KR100958676B1 - Synthesis, Characterization, and Polymerization of dinuclear CGC Complexes - Google Patents

Abstract

The heteronuclear catalyst of the present invention is represented by the following general formula (1), characterized in that the heteronuclear metallocene catalyst of the following general formula (1) is connected to arylene and alkylene having an alkyl substituent.

[Formula 1]

Polyethylene polymerization, CGC, metallocenes, alkylaluminoxanes

Description

Synthesis method of homogeneous catalyst having a constrained arrangement with binary nucleus and linear alpha olefin copolymer prepared by using same {Synthesis, Characterization, and Polymerization of dinuclear CGC Complexes}

The present invention relates to a catalyst which is an important factor for determining physical properties in linear low density polyethylene (LLDPE) polymers, and more particularly to a heteronuclear homogeneous catalyst having a constrained arrangement. It also relates to a process for preparing polyolefin homopolymers or copolymers by polymerization of ethylene or / and alphaolefins under the heteronuclear homogeneous catalyst.

Polyolefin polymerization catalysts have been developed since K. Ziegler and G. Natta have made ethylene polymerization using transition metal compounds possible. Since not only polymerization activity but also copolymerizability and stereoregularity are determined by the structure of the olefin polymerization catalyst, catalysts having various structures and performances have been developed according to the use. The Ziegler-Natta catalyst is a non-uniform catalyst, and the exact shape of the activated catalyst is not known.Therefore, the Ziegler-Natta catalyst has a limited molecular structure. Not. On the other hand, the metallocene catalyst can accurately know the shape of the activated catalyst as a homogeneous single site catalyst and the microstructure of the obtained polymer is uniform.

Since the structure of Ferrocene was identified by Fischer in 1952, the development of metallocene, a single active site homogeneous catalyst, was developed as an olefin polymerization catalyst. Metallocene is basically a sandwich metal transition metal compound in which a cyclopentadienyl ligand is coordinately bonded, and has various molecular structures according to the change of ligand type and core metal. The use of earlier metallocene compounds with alkyl aluminum, which is used as a co-catalyst for Ziegler-Natta catalysts, has been shown to have olefin polymerization activity and to add trace amounts of water. It was found that the activity was increased. Later, it was known that the increase in activity due to the addition of water by Kaminsky et al. Was caused by the formation of methylaluminoxane (MAO) by the reaction of water and aluminum trichloride (AlMe ₃ ). It was found to exhibit high activity when used in. Metallocene does not have activity on its own, but a vacant site is generated by methylaluminoxane (MAO) as a promoter and polymerization proceeds as a monomer is coordinated thereto. This content is described in EP129,368, US4,874,880, US5,324,800, Macromol. Chem. 4,417 (1983). German Patent Nos. 2,608,933, 3,007,725 and the like disclose a metallocene catalyst compound composed of a main group 4 transition metal of zirconium (Zr), titanium (Ti) and hafnium (Hf) and a ligand of a cyclopentadienyl-based structure. The use of it as a catalyst for olefin polymerization with cocatalysts, etc., was announced. Examples of a compound having a cyclopentadiene-based structure shown in the known patents include cyclopentadiene, indene, fluorene, alkyl substituted cyclopentadiene, and alkyl substitution. Indene, alkyl substituted fluorene, and the like. Many types of cyclopentadiene-based metallocene compounds can be used in the catalyst system for olefin polymerization. The chemical structure change of the cyclopentadiene-based metallocene is very important for its suitability as a polymerization catalyst. The chemical structure of the metallocene catalyst can be basically divided into the type of the transition metal and the form of the ligand. Since the type of the general transition metal is limited, the polymerization activity and the physical properties of the polymer can also be controlled by modifying various ligands. The size and position of the ligand substituents greatly influence the activity, stereospecificity, physical properties and stability of the catalyst. After the general form of metallocene was developed, a constrained geometry catalyst (CGC), a constrained array homogeneous catalyst, US5055438 (US5055438) was developed and used to develop various polymers. Compared to the previous metallocenes, CGC has excellent thermal stability, high activity even with a small amount of cocatalyst, thereby reducing the catalyst residue of the polymer, and producing a polymer having a higher molecular weight than the conventional metallocene catalyst. Can be. Since then, many catalysts have been developed to binarize mononuclear CGC (J Am Chem Soc. 125 (2003), Korean Patent Publication 2001-0109794, Korean Patent Publication 2001-0057201, Korean Patent Publication 1998-0009293) .

However, the prior art has a problem that it is difficult to obtain the effect of ensuring a wide molecular weight distribution while maintaining excellent catalytic activity and excellent reactivity with the comonomer in the production of ethylene / linear α-olefin copolymer.

An object of the present invention is to provide a metallocene catalyst that can ensure a wide molecular weight distribution while maintaining the excellent activity of the existing CGC catalyst and reactivity with the comonomer in the production of ethylene / linear α-olefin copolymer.

Still another object of the present invention is to provide a method for efficiently preparing a polyethylene copolymer using the metallocene catalyst.

In order to solve the above technical problem, the inventors of the present invention have found that an alkyl ring-substituted aromatic ring (arylene) and a alkylene-substituted heteronuclear catalyst have excellent catalytic activity and have a wide molecular weight distribution unlike other homogeneous catalysts. The present invention has been found to be suitable for the production of polyethylene copolymers.

The present invention provides a dinuclear CGC type metallocene catalyst connected by arylene and alkylene substituted with an alkyl group to have a wide molecular weight distribution and high catalytic activity in preparing a polyolefin homopolymer or copolymer.

In another aspect, the present invention provides a catalyst for producing polyolefin containing an organoaluminum compound as a dinuclear CGC type metallocene catalyst and a co-catalyst of the alkyl group substituted by arylene and alkylene.

In another aspect, the present invention provides a method for producing a polyolefin using the binuclear CGC type metallocene catalyst or a catalyst system containing the metallocene catalyst and a promoter.

The heteronuclear CGC-type metallocene catalyst connected by arylene and alkylene substituted with an alkyl group according to the present invention can produce polyethylene or ethylene / α-olefin copolymers having a wide molecular weight distribution unlike conventional polyolefin production catalysts. There is an advantage.

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

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

The metallocene catalyst having a nucleus-constrained arrangement according to the present invention is represented by the following Chemical Formula 1 and has a heteronuclear CGC form in which an alkyl group is substituted with arylene and alkylene.

[Formula 1]

[In Formula 1, M ₁ and M ₂ are independently selected from titanium (Ti), zirconium (Zr), or hafnium (Hf); Ar is (C3-C20) arylene substituted with a (C1-C20) alkyl group; Cp ₁ and Cp ₂ are independently selected from cyclopentadienyl, indenyl, or fluorenyl groups; Y ₁ and Y ₂ are independently (C 1 -C 10) alkylene, (C 3 -C 20) arylene, (C 3 -C 20) ar (C 1 -C 10) alkylene, or silyl (-Si (R ₁₁ ) _2- , R ₁₁ is selected from hydrogen, a (C1-C10) alkyl, or a (C3-C20) aryl group; A ₁ and A ₂ are independently selected from nitrogen (N), phosphorus (P), or sulfur (S); R ₁ and R ₂ are independently selected from hydrogen, (C 1 -C 10) alkyl, or (C 3 -C 20) aryl groups; X ₁ to X ₄ are independently selected from halogen elements, (C 1 -C 10) alkyl, or (C 3 -C 20) aryl groups; m and n are independently an integer from 1 to 4; The cyclopentadienyl, indenyl or fluorenyl group of Cp ₁ and Cp ₂ may independently have a substituent selected from a halogen element, a (C 1 -C 10) alkyl, or a (C 1 -C 10) alkoxy group.]

In Formula 1, Ar is more preferably phenylene substituted with (C1-C20) alkyl group or naphthylene substituted with (C1-C20) alkyl group, and the number of substituted (C1-C20) alkyl groups is one or more. It may be substituted by the number of hydrogen that can be substituted with. In particular, when Ar is a catalyst for preparing polyolefin using a catalyst of formula (1) in which phenylene substituted with (C3-C10) alkyl group is used, the molecular weight distribution (PDI) is far more unexpected than conventional catalysts. desirable.

In Formula 1, Y ₁ and Y ₂ are independently selected from silyl (-Si (R ₁₁ ) _2- , R ₁₁ is a (C1-C10) alkyl group), and X1 to X4 are selected from halogen elements. More preferably, M ₁ and M ₂ are titanium (Ti), and Cp ₁ and Cp ₂ are more preferably indenyl groups.

The heteronuclear catalyst of the present invention can be prepared using techniques similar to those commercialized for the production of general CGC based catalysts. A strong base is reacted with a cyclopentadienyl compound to form a salt containing an alkali metal. This is reacted with a cyclic compound substituted with an alkyl group to form a bridge. In this way, cyclopentadienyl forms can be synthesized on both sides of the cyclic compound having an alkyl substituent. The compound is reacted with a strong base to form a salt form, and then reacted with a silane to have a silyl group, followed by reaction with an amine to synthesize a ligand. The catalyst can be synthesized by metallization by reacting a Group 4 transition metal compound with a salt form of the ligand. Oxidizers are sometimes used in metallation reactions. Since the finished catalyst is in a solid phase, it can be recrystallized from hexane and purified into a high purity compound.

Diluents used in the synthesis process are non-halogen liquid diluents, and examples of suitable diluents include hydrocarbons such as toluene, pentane and hexane, diethyl ether and tetrahydrofuran. The alkali metal of the alkali metal alkyl which makes cyclopentadienyl in the salt form can be selected from the group which consists of sodium, potassium, and lithium, and an alkyl group has C1-C4 carbon number.

The molar ratio of the alkali metal salt to the transition metal compound of the cyclopentadienyl compound can be varied in various ranges depending on the purpose. Typically, however, alkali metal salts of cyclopentadienyl compounds are used in molar ratios of about 1: 1 relative to the transition metal compound.

The binuclear metallocene catalyst of Chemical Formula 1 is composed of a catalyst system together with a promoter when used for producing polyethylene or polyethylene copolymer. Examples of suitable cocatalysts generally include cocatalysts that have been used in the prior art in parallel with metallocene catalysts for olefin polymerization. Typical examples of some of these cocatalysts include organometallic compounds of Groups IA, IIA and IIIB metals on the periodic table. Examples of the organometallic compound include organometallic halides, organometallic hydrides, metal hydrides, and more specifically organoaluminum compounds. The organoaluminum compound includes trialkylaluminum compounds such as triethylaluminum and triisobutylaluminum and alkylaluminoxanes.

More preferred cocatalysts are alkylaluminoxanes having repeating units represented by the following formula (2):

[Formula 2]

[In Formula 2, R ₃ is an alkyl group of C1 ~ C5.]

Examples of the alkylaluminoxane include methylalumioxane (MAO), modified methylaluminoxane, and the like.

The amount of promoter can vary over a wide range. The molar ratio of the transition metal in the aluminum to metallocene catalyst in the alkylaluminoxane is about 1: 1 to 10,000: 1 and more preferably in the range of about 100: 1 to 500: 1.

The dinuclear CGC-based catalyst combined with the dinuclear metallocene catalyst and the organoaluminum compound promoter according to the present invention can be suitably used for polymerizing olefins, in particular ethylene copolymers. The catalyst system can be carried out in a uniform system in which the catalyst and the promoter are dissolved by the medium. In addition, the heteronuclear CGC-based catalyst may be supported on the inorganic carrier to be suitable for the gas phase process and the slurry process. As the inorganic carrier, one or a mixture of two or more selected from silica, alumina, magnesium chloride, zeolite, aluminum phosphate, or zirconia can be used. Therefore, the binary nucleus CGC catalyst of the present invention is a solution polymerization process in which the resulting polymer is not precipitated but dissolved in the liquid phase of the reactor and polymerization occurs in a homogeneous phase, slurry polymerization in which the resulting polymer is not dissolved in a solvent, or a gas phase without using a solvent. It can be applied to all polymerization processes.

Hereinafter, a method for preparing polyolefin using a heteronuclear metallocene catalyst according to the present invention will be described.

The method for producing a polyolefin according to the present invention is characterized by reacting at least one unsaturated ethylenic monomer in the presence of the heteronuclear metallocene catalyst. The unsaturated ethylenic monomers include ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like. In the production method according to the present invention, the unsaturated ethylenic monomer is used as ethylene alone or polyethylene homopolymer or ethylene / α using α-olefins such as ethylene and propylene, 1-butene, 1-hexene and 1-octene. It is more preferable to prepare a copolymer of -olefin.

Most olefin polymerization processes are carried out in the presence of a liquid diluent which does not adversely affect the catalyst system. Examples of such liquid diluents include propane, butane, isobutane, pentane, hexane, heptane, octane, toluene and the like. The polymerization temperature for polymerizing the olefin polymer using the catalyst system of the present invention can be varied over a wide range, typically in the range of 50-130 ° C. The pressure in the polymerization process is set within a typical range of 5-10 kg / cm ² .

The heteronuclear catalyst of the present invention is connected to the aromatic ring (arylene) and alkylene substituted by the alkyl group, and the polyethylene air is significantly improved in the narrow molecular weight distribution, which serves as a disadvantage while maintaining the excellent activity and copolymerizability of other homogeneous catalysts. The coalescence can be prepared.

The novel heteronuclear catalyst of the present invention can be more clearly understood by the following examples, which are merely illustrative of the present invention and are not intended to limit the scope of the invention.

EXAMPLE

In the following examples, the heteronuclear CGC-based catalyst was prepared using Schlenk's technique with strictly excluding air and moisture by purified inert gas and the solvent used was dried by sodium or potassium hydride, sodium-potassium alloy and inert Distillation was carried out using a vacuum under an atmosphere of gas. In addition, the synthesized intermediate compound and catalyst were dissolved in deuterium-substituted NMR solvent CDCl ₃ , C ₆ D ₆ and analyzed by NMR.

Comparative Example 1

By the method of EP 0,416,815A2 Example 2 (t- butylamido) dimethyl (tetramethyl -η ⁵ - cyclo pentadienyl) silane titanium dichloride ((Tert-butylamido) dimethyl ( tetramethyl-η 5 -cyclopentadinyl) silane Titanium dichloride) was prepared.

Comparative Example 2

[TBu-N-Si (Me) ₂ -Ind- (CH ₂ ) ₇ -Ind-Si (Me) ₂ -N-tBu] Ti ₂ Cl ₄ was prepared by the method of Example 6 of Korean Patent Publication No. 2001-0109794. Prepared.

Example 1

[ C ₉ H ₇ - CH ₂ [ C ₆ H ₁₃ - C ₆ H ₂ - C ₆ H ₁₃ ]- CH ₂ - C ₉ H ₇ Manufacture of

1,4-bis (chloromethyl) -2,5-dihexylbenzene (1,4-bis (chloromethyl) -2,5-dihexyl benzene) (2.5 g, 7.3 mmol) was stirred in THF (20 ml) at room temperature The solution was slowly injected into Indenyl lithium salt (1.91 g, 15.7 mmol) / THF (40 ml) solution maintained at -78 ° C.

After removing the cooling water bath, the temperature was gradually raised and reacted at 60 ° C. for 48 hours. You can visually see the solution gradually turning dark yellow. After the reaction was completed, THF was removed under reduced pressure, hexane was added to remove insoluble LiCl under celite, and the hexane was removed.

(3.5 g, yield 95%)

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.47 (d, 2H, C ₉ H ₇ ), 7.39 (d, 2H, C ₉ H ₇ ), 7.31 (t, 2H, C ₉ H ₇ ), 7.25 (t, 2H, C ₉ H ₇ ), 6,99 (s, 2H, C ₆ H ₂ ), 5,87 (s, 2H, C ₉ H ₇ ), 3.82 (s, 4H, CH ₂ ), 3.30 (s, 4H, C ₉ H ₇ ), 2.50 (t, 4H, CH ₂ ), 1.48 (m, 4H, CH ₂ -CH ₂ ), 1.19 (s, 12H, CH ₂ -CH _2- (CH ₂ ) ₃ ), 0.83 (s, 6H, CH ₃ )

[Li ( C ₉ H ₆ ) CH ₂ ] ₂ [( C ₆ H ₁₃ ) ₂ C ₆ H ₂ Manufacture

The compound (3.5 g, 7 mmol) / THF (50 ml) solution was maintained at -78 ° C, and n-BuLi was slowly added dropwise, and then gradually heated up to react at 60 ° C for 24 hours to obtain a dark green solution. After the reaction was completed, the THF was removed under reduced pressure and washed with hexane to obtain a yellow powder (3.43 g, 96%).

[( CH ₃ ) ₂ SiCl ( C ₉ H ₆ ) CH ₂ ] ₂ [( C ₆ H ₁₃ ) ₂ C ₆ H ₂ Manufacture of

After slowly injecting the above compound (3.43g, 6.7mmol) / THF (40ml) solution into dichlorodimethylsilane (2.427ml, 16.75ml) / THF (20ml) solution maintained at -78 ° C, The mixture was slowly heated up and reacted at room temperature for 12 hours. After completion of the reaction, THF was removed under reduced pressure, hexane was added to filter the undissolved material under celite, and hexane was removed under reduced pressure to obtain yellow oil (4.28 g, 93%). .

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.57 (d, 2H, C ₉ H ₆ ), 7.41 (d, 2H, C ₉ H ₆ ), 7.31 (t, 2H, C ₉ H ₆ ), 7.22 (t, 2H, C ₉ H ₆ ), 6,94 (s, 2H, C ₆ H ₂ ), 6.00 (s, 2H, C ₉ H ₆ ), 3.89 (s, 4H, CH ₂ ), 3.60 ( s, 2H, C ₉ H ₆ ), 2.51 (m, 4H, CH ₂ ), 1.53 (m, 4H, CH ₂ -CH ₂ ), 1.19 (s, 12H, CH ₂ -CH _2- (CH ₂ ) ₃ ), 0.86 (s, 6H, CH ₃ ), 0.18 (s, 12H, Si-CH ₃ )

[( NH ^t Bu ) ( CH ₃ ) ₂ Si ( C ₉ H ₆ ) CH ₂ ] ₂ [( C ₆ H ₁₃ ) ₂ C ₆ H ₂ Manufacture of

t-butylamine (3.76ml, 31mmol) / THF (20ml) solution was slowly injected into the above compound (4.26g, 6.2mmol) / THF (50ml) solution maintained at -78 ° C and then slowly It heated up and made it react at 60 degreeC for 12 hours. After the reaction was completed, THF was removed under reduced pressure, hexane was added, filtered under celite, and hexane was removed under reduced pressure to obtain orange oil (4.55 g, 97%).

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.53 (d, 2H, C ₉ H ₆ ), 7.38 (d, 2H, C ₉ H ₆ ), 7.22 (t, 4H, C ₉ H ₆ ), 6,94 (s, 2H, C ₆ H ₂ ), 6.04 (s, 2H, C ₉ H ₆ ), 3.88 (s, 4H, CH 2), 3.45 (s, 2H, C ₉ H ₆ ), 2.53 (m , 4H, CH ₂ ), 1.53 (m, 4H, CH ₂ -CH ₂ ), 1.19 (s, 12H, CH ₂ -CH _2- (CH ₂ ) ₃ ), 1.17 (s, 18H, t-Bu), 0.86 (m, 6H, CH ₃ ), 0.63 (s, 2H, NH), -0.04 (d, 6H, Si-CH ₃ ), -0.19 (d, 6H, Si-CH ₃ )

[ Me ₃ CNHSiMe ₂ -[ C ₉ H ₅ - CH ₂ -[ C ₆ H ₁₃ - C ₆ H ₂ - C ₆ H ₁₃ ]- CH ₂ - C ₉ H ₅ ]- SiMe ₂ NHCMe ₃ ] ₂ Li Manufacture

N-BuLi (14.1ml, 30mmol) was slowly injected into the above compound (4.55g, 6mmol) / THF (60ml) solution maintained at -78 ° C, and the temperature was gradually raised to react at 60 ° C for 24 hours. After the reaction was completed, the THF was removed under reduced pressure and hexane was added to give a yellow-brown product (4.6 g, 98%).

[(Ti (η ⁵ : η ^One - C ₉ H ₅ SiMe - ₂ NCMe ₃ ) ( CH ₂ )] ₂ [( C ₆ H ₁₃ ) ₂ C ₆ H ₂ Manufacture of

The above Li salt (1.00 g, 1.27 mmol) was dissolved in THF (20 ml) at room temperature and stirred, and the solution was slowly added to TiCl ₃ (THF) ₃ (0.992 g, 2.67 mmol) / THF (30 ml) at -78 ° C. Injected.

The temperature was raised to room temperature and further reacted for 3 hours. After the reaction was completed for 3 hours, an excess of AgCl (0.383 g, 2.67 mmol) was added at room temperature, followed by further reaction for 1 hour. After the reaction was completed, the produced Ag and the trace amount of AgCl were removed by filtration, and the THF was removed under reduced pressure. Toluene was added and filtered under celite to remove LiCl and reduced pressure to remove toluene. Subsequently, hexane is added to filter under celite to recrystallize the remaining solution to obtain a reddish brown color product.

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C): δ 7.73 (d, 2H, C ₉ H ₅ ), 7.59 (d, 2H, C ₉ H ₅ ), 7,41 (t, 2H, C ₉ H ₅ ), 7.29 (t, 2H, C ₉ H ₅ ), 6.85 (s, 2H, C ₆ H ₂ ) 6.28 (s, 2H, C ₉ H ₅ ), 4.37 (m, 4H, CH ₂ ), 2.46 (t , 4H, CH ₂ ), 1.40 (s, 4H, CH ₂ -CH ₂ ), 1.35 (s, 18H, C (CH ₃ ) ₃ ), 1.15 (s, 12H, CH ₂ -CH _2- (CH ₂ ) ₃ ), 0.89 (s, 6H, Si-CH ₃ ), 0.86 (s, 6H, CH ₃ ), 0.6 (s, 6H, Si-CH ₃ )

[Example 2]

1,4-bis (chloromethyl) having the following structure instead of 1,4-bis (chloromethyl) -2,5-dihexylbenzene in Example 1 A catalytic material was synthesized in the same manner as in Example 1 except for using -2,5-dipropylbenzene (1,4-bis (chloromethyl) -2,5-dipropylbenzene).

[( C ₉ H ₇ ) CH ₂ ] ₂ [( C ₃ H ₇ ) ₂ C ₆ H ₂ Manufacture of

Yield: 82.6%

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.43 (t, 4H, C ₉ H ₇ ), 7.29 (t, 2H, C ₉ H ₇ ), 7.19 (t, 2H, C ₉ H ₇ ), 7.09 (s, 2H, C ₆ H ₂ ), 5,80 (s, 2H, C ₉ H ₇ ), 3.85 (s, 4H, CH ₂ ), 3.27 (s, 4H, C ₉ H ₇ ), 3.06 ( m, 2H, CH), 1.20 (d, 6H, CH (CH ₃ ) ₂ ), 1.10 (d, 6H, CH (CH ₃ ) ₂ ).

[( CH ₃ ) ₂ SiCl ( C ₉ H ₆ ) CH ₂ ] ₂ [( C ₃ H ₇ ) ₂ C ₆ H ₂ Manufacture of

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.58 (d, 2H, C ₉ H ₆ ), 7.49 (d, 2H, C ₉ H ₆ ), 7.35 (t, 4H, C ₉ H ₆ ), 7.09 (s, 2H, C ₆ H ₂ ), 5.88 (s, 2H, C ₉ H ₆ ), 3.95 (s, 4H, CH ₂ ), 3.59 (s, 2H, C ₉ H ₆ ), 3.08 (m, 2H, CH), 1.12 (d, 12H, CH (CH ₃ ) ₂ ), 0.17 (s, 12H, Si-CH ₃ )

[( NH ^t Bu ) ( CH ₃ ) ₂ Si ( C ₉ H ₆ ) CH ₂ ] ₂ [( C ₃ H ₇ ) ₂ C ₆ H ₂ Manufacture of

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.54 (d, 2H, C ₉ H ₆ ), 7.45 (d, 2H, C ₉ H ₆ ), 7.28 (t, 2H, C ₉ H ₆ ), 7.25 (t, 2H, C ₉ H ₆ ), 7.09 (s, 2H, C ₆ H ₂ ), 5.93 (s, 2H, C ₉ H ₆ ), 3.93 (s, 4H, CH ₂ ), 3.43 (s, 2H, C ₉ H ₆ ), 3.09 (m, 2H, CH), 1. 15 (s, 18H, t-Bu), 1.13 (s, 12H, CH (CH ₃ ) ₂ ), 0.60 (s, 2H, NH), -0.05 (d, 6H, Si-CH ₃ ), -0.19 (d, 6H, Si-CH ₃ )

[(Ti (η ⁵ : η ^One - C ₉ H ₅ SiMe - ₂ NCMe ₃ ) Cl ₂ CH ₂ ] ₂ [( C ₃ H ₇ ) ₂ C ₆ H ₂ Manufacture of

¹ H NMR (300 MHz, CDCl ₃ , 25 ° C.): δ 7.70 (d, 2H, C ₉ H ₅ ), 7.69 (d, 2H, C ₉ H ₅ ), 7,34 (t, 2H, C ₉ H ₅ ), 7.23 (t, 2H, C ₉ H ₅ ), 7.08 (s, 2H, C ₆ H ₂ ), 6.27 (s, 2H, C ₉ H ₅ ), 4.42 (m, 4H, CH ₂ ), 3.09 ( m, 2H, CH), 1.14 (s, 18H, C (CH ₃ ) ₃ ), 1.01 (s, 6H, CH (CH ₃ ) ₂ ), 0.87 (s, 6H, Si-CH ₃ ), 0.58 (s , 6H, Si-CH ₃ )

Example 3 Polymer Preparation

The polymers were prepared as shown in Table 1 using the catalyst materials of Comparative Example 1, Comparative Example 2, Example 1 and Example 2.

The polymerization experiment was carried out using a metal 2L pressure reactor.

Normal hexane, a polymerization solvent, was stored and used while removing impurities through a molecular sieve dried at high temperature. 3 mg of the catalyst material of Comparative Example 1, Comparative Example 2, Example 1 and Example 2 was dissolved in 800 ml of hexane from which impurities were removed, and then 3 ml of alkylaluminoxane was injected, mixed well, and immediately injected into the reactor. Ethylene was filled with the pressure in the reactor such that the 8kg / cm ^2, was fed during the reaction to maintain a constant reactor pressure at 8kg / cm ^2.

Cooling and temperature increase were controlled by circulating coolant and oil in a jacket outside the reactor. The polymerization time was 15 minutes, the temperature was 85 ℃ and after the completion of the polymerization experiment, the inside of the reactor was cooled, the gas inside was replaced with nitrogen and the polymer was recovered.

Catalytic activity

The polyethylene polymer obtained in the polymerization was weighed and exhibited catalytic activity in units of 10 ⁶ g PE / cat mol · hr.

Molecular Weight and Molecular Weight Distribution Analysis

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC at high temperature using a solution of 20 mg of polyethylene polymer in 10 ml of benzene trichloride, and the polydispersity index (PDI, polydispersity) was obtained by dividing Mw by Mn. .

Xylene extraction ( Xylene soluble , X.S) measurement

2g polyethylene (PE) polymer sample was put in 200ml xylene and stirred at 135 ° C and 150rpm for 40 minutes, and then the temperature was lowered to 100 ° C. After stirring in a 25 ° C. thermostat for 30 minutes, the solution is filtered and dried. Weigh the remaining polymer after drying and measure X.S. The polymer dissolved in xylene is a polymer having a low molecular weight (raw polymer) or having a short chain branch and is considered to be a polymer having high solubility.

TABLE 1 Polymer analysis results of Comparative Examples 1 and 2 and Examples 1 and 2

As shown in Table 1, the catalyst of Comparative Example 2 exhibits lower activity and lower molecular weight than that of Comparative Example 1 in the case of ethylene / 1-hexene copolymerization. However, in Examples 1 and 2, the activity is equivalent to that of Comparative Example 1 under the same conditions, and 1-hexene copolymerizability is greatly excellent. In addition, the molecular weight distribution (PDI), which serves as a disadvantage in the homogeneous catalyst system, has also been shown to be twice as large as the conventional CGC (Comparative Example 1). If the molecular weight distribution is wide, there are also many relatively small molecular weight (raw polymer), so the amount extracted by xylene is increased, which may lead to inferior physical properties. Nevertheless, the catalysts of Examples 1 and 2 produced a polymer in which the amount of xylene extracted was similar to that of Comparative Example 1, while maintaining the advantages of the homogeneous catalyst while significantly improving the molecular weight distribution. This result showed the same tendency not only for 1-hexene but also for 1-butene.

Claims (13)

A metallocene catalyst having an arrangement bound by a nucleus represented by Formula 1 below. [Formula 1]

[In Formula 1, M ₁ and M ₂ are independently selected from titanium (Ti), zirconium (Zr), or hafnium (Hf); Ar is (C3-C20) arylene substituted with a (C1-C20) alkyl group; Cp ₁ and Cp ₂ are independently selected from cyclopentadienyl, indenyl, or fluorenyl groups; Y ₁ and Y ₂ are independently (C 1 -C 10) alkylene, (C 3 -C 20) arylene, (C 3 -C 20) ar (C 1 -C 10) alkylene, or silyl (-Si (R ₁₁ ) _2- , R ₁₁ is selected from hydrogen, a (C1-C10) alkyl, or a (C3-C20) aryl group; A ₁ and A ₂ are independently selected from nitrogen (N), phosphorus (P), or sulfur (S); R ₁ and R ₂ are independently selected from hydrogen, (C 1 -C 10) alkyl, or (C 3 -C 20) aryl groups; X ₁ to X ₄ are independently selected from halogen elements, (C 1 -C 10) alkyl, or (C 3 -C 20) aryl groups; m and n are independently an integer from 1 to 4; The cyclopentadienyl, indenyl or fluorenyl group of Cp ₁ and Cp ₂ may independently have a substituent selected from a halogen element, (C 1 -C 10) alkyl, or (C 1 -C 10) alkoxy group. ] The method of claim 1, Ar in Formula 1 is a metallocene catalyst, characterized in that phenylene substituted (C1 ~ C20) alkyl group or naphthylene substituted (C1 ~ C20) alkyl group. The method of claim 2, Ar in Formula 1 is a metallocene catalyst, characterized in that (phenyl) substituted (C3 ~ C10) alkyl group. The method of claim 3, wherein In Formula 1, Y ₁ and Y ₂ are independently selected from silyl (-Si (R ₁₁ ) _2- , R ₁₁ is a (C1-C10) alkyl group), and X ₁ to X ₄ are selected from halogen elements. Metallocene catalyst to be used. The method of claim 4, wherein In Chemical Formula 1, M ₁ and M ₂ are titanium (Ti), and Cp ₁ and Cp ₂ are indenyl groups. The method of claim 1, The metallocene catalyst is a metallocene catalyst, characterized in that supported on at least one inorganic carrier selected from silica, alumina, magnesium chloride, zeolite, aluminum phosphate, and zirconia. A catalyst for producing a polyolefin comprising an organoaluminum compound as a metallocene catalyst and a cocatalyst having an arrangement bound by a nucleus of the general formula (1). [Formula 1]

[In Formula 1, M ₁ and M ₂ are independently selected from titanium (Ti), zirconium (Zr), or hafnium (Hf); Ar is (C3-C20) arylene substituted with a (C1-C20) alkyl group; Cp ₁ and Cp ₂ are independently selected from cyclopentadienyl, indenyl, or fluorenyl groups; Y ₁ and Y ₂ are independently (C 1 -C 10) alkylene, (C 3 -C 20) arylene, (C 3 -C 20) ar (C 1 -C 10) alkylene, or silyl (-Si (R ₁₁ ) _2- , R ₁₁ is selected from hydrogen, a (C1-C10) alkyl, or a (C3-C20) aryl group; A ₁ and A ₂ are independently selected from nitrogen (N), phosphorus (P), or sulfur (S); R ₁ and R ₂ are independently selected from hydrogen, (C 1 -C 10) alkyl, or (C 3 -C 20) aryl groups; X ₁ to X ₄ are independently selected from halogen elements, (C 1 -C 10) alkyl, or (C 3 -C 20) aryl groups; n is an integer from 1 to 4; The cyclopentadienyl, indenyl or fluorenyl group of Cp ₁ and Cp ₂ may independently have a substituent selected from a halogen element, a (C 1 -C 10) alkyl, or a (C 1 -C 10) alkoxy group.] The method of claim 7, wherein The organoaluminum compound is a catalyst for producing a polyolefin, characterized in that the alkyl aluminoxane having a repeating unit of the formula (2). [Formula 2]

[In Formula 2, R ₃ is an alkyl group of C1 ~ C5.] A method for producing a polyolefin, comprising reacting an unsaturated ethylenic monomer which is an olefin having at least one C2 to C8 carbon number under the catalyst of any one of claims 1 to 8. The method of claim 9, The unsaturated ethylenic monomer which is an olefin which has C2-C8 carbon number contains the ethylene, The manufacturing method of the polyolefin characterized by the above-mentioned. The method of claim 10, The polyolefin is a method of producing a polyolefin, characterized in that the copolymer of ethylene and α-olefin. delete delete