KR19990069077A - Novel metallocene catalyst for styrene polymerization and preparation method thereof - Google Patents

Novel metallocene catalyst for styrene polymerization and preparation method thereof Download PDF

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KR19990069077A
KR19990069077A KR1019980003097A KR19980003097A KR19990069077A KR 19990069077 A KR19990069077 A KR 19990069077A KR 1019980003097 A KR1019980003097 A KR 1019980003097A KR 19980003097 A KR19980003097 A KR 19980003097A KR 19990069077 A KR19990069077 A KR 19990069077A
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amino
metallocene catalyst
propanol
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김영조
이민형
도영규
류이열
임진형
김현준
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유현식
삼성종합화학 주식회사
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/16—Syndiotactic

Abstract

본 발명에 따른 신규의 메탈로센 촉매는 전형적인 반쪽 메탈로센(half metallocene) 구조와 유사한 구조로서, 주기율표 Ⅳ족의 전이금속의 한쪽에 η5결합을 생성하는 시클로알칸디에닐기 또는 그 유도체가 결합되고 다른 한쪽에 알코올아민 화합물(alcoholamine compound)이 도입된 구조를 갖는다. 본 발명의 메탈로센 촉매는 시클로알칸디에닐기 유도체 리간드를 알칼리금속 화합물 또는 탈륨 화합물과 반응시켜 알칼리금속 또는 탈륨 양이온을 함유하는 염(salt) 상태의 리간드를 제조한 후, 산에 잘 떨어져 나가는 화합물을 도입시키고, 여기에 Ⅳ족의 전이금속 화합물을 반응시켜 반쪽 메탈로센 화합물을 제조하고, 상기 반쪽 메탈로센 화합물에 알코올아민 화합물을 반응시켜 메탈로센 촉매를 제조한다. 또한 Ⅳ족의 전이금속 화합물과 알코올아민 화합물을 반응시키고, 상기 생성물에 시클로알칸디에닐기 유도체 리간드와 알칼리금속 화합물 또는 탈륨 화합물을 반응시켜 얻은 염상태의 리간드를 반응시켜 본 발명의 메탈로센 촉매를 제조한다.The novel metallocene catalyst according to the present invention has a structure similar to that of a typical half metallocene structure, in which a cycloalkanedienyl group or a derivative thereof, which generates a η 5 bond to one side of a transition metal of Group IV of the periodic table, is bonded. And an alcohol amine compound on one side thereof. In the metallocene catalyst of the present invention, a cycloalkanedienyl derivative ligand is reacted with an alkali metal compound or thallium compound to prepare a ligand in the salt state containing an alkali metal or thallium cation, and then falls off well in an acid. The half metallocene compound was prepared by reacting the Group IV transition metal compound, and the alcoholamine compound was reacted with the half metallocene compound to prepare a metallocene catalyst. In addition, a metallocene catalyst of the present invention is prepared by reacting a Group IV transition metal compound with an alcoholamine compound, and reacting the product with a cycloalkanedinyl derivative derivative ligand and an alkali metal compound or a thallium compound. do.

Description

스티렌 중합용 신규 메탈로센 촉매 및 그 제조방법Novel metallocene catalyst for styrene polymerization and preparation method thereof

본 발명은 스티렌계 중합체를 제조하기 위한 메탈로센(metallocene) 촉매에 관한 것이다. 더욱 상세하게는 적은 양의 조촉매를 사용하고도 높은 활성, 우수한 입체규칙성 및 높은 용융온도를 가지며, 분자량 분포가 양호한 신디오탁틱 폴리스티렌(sydiotactic polystyrene)의 제조가 가능한 높은 활성의 신규 메탈로센 촉매 및 그의 제조방법과 이를 이용한 스티렌의 중합에 관한 것이다.The present invention relates to a metallocene catalyst for preparing a styrenic polymer. More specifically, highly active novel metallocenes having high activity, good stereoregularity and high melting temperature and low molecular weight distribution, and capable of producing sydiotactic polystyrene with good molecular weight distribution It relates to a catalyst, a method for producing the same, and polymerization of styrene using the same.

