of ethylene homopolymer or ethylene and an? -Olefin containing a Group 4 transition metal compound .

The present invention also relates to an ethylene homopolymer or a copolymer of ethylene and an? -Olefin prepared using a transition metal catalyst composition for preparing a Group 4 transition metal compound or an ethylene homopolymer or a copolymer of ethylene and an? will be.

Conventionally, the so-called Ziegler-Natta catalyst system composed of the main catalyst component of a titanium or vanadium compound and the cocatalyst component of an alkyl aluminum compound has been generally used for preparing a copolymer of ethylene with a homopolymer or an? -Olefin. However, although the Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization, the molecular weight distribution of the resulting polymer is generally broad due to the uneven catalytic activity point, and in particular, the disadvantage that the composition distribution is not uniform in the copolymer of ethylene and? .

Since the metallocene catalyst system composed of the metallocene compound of the transition metal of the periodic table group 4, such as titanium, zirconium, and hafnium, and methylaluminoxane, which is a cocatalyst, is a homogeneous catalyst having a single catalytic active site, - It is characterized that the polyethylene having narrow molecular weight distribution and homogeneous composition distribution can be produced compared with the Natta catalyst system. For example, European Patent Publication Nos. 320,762, 372,632 or 63-092621, Nos. 02-84405 and 03-2347 disclose that Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp (Mw / Mn) in the range of 1.5 to 2.0, by polymerizing ethylene in a high activity by activating the metallocene compound with the promoter methyl aluminoxane in the presence of a catalyst such as ₂ ZrMeCl, Cp ₂ ZrMe ₂ , ethylene (IndH ₄ ) ₂ ZrCl ₂ , Polyethylene can be produced. However, it is difficult to obtain a polymer having a high molecular weight in the catalyst system. Particularly, when applied to a solution polymerization method which is carried out at a high temperature of 120 ° C or higher, the polymerization activity rapidly decreases and the? Are not suitable for preparing high molecular weight polymers of 100,000 or more.

On the other hand, as a catalyst capable of producing a polymer having high catalytic activity and high molecular weight by ethylene homopolymerization or copolymerization of ethylene and an -olefin under solution polymerization conditions, a so-called geometrically constrained nonmetalocene catalyst (Aka single-site catalyst). EP 0416815 and EP 0420436 disclose an example in which an amide group is linked in the form of a ring to one cyclopentadiene ligand. In EP 0842939, a phenol-based ligand as an electron donor compound is reacted with a cyclopentadiene ligand An example of a catalyst in the form of a ring is shown. However, since the yield of the ring-forming reaction process between the ligand and the transition metal compound is very low during the synthesis step of the geometric constrained catalyst, there are many difficulties in commercial use.

On the other hand, examples of non-metallocene catalysts that are not geometrically constrained include US 6,329,478 and WO 00/005238. In this patent, it can be seen that a single active-site catalyst using at least one phosphine-imine compound as a ligand exhibits a high ethylene conversion when ethylene and alpha -olefin copolymerization is carried out under high temperature solution polymerization conditions of 120 ° C or higher. US 5,079,205 discloses a bis-phenoxide ligand, and US 5,043,408 discloses an example of a catalyst having a chelate-type bispenacide ligand. However, such a catalyst is too low in activity to produce an ethylene homopolymer or an? -Olefin And it is difficult to use the copolymer commercially.

Japanese Patent Application Laid-Open Nos. 1996-208732 and 2002-212218 disclose use as an olefin-based polymerization catalyst having an anilido ligand, but an example in a commercially meaningful polymerization temperature range is not disclosed. An example of using an anilido ligand as a non-metallocene catalyst for polymerization was reported in " Organometallics 2002 , 21 , 3043 (Nomura et al.)", But this case was limited to a methyl group as a simple alkyl substituent.

European Patent Publication No. 320,762 (June 21, 1989) European Patent Publication No. 372,632 (June 14, 1990) Japanese Patent Laid-Open No. 63-092621 (Apr. 23, 1988) Japanese Patent Application Laid-Open No. 02-84405 (1990.02.26) Japanese Patent Application Laid-Open No. 03-2347 (1991.01.08) European Patent No. 0416815 (Mar. 13, 1991) European Patent No. 0420436 (Apr. 03, 1991) European Patent No. 0842939 (May 20, 1998) U.S. Patent No. 6,329,478 (December 12, 2001) International Patent No. 00/005238 (2000.03.03) U.S. Patent No. 5,079,205 (Jan. 1, 1992) U.S. Patent No. 5,043,408 (Aug. 27, 1991) Japanese Patent Application Laid-Open No. 1996-208732 (Aug. 13, 1996) Japanese Patent Application Laid-Open No. 2002-212218 (July 31, 2002)

 Organometallics 2002, 21, 3043 (Nomura et al.)

In order to overcome the problems of the prior art, the present inventors have conducted extensive studies and found that cyclopentadiene derivatives around a Group 4 transition metal; And an aryl group and an alkyl group and has a fused structure at the same time, minimizing steric hindrance, facilitating the injection of comonomer, reducing the vibronic mode at high temperature, (2H) -based ligand exhibits excellent catalytic activity in the polymerization of ethylene and olefins. In view of such fact, a catalyst capable of producing a high molecular weight ethylene homopolymer or a copolymer of ethylene and an a-olefin with high activity has been developed in a polymerization process carried out at 60 ° C or higher, and the present invention has been completed on the basis thereof .

Accordingly, it is an object of the present invention to provide a transition metal compound useful as a catalyst for the production of an ethylene homopolymer or a copolymer of ethylene and an a-olefin, and to provide a catalyst composition containing the same.

Another object of the present invention is to provide an ethylene homopolymer or a copolymer of ethylene and an a-olefin prepared using a catalyst composition comprising the transition metal compound.

It is still another object of the present invention to provide a single-site catalyst having a simple synthesis route, which is very economical in catalyst synthesis, high activity in olefin polymerization, and an ethylene homopolymer or ethylene having a variety of physical properties, Olefin copolymer can be economically produced from a commercial point of view.

According to an aspect of the present invention, there is provided a process for preparing a cyclopentadiene derivative, And an aryl group and an alkyl group, and at the same time has a fused guar, thereby minimizing steric hindrance, facilitating the injection of comonomer, reducing the vibronic mode at high temperature, (2H) -based ligand; and a structure that is not cross-linked between the ligands is used as a catalyst for the preparation of a homopolymer of ethylene or a copolymer of ethylene and an a-olefin.

[Chemical Formula 1]

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

Cp is a fused ring containing a cyclopentadienyl ring or cyclopentadienyl ring which is capable of bonding to M and 侶⁵ -, and the fused ring including the cyclopentadienyl ring or cyclopentadienyl ring is (C1- (C6-C20) alkylsilyl group, (C6-C20) arylsilyl group, (C6-C20) arylsilyl group, (C1-C20) alkylsilyl group, (C2-C20) alkenyl group and (C6-C30) aryl (C1-C20) alkyl group;

R ¹ to R ¹⁰ are independently of each other a hydrogen atom or a (C 1 -C 20) alkyl group;

X ¹ and X ² independently represent a halogen atom, a (C 1 -C 20) alkyl group, a (C 3 -C 20) cycloalkyl group, a (C 6 -C 30) aryl (C1-C60) alkoxy group, (C6-C60) aryloxy group, (C1-C60) O, S, Si, halogen, etc.]]

According to another aspect of the present invention, there is provided a transition metal compound, And a cocatalyst selected from an aluminum compound, a boron compound or a mixture thereof, or a catalyst composition for producing a copolymer of ethylene and an a-olefin.

According to another aspect of the present invention, there is provided a process for producing a copolymer of ethylene homopolymer or ethylene and an a-olefin using the catalyst composition.

According to another aspect of the present invention, there is provided an ethylene homopolymer or a copolymer of ethylene and an a-olefin prepared using the transition metal compound or the catalyst composition.

The transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by an economical method because of simple synthesis process and excellent thermal stability of the catalyst, Since the copolymerization reaction with olefins is good and a high molecular weight polymer can be produced at a high yield, commercial utility is higher than the known metallocene and nonmetallocene single-site catalysts. Therefore, the transition metal and the catalyst composition containing the same according to the present invention can be usefully used for preparing a copolymer with an ethylene homopolymer or an a-olefin having various physical properties.

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

The Group 4 transition metal compound according to one embodiment of the present invention includes a cyclopentadiene derivative around the Group 4 transition metal, And an aryl group and an alkyl group and has a fused structure at the same time, minimizing steric hindrance, facilitating the injection of comonomer, reducing the vibronic mode at high temperature, (2H) -based ligand and has a structure that is not cross-linked between the ligands.

[Chemical Formula 1]

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

Cp is a fused ring containing a cyclopentadienyl ring or cyclopentadienyl ring which is capable of bonding to M and 侶⁵ -, and the fused ring including the cyclopentadienyl ring or cyclopentadienyl ring is (C1- (C6-C20) alkylsilyl group, (C6-C20) arylsilyl group, (C6-C20) arylsilyl group, (C1-C20) alkylsilyl group, (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group;

R ¹ to R ¹⁰ are independently of each other a hydrogen atom or a (C 1 -C 20) alkyl group;

X ¹ and X ² independently represent a halogen atom, a (C 1 -C 20) alkyl group, a (C 3 -C 20) cycloalkyl group, a (C 6 -C 30) aryl (C1-C60) alkoxy group, (C6-C60) aryloxy group, (C1-C60) O, S, Si, halogen, etc.).

M, which is a transition metal of Group 4 in the Periodic Table of the Chemical Formula 1, is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

The term "alkyl" as used herein includes both linear and non-linear forms.

The "aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, including a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyreneyl, perylenyle, klycenyl, naphthacenyl, fluoranthenyl and the like.

In addition, Cp is a central metal and η ⁵ - as a fused ring or a substituted fused ring including the cyclopentadienyl ring, such as capable of binding to a cyclopentadiene ring, and inde-substituted cyclopentadienyl ring, a carbonyl, Floresta carbonyl, here (C6-C20) alkylsilyl group, a (C1-C20) alkyldi (C6-C20) alkylsilyl group, (C6-C60) arylsilyl group, (C6-C20) aryldi (C1-C20) alkylsilyl group, (C2- C20) alkenyl group or ≪ / RTI > Specific examples thereof include cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopentadienyl Isopropylidene, isopropylidene, fluorenyl, methylfuranyl, dimethylfluorenyl, cyclopentadienyl, cyclopentadienyl, trimethylsilylcyclopentadienyl, tert -butylmethylcyclopentadienyl, Ethyl fluorenyl, isopropyl fluorenyl, and the like.

R ¹ to R ¹⁰ substituted in the quinolin-1 (2H) -yl ligand are each independently a hydrogen atom; Linear or non-linear (C1-C20) alkyl group, for, example, methyl, ethyl, n- propyl, isopropyl, n- butyl, sec - butyl, tert - butyl group, n- pentyl group, neopentyl group An n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-pentadecyl group or an n-eicosyl group, among which a methyl group, , An isopropyl group, an n-butyl group, tert -butyl group.

In Formula 1, X ¹ and X ² are each independently a halogen atom, for example, a fluorine, chlorine, bromine or iodine atom; (C1-C20) alkyl group, a methyl group as an example, ethyl, n- propyl, isopropyl, n- butyl, sec - butyl, tert - butyl group, n- pentyl group, neopentyl group, amyl group, n -hexyl, n- octyl group, n- decyl group, n- dodecyl group, n- penta-decyl or n- eicosyl group, and the one preferred is methyl, ethyl, isopropyl, tert-butyl group or amyl group ; Examples of the (C3-C20) cycloalkyl group include a cyclopropane group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or an adamantyl group; Examples of the (C6-C30) aryl (C1-C20) alkyl group or the ((C1-C20) (2, 4-dimethylphenyl) methyl group, (2, 4-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (2,3,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,4,5-trimethylphenyl) methyl group, (2,3,4,5-trimethylphenyl) Methylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-pentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-butylphenyl) methyl group, Octylphe ) Methyl group, (n- decyl phenyl) methyl group, (n- decyl phenyl) 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 groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec -butoxy, tert- - hexyl, n-octyl, n-dodecyl, n-pentadecyl or n-eicosyl. Of these, preferred are methoxy, ethoxy, isopropoxy or tert- ; Examples of (C6-C20) aryloxy groups are phenoxy, 1-naphthoxy or 2-naphthoxy; Examples of (C 1 -C 20) alkyl (C 6 -C 20) aryloxy groups are 4-methylphenoxy, 4-t-butylphenoxy or 4-t-octylphenoxy; Except hydrogen N, P, O, S, Si, reactors made of anion ligand of less than 60 comprising a halogen lamp is ^{-OSiR f R g R h, -SR} i [R f to R ⁱ are independently selected from (C1 each other (C 1 -C 20) alkyl, (C 6 -C 30) aryl or (C 3 -C 20) cycloalkyl, -NR ^j R ^k or -PR ^l R ^{m where} R ^j to R ^m independently of one another are (C1-C60) alkylsilyl or tri (C6-C30) arylsilyl, (C6-C30) aryl . Examples of the -OSiR ^f R ^g R ^h is a trimethylsiloxy group, a siloxy triethyl, tri -n- propyl siloxy, triisopropyl siloxy, tri -n- butyl siloxy, tri - sec - butyl-siloxy group, N -hexylsiloxy group, tricyclohexylsiloxy group, and the like, and -NR < 1 > Examples of ^j R ^k include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di- sec -butylamino group, di- tert -butylamino group, diisobutylamino group , tert - butyl isopropyl group, a di -n- hexyl group, a di -n- octyl group, a di -n- decyl amino group, diphenyl amino group, dibenzyl amino group, methyl ethyl amino group, a phenyl group, a cyclohexyl benzyl group, a bis-trimethyl Silylamino group or bis-tert-butyldimethylsilyl Include an amino group and; As examples of the phosphine group -PR ^l R ^m dimethyl, diethyl phosphine group, di -n- propyl phosphine group, diisopropyl phosphine group, di -n- butyl phosphine group, di - sec - butyl phosphine group, di - tert -Butylphosphine group, diisobutylphosphine group, tert -butylisopropylphosphine group, di-n-hexylphosphine group, di-n-octylphosphine group, di-n-decylphosphine group, diphenylphosphine group, dibenzyl A phosphine group, a methylethylphosphine group, a methylphenylphosphine group, a benzylhexylphosphine group, a bistrimethylsilylphosphine group or a bis-tert-butyldimethylsilylphosphine group; Examples of -SR ⁱ include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a 1-butylthio group or an isopentylthio group.

The transition metal compound of the present invention may be selected from compounds having the following structures, but is not limited thereto.

[Wherein Cp is cyclopentadienyl or pentamethylcyclopentadienyl; X ¹ and X ² are, independently of each other, chlorine, a methyl group, a methoxy group or a (C6-C20) aryloxy group.

On the other hand, the transition metal compound of the above formula (1) is preferably an X ¹ and X ² ligand in the transition metal complex to be an active catalyst component used for preparing a copolymer of ethylene homopolymer or ethylene and an alpha -olefin A catalyst composition comprising a transition metal compound and a cocatalyst, which can cooperate with a counter ion having weak bonding force, that is, an aluminum compound, a boron compound or a mixture thereof capable of acting as an anion, And are within the scope of the present invention.

The boron compound which can be used as a cocatalyst in the present invention is a boron compound known in U.S. Patent No. 5,198,401, specifically, a compound represented by the following formulas (2) to (4).

(2)

B (R ¹¹ ) ₃

(3)

[R ¹² ] ⁺ [B (R ¹¹ ) ₄ ] ^-

[Chemical Formula 4]

_{^{[(R 13) p ZH]}} + [B (R 11) 4] -

[In the above Chemical Formulas 2 to 4, B is a boron atom; (C 1 -C 20) alkyl group substituted by a fluorine atom, a (C 1 -C 20) alkoxy group and a (C 1 -C 20) alkoxy group substituted by a fluorine atom, R ¹¹ is a phenyl group, ) Alkoxy group; < / RTI > R ¹² is a (C 5 -C 7) aromatic radical or a (C 1 -C 20) alkyl (C 6 -C 20) aryl radical or a (C 6 -C 30) aryl (C 1 -C 20) alkyl radical such as triphenylmethylium, Radical; Z is a nitrogen or phosphorus atom; R ¹³ is an (Cl-C20) alkyl radical or an Anilinium radical substituted with two (C1-C10) alkyl groups together with the nitrogen atom; And p is an integer of 2 or 3.]

Preferable examples of the boron-based co-catalyst include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (triphenylphosphine) borane, (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis , 5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate or tetrakis (3,5-bistrifluoromethylphenyl) . Specific examples of these compounds include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (Pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, triphenylmethyllithium tetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluoro Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl anilinium tetrakis (pentafluorophenyl) , 6-phen (Pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) Borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (dimethylphenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate, of which the most preferred are N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylmethylniumtetrakis (pentafluorophenyl) Borate or tris (pentafluoro) borane.

Examples of aluminum compounds that can be used as cocatalysts in the catalyst composition according to one embodiment of the present invention include aluminoxane compounds of the formula 5 or 6, organoaluminum compounds of the formula 7 or organoaluminum alkyl oxides of the formula 8 or 9 Or an organoaluminum aryloxide compound.

 [Chemical Formula 5]

^{(-Al (R 14) -O-)} m

[Chemical Formula 6]

(R ¹⁴ ) ₂ Al - (- O (R ¹⁴ ) -) _q - (R ¹⁴ ) ₂

(7)

(R ¹⁵ ) _r Al (E) _3-r

[Chemical Formula 8]

(R ¹⁶ ) ₂ AlOR ¹⁷

[Chemical Formula 9]

R ^{16 is} Al (OR ¹⁷ ) ₂

[In the formulas (5) to (9), R ¹⁴ is a (C 1 -C 20) alkyl group, preferably a methyl group or an isobutyl group; m and q are each independently an integer of 5 to 20; R ¹⁵ and R ¹⁶ are (C 1 -C 20) alkyl groups; E is a hydrogen atom or a halogen atom; r is an integer from 1 to 3; R ¹⁷ is (C 1 -C 20) alkyl group or (C 6 -C 30) aryl group]

Specific examples of the aluminum compound that can be used include aluminoxane compounds such as methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane; Examples of the organoaluminum compound include trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; Dialkyl aluminum chlorides, including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, and dihexyl aluminum chloride; Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; There may be mentioned dialkylaluminum hydrides including dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride, preferably trialkylaluminum, Preferably triethylaluminum and triisobutylaluminum.

In the transition metal catalyst composition for the preparation of the ethylene homopolymer or the copolymer of ethylene and an? -Olefin containing the cocatalyst according to the present invention, when the aluminum compound is used as a cocatalyst, the transition metal (M): aluminum atom Al) is 1:10 to 1: 5,000 based on the molar ratio. Further, in the transition metal catalyst composition for preparing the ethylene homopolymer or copolymer of ethylene and? -Olefin containing the cocatalyst according to the present invention, the preferable range of the ratio between the transition metal compound of formula (1) and the cocatalyst is, The ratio of boron atom (M): boron atom (B): aluminum atom (Al) is 1: 0.1-100: 10-1,000, more preferably 1: 0.5-5: 25-500. It is possible to prepare a copolymer of ethylene homopolymer or ethylene and alpha -olefin at the above ratio, and the range of the ratio varies depending on the purity of the reaction.

In another aspect of the present invention, the process for preparing an ethylene polymer using the transition metal catalyst composition can be carried out by contacting the transition metal catalyst, the cocatalyst, and ethylene or, if desired, an alpha-olefin comonomer, in the presence of a suitable organic solvent . At this time, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or the components may be premixed and introduced into the reactor, and the mixing conditions such as the order of introduction, temperature, and concentration are not limited.

Preferred organic solvents that can be used in the above production process are (C3-C20) hydrocarbons. Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, Hexane, benzene, toluene, xylene, and the like.

Specifically, when ethylene homopolymer is prepared, ethylene alone is used as a monomer, and the pressure of ethylene is suitably 1 to 1000 atm, and more preferably 10 to 150 atm. It is also effective that the polymerization reaction is carried out at a temperature of 60 to 300 ° C, preferably at 80 to 250 ° C.

When a copolymer of ethylene and an? -Olefin is prepared, C3-C18? -Olefins may be used as a comonomer together with ethylene, preferably propylene, 1-butene, 1-pentene, - pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene. More preferably, 1-butene, 1-hexene, 1-octene, or 1-decene and ethylene can be copolymerized. In this case, the preferred ethylene pressure and polymerization reaction temperature may be the same as in the case of the ethylene homopolymer production, and the copolymer prepared according to the process of the present invention usually contains not less than 50% by weight of ethylene, preferably not more than 60% % Ethylene, more preferably from 60 to 99 wt%, based on the total weight of the composition.

As described above, the linear low-density polyethylene (LLDPE) prepared by using C3-C18 alpha -olefin as the comonomer has a density range of 0.910 to 0.940 g / cc and an ultra low density polyethylene (VLDPE Or ULDPE) or an olefin elastomeric region. In order to control the molecular weight of the ethylene homopolymer or copolymer according to the present invention, hydrogen may be used as a molecular weight modifier and has a weight average molecular weight (Mw) generally in the range of 80,000 to 500,000.

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

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

Except where otherwise noted, all ligand and catalyst synthesis experiments were carried out using standard Schlenk or glove box techniques under nitrogen atmosphere and organic solvents used in the reaction were refluxed under sodium metal and benzophenone to remove water And used by distillation just before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was carried out using Bruker 500 MHz at room temperature.

Cyclohexane, a polymerization solvent, was used after thoroughly removing water, oxygen, and other catalyst poison substances through a 5 Å molecular sieve and a pipe filled with activated alumina and bubbling with high purity nitrogen. The polymerized polymer was analyzed by the method described below.

1. Melt Flow Index (MI)

It was measured according to ASTM D 2839.

2. Density

ASTM D 1505, using a mill tool piping.

[Example 1] (2-methyl-3,4-dihydro-quinoline -1 (2H) - yl) (1,2,3,4,5-pentamethyl cyclopentadienyl-2,4-en-1 yl) titanium (IV) dichloride [(2- methyl -3,4- dihydroquinolin -1 ( 2H) - yl) (1,2,3,4,5- pentamethylcyclopenta -2,4- dien -1-yl) titanium (IV) dichloride ]

2-methyl-1,2,3,4-tetrahydroquinoline (0.46 g, 3.1 mmol) was dissolved in 20 mL of toluene, and then n-butyllithium (2.5 M hexane solution, 1.55 mL) The mixture was stirred at room temperature for 12 hours. Titanium (IV) trichloride (0.94 g, 3.1 mmol) was added dropwise to the temperature of the reaction to -78 < 0 > C and then (1,2,3,4,5-pentamethylcyclopenta- Was dissolved in 5 mL of toluene, and the reaction was allowed to proceed at room temperature for 12 hours. After the completion of the reaction, the reaction mixture was filtered through celite to remove the solvent, and the residue was recrystallized with purified toluene and hexane at -35 ° C., followed by filtration and drying under reduced pressure to obtain (2-methyl-3,4-dihydroquinoline- (2H) -yl) (1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl) titanium (IV) chloride 2 mmol (63%). _{^{1 H NMR (CDCl 3, 500}} MHz) δ 7.69 (d, 1 H, J = 7.7 Hz), 7.02 (t, 1 H, J = 7.1 Hz), 6.90 (d, 1 H, J = 7.5 Hz), (M, 1H), 1.88 (m, 1H), 1.84 (s, 1H), 6.84 (t, 1H, J = 7.1 Hz) H), 1.36 (m, 1H), 1.15 (d, 3H, J = 6.1 Hz) ppm

[Example 2]

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

To a 2 L stainless steel reactor thoroughly dried and replaced with nitrogen, 1100 mL of cyclohexane and 100 mL of 1-octene were charged, and then 54.3 mM (alumina) of modified methylaluminoxane-7 (Akzo Nobel, modified MAO-7, 7 wt% Al Isopar solution) 22.1 mL of toluene solution was added to the reactor. Thereafter, the temperature of the reactor was heated to 80 DEG C, and then (2-methyl-3,4-dihydroquinoline-1 (2H) -yl) (1,2,3,4,5- (99%, commercially available from Boulder Scientific, Inc.) (5.7 mL) was mixed with 5.4 mL of tetrahydrofuran ) 10 ml toluene solution were sequentially charged, and then the pressure in the reactor was filled up to 30 kg / cm ² with ethylene, and the mixture was continuously supplied to polymerize. The reaction was allowed to proceed for 3 minutes at a maximum temperature of 149 ° C. After 1 minute, 100 mL of ethanol containing 10 vol% aqueous hydrochloric acid solution was added to terminate the polymerization. The reaction mixture was stirred with 10 L of ethanol for 1 hour, . The weight, catalytic activity, melt flow index (MI) and density of the polymers prepared in Table 1 are listed below.

[Example 3]

Copolymerization of ethylene and 1-octene was carried out using a batch polymerization apparatus as follows: To a 2 L stainless steel reactor thoroughly dried and replaced with nitrogen, 1100 mL of cyclohexane and 100 mL of 1-octene were placed, (Aldrich), 10.3 mL of a 194 mM cyclohexane solution was added to the reactor. Thereafter, the temperature of the reactor was heated to 80 DEG C, and then (2-methyl-3,4-dihydroquinolin-1 (2H) -yl) (1,2,3,4,5- (Pentafluorophenyl) borate (99%, Boulder Scientific) 10 mM toluene (0.37 uM toluene solution), 5.4 mL of toluene And then the pressure in the reactor was filled up to 30 kg / cm < ² > with ethylene, followed by continuous feeding to polymerize. The reaction mixture was allowed to react for 3 hours at a maximum temperature of 97.4 ° C. After 1 minute, 100 mL of ethanol containing 10 vol% aqueous hydrochloric acid solution was added to terminate the polymerization. The reaction mixture was stirred for 1 hour with 4 L of ethanol. Followed by vacuum drying. The weight, catalytic activity, melt flow index (MI) and density of the polymers prepared in Table 1 are listed below.

Polymer weight (g) Activity
(Weight of polymer (Kg) / catalyst (mmol)) MI Density Example 2 57.16 28.6 0.14 0.8960 Example 3 12.01 6.0 0.606 0.8824

According to Examples 2 and 3, high copolymers having a high 1-octene content and an MI of 1 or less could be produced even under a high temperature condition.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the invention as defined by the appended claims. It will be possible to carry out various modifications. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.

Claims (13)

A transition metal compound represented by the following formula (1)
[Chemical Formula 1]

Wherein M is titanium, zirconium or hafnium;
Cp is a fused ring containing a cyclopentadienyl ring or cyclopentadienyl ring which is capable of bonding to M and 侶⁵ -, and the fused ring including the cyclopentadienyl ring or cyclopentadienyl ring is (C1- C20) alkyl group;
R ¹ to R ¹⁰ are independently of each other a hydrogen atom or a (C 1 -C 20) alkyl group;
X ¹ and X ² are each independently a halogen atom, (C 1 -C 20) alkyl group, (C 1 -C 20) alkoxy group or (C 6 -C 20) aryloxy group.
delete The method according to claim 1,
Wherein the transition metal compound is represented by the following structure.

[Wherein Cp is cyclopentadienyl or pentamethylcyclopentadienyl; X ¹ and X ² are, independently of each other, chlorine, a methyl group, a methoxy group or a (C6-C20) aryloxy group.
A transition metal compound according to any one of claims 1 to 3; And
An aluminate, a boron compound or a mixture thereof;
Or a transition metal catalyst composition for the production of a copolymer of ethylene and an a-olefin.
5. The method of claim 4,
Wherein the aluminum compound used as the cocatalyst is an ethylene homopolymer or a mixture of one or two or more selected from alkyl aluminoxane or organoaluminum or a transition metal catalyst composition for the production of a copolymer of ethylene and an a-olefin.
5. The method of claim 4,
Wherein the aluminum compound co-catalyst is a transition metal catalyst composition for the production of a copolymer of an ethylene homopolymer or an ethylene and an a-olefin having a molar ratio of transition metal (M): aluminum atom (Al) of 1:10 to 1: 5,000.
5. The method of claim 4,
The boron compound used as the cocatalyst is selected from the group consisting of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylmethylniniumtetrakis (pentafluorophenyl) borate, Polymer or a transition metal catalyst composition for the production of a copolymer of ethylene and an a-olefin.
5. The method of claim 4,
The ratio of the transition metal compound and the cocatalyst is preferably from 1: 0.1 to 100: 10 to 1000 based on the molar ratio of the transition metal (M): boron atom (B): aluminum atom (Al) Transition metal catalyst composition for the preparation of a copolymer of olefins.
A process for producing a copolymer of an ethylene homopolymer or an ethylene and an a-olefin comprising using the transition metal catalyst composition according to claim 4
10. The method of claim 9,
1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1 -Hexadecene and 1-aicosene, or a mixture thereof, and an ethylene homopolymer having an ethylene content of 60 to 99% by weight in the copolymer of ethylene and an a-olefin or a copolymer of ethylene and an a- Gt;
10. The method of claim 9,
Wherein the pressure of the ethylene monomer in the reactor is from 1 to 1000 atm and the polymerization reaction temperature is from 60 to 300 ° C or a copolymer of ethylene and an a-olefin.
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