물성이 향상된 폴리올레핀 또는 입체 규칙성을 갖는 폴리스티렌을 제조하기 위하여 메탈로센 촉매가 개발되었다. 메탈로센계 촉매는 주기율표 Ⅳ족의 전이금속(예: 티탄(titanium), 지르코늄(zirconium), 하프늄(hafnium))의 화합물로서 금속화합물과 1개 또는 2개의 시클로알칸디에닐기(cycloalkanedienyl groups)(예: 시클로펜타디에닐기(cyclopentadienyl groups), 인데닐기(indenyl groups), 플루오레닐기(fluorenyl groups) 및 이들의 유도체)로 이루어진 리간드와 결합된 구조를 갖는다.Metallocene catalysts have been developed to produce polyolefins having improved physical properties or polystyrenes having stereoregularity. Metallocene-based catalysts are compounds of transition metals (eg titanium, zirconium, hafnium) of the Group IV of the periodic table, and metal compounds and one or two cycloalkanedienyl groups (eg : Has a structure coupled with a ligand consisting of cyclopentadienyl groups, indenyl groups, fluorenyl groups and derivatives thereof.

이러한 형태의 메탈로센계 촉매는 조촉매와 함께 사용된다. 사용되는 조촉매로는 종래의 지글러-나타 촉매(Ziegler-Natta catalysts)에서 사용되는 것과는 달리 물과 알킬알루미늄 화합물과의 반응 생성물인 알킬알루미늄옥산(예: 메틸알루미늄옥산)이 있다. 이러한 메탈로센 촉매를 이용하여 현재까지 제조가 불가능했던 입체규칙성 폴리스티렌(예: 신디오탁틱 폴리스티렌 또는 아이소탁틱(isotactic) 폴리스티렌)의 제조가 가능하게 되었다. 특히 신디오탁틱 폴리스티렌은 고분자 주쇄중의 벤젠고리가 교대로 위치하는 구조로서 종전의 무정형 범용 아탁틱(atactic) 폴리스티렌과는 달리 결정성구조를 갖는 고분자로서 녹는점(Tm)이 270℃ 정도로 내열성 및 기계적 성질이 우수한 고분자로 관심의 대상이 되어왔다.This type of metallocene catalyst is used in conjunction with a promoter. Cocatalysts used are alkylaluminum oxanes (eg, methylaluminum oxane), which are reaction products of water and alkylaluminum compounds, unlike those used in conventional Ziegler-Natta catalysts. The use of such metallocene catalysts has made it possible to produce stereoregular polystyrenes (eg, syndiotactic polystyrenes or isotactic polystyrenes) which have not been produced until now. In particular, syndiotactic polystyrene is a structure in which the benzene rings in the polymer main chain are alternately positioned. Unlike conventional amorphous general atactic polystyrene, syndiotactic polystyrene has a crystalline structure and has a melting point (Tm) of about 270 ° C. Polymers with excellent mechanical properties have been of interest.

이러한 입체규칙성을 갖는 올레핀계 또는 스티렌계 중합체를 제조하는데 있어서, 전이금속 화합물 및 알킬알루미늄옥산으로 이루어지는 촉매가 사용된다는 것이 알려져 있다(예를 들면, 일본특허출원 공개번호 19309/1983, 95292/1984, 135408/1985, 유럽특허번호 EP 210615, 미합중국 특허번호 US 4,680,353 및 PCT 특허공개번호 WO 8,810,275).In preparing an olefinic or styrene polymer having such stereoregularity, it is known that a catalyst consisting of a transition metal compound and an alkylaluminum oxane is used (for example, Japanese Patent Application Laid-open No. 19309/1983, 95292/1984). , 135408/1985, European Patent No. EP 210615, United States Patent No. US 4,680,353 and PCT Patent Publication No. WO 8,810,275.

그러나 이러한 촉매는 값이 비싸고 충분한 활성을 갖지 못하다는 단점과, 또한 조촉매로 함께 쓰이는 알킬알루미늄옥산의 값이 매우 비쌀 뿐만 아니라 많은 양이 함께 사용되어야 하기 때문에 상업화하는 데 불리한 점이 매우 많다.However, these catalysts are disadvantageous in that they are expensive and do not have sufficient activity, and are also disadvantageous in commercialization because of the high cost of the alkylaluminum oxane used as a co-catalyst, as well as a large amount.

따라서 기존 촉매와 유사한 가격을 갖는 촉매로 높은 활성을 지니게 하는 촉매의 개발이 필요시되며, 또한 조촉매로 사용되는 알킬알루미늄옥산을 적게 사용하고도 높은 활성을 지니는 촉매가 필요한 실정이다.Therefore, it is necessary to develop a catalyst having high activity as a catalyst having a similar price to that of the existing catalyst, and a situation in which a catalyst having high activity even with less alkyl aluminum oxane used as a promoter is required.

상기와 같은 문제점을 극복하기 위하여 본 발명자는 높은 신디오탁틱시티(syndiotacticity)를 갖는 스티렌계 중합체를 효율적으로 제조하기 위한 신규의 촉매를 개발하게 되었다.In order to overcome the above problems, the present inventors have developed a novel catalyst for efficiently preparing a styrene polymer having high syndiotacticity.

본 발명의 목적은 입체규칙성이 우수하고, 높은 용융온도를 가지며, 분자량 분포가 양호한 신디오탁틱 폴리스티렌을 제조하기 위한 높은 활성을 갖는 메탈로센 촉매를 제공하기 위한 것이다.An object of the present invention is to provide a metallocene catalyst having high activity for producing syndiotactic polystyrene having excellent stereoregularity, high melting temperature, and good molecular weight distribution.

본 발명의 다른 목적은 적은 양의 조촉매를 사용하여 신디오탁틱 폴리스티렌을 제조할 수 있는 메탈로센 촉매를 제공하기 위한 것이다.Another object of the present invention is to provide a metallocene catalyst capable of producing syndiotactic polystyrene using a small amount of promoter.

본 발명의 또 다른 목적은 상기 메탈로센 촉매를 제조하는 방법 및 상기 메탈로센 촉매를 이용하여 신디오탁틱 폴리스티렌을 제조하기 위한 방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a method for preparing the metallocene catalyst and a method for producing syndiotactic polystyrene using the metallocene catalyst.

본 발명의 상기의 목적 및 기타의 목적들은 하기 설명되는 본 발명에 의하여모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.

본 발명에 따른 신규의 메탈로센 촉매는 전형적인 반쪽 메탈로센(half metallocene) 구조와 유사한 구조로서, 주기율표 Ⅳ족의 전이금속의 한쪽에 η5결합을 생성하는 시클로알칸디에닐기 또는 그 유도체가 결합되고 다른 한쪽에 알코올아민 화합물(alcoholamine compound)이 도입된 하기 화학식 1a, 1b, 1c, 1d 및 1e 의 구조를 갖는다:The novel metallocene catalyst according to the present invention has a structure similar to that of a typical half metallocene structure, in which a cycloalkanedienyl group or a derivative thereof, which generates a η 5 bond to one side of a transition metal of Group IV of the periodic table, is bonded. And an alcohol amine compound on one side thereof has the structure of Formulas 1a, 1b, 1c, 1d and 1e:

상기 화학식 1a 내지 1e에서, M은 주기율표 Ⅳ족의 전이금속으로 티탄, 지르코늄 또는 하프늄이며, L1, L2, L3, L4및 L5는 주기율표 Ⅳ족의 전이금속 M과 η5결합을 생성하는 각각 시클로펜타디에닐기(cyclopentadienyl group), 인데닐기(indenyl group), 플루오레닐기(fluorenyl group) 또는 그것의 유도체중의 하나로서, 이들은 하기 구조식(Ⅰ), (Ⅱ) 또는 (Ⅲ)으로 표시되며:In Formula 1a to 1e, M is titanium, zirconium or hafnium as the transition metal in the periodic table Ⅳ group, L 1, L 2, L 3, L 4 and L 5 are the transition metal M and η 5 bonding of the periodic table Ⅳ group As one of the cyclopentadienyl group, indenyl group, fluorenyl group, or derivatives thereof, each of which is produced, they are represented by the following structural formulas (I), (II) or (III): Is displayed:

(상기 구조식 Ⅰ내지 Ⅲ에서 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12및 R13은 각각 독립적으로 수소원자(hydrogen atom), 탄소수 1 내지 20의 알킬기(alkyl group), 시클로알킬기(cycloalkyl group), 알콕시기(alkoxy group), 아실옥시기(acyloxy group), 알킬실릴기(alkylsilyl group), 탄소수 6 내지 20의 아릴기(aryl group), 알킬아릴기(alkylaryl group) 또는 아릴알킬기(arylalkyl group)이며, 상기 실릴기는 -Sir1r2r3로나타낼 수 있으며, 여기서 r1, r2및 r3는 독립적으로 수소원자, 탄소수 1 내지 10의 알킬기, 또는 탄소수 6 내지 20의 아릴기임),(In the above formulas I to III, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently hydrogen. Hydrogen atom, alkyl group having 1 to 20 carbon atoms, cycloalkyl group, alkoxy group, acyloxy group, alkylsilyl group, 6 to 20 carbon atoms An aryl group, an alkylaryl group, or an arylalkyl group of 20, wherein the silyl group may be represented by -Sir 1 r 2 r 3 , where r 1 , r 2 and r 3 are Independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

A1, A2, A3, A4, A5, A6, A7, A8, A9, A10및 A11는 독립적으로 산소원자(oxygen atom)이고, B1, B2, B3, B4, B5, B6, B7, B8, B9, B10및 B11는 각각 독립적으로 탄소수 1 내지 20의 알킬기 또는 시클로알킬기이고, C1, C2, C3, C4및 C6는 각각 질소원자(nitrogen atom), -NR1', -NR2'R3', -NR4'R5', 또는 -NR6'R7'으로 표현할 수 있으며, C5, C7및 C8는 각각 독립적으로 -NR8'R9' 또는 -CR10'R11'R12'로 나타낼 수 있고, 상기에서 R1', R2', R3', R4', R5', R6', R7', R8', R9', R10', R11' 및 R12'은 각각 독립적으로 수소원자 또는 탄소수 1 내지 10의 알킬기이고, X1, X2, X3및 X4는 각각 독립적으로 할로겐 원자(halogen atom), 탄소수 1 내지 10의 알킬기, 시클로알킬기, 알콕시기, 아실옥시기, 탄소수 6 내지 20의 아릴기, 알킬아릴기 또는 아릴알킬기이다.A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 and A 11 are independently oxygen atoms, B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 , B 8 , B 9 , B 10 and B 11 are each independently an alkyl or cycloalkyl group having 1 to 20 carbon atoms, and C 1 , C 2 , C 3 , C 4 and C 6 may be represented by a nitrogen atom, -NR 1 ', -NR 2 ' R 3 ', -NR 4 ' R 5 ', or -NR 6 ' R 7 ', and C 5 , C 7 and C 8 may be each independently represented by -NR 8 'R 9 ' or -CR 10 'R 11 ' R 12 ', wherein R 1 ', R 2 ', R 3 ', R 4 ', R 5 ′, R 6 ′, R 7 ′, R 8 ′, R 9 ′, R 10 ′, R 11 ′ and R 12 ′ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X 1 , X 2 , X 3 and X 4 are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkoxy group, an acyloxy group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group .

상기 화학식 1a 및 1b의 메탈로센 촉매는 C1및 C2가 각각 질소 원자 또는 -NR1'일 때 고리횡단 결합(transannular bond)이 존재하고, 화학식 1c, 1d 및 1e의 메탈로센 촉매는 각각 M-C3, M-C4및 M-C6의 금속-질소 결합이 존재한다.The metallocene catalysts of Chemical Formulas 1a and 1b have a transannular bond when C 1 and C 2 are nitrogen atoms or -NR 1 ', respectively, and the metallocene catalysts of Chemical Formulas 1c, 1d, and 1e are There are metal-nitrogen bonds of MC 3 , MC 4 and MC 6 , respectively.

본 발명의 메탈로센 촉매는 시클로알칸디에닐기 유도체 리간드를 알칼리금속 화합물 또는 탈륨 화합물과 반응시켜 알칼리금속 또는 탈륨 양이온을 함유하는 염(salt) 상태의 리간드를 제조한 후, 산에 잘 떨어져 나가는 화합물을 도입시키고, 여기에 Ⅳ족의 전이금속 화합물을 반응시켜 반쪽 메탈로센 화합물을 제조하고, 상기 반쪽 메탈로센 화합물에 알코올아민 화합물을 반응시켜 메탈로센 촉매를 제조한다.In the metallocene catalyst of the present invention, a cycloalkanedienyl derivative ligand is reacted with an alkali metal compound or thallium compound to prepare a ligand in the salt state containing an alkali metal or thallium cation, and then falls off well in an acid. The half metallocene compound was prepared by reacting the Group IV transition metal compound, and the alcoholamine compound was reacted with the half metallocene compound to prepare a metallocene catalyst.

상기 알칼리금속 화합물은 알킬기 또는 알콕시기를 가지며, 탈륨 화합물은 알콕시기를 갖는다. 이들의 대표적인 예로는 부틸리튬(butyllithium), 세크-부틸리튬(sec-butyllithium), 터셔리-부틸리튬(tert-butyllithium), 메틸리튬(methyllithium), 나트륨 메톡사이드(sodium methoxide), 나트륨 에톡사이드(sodium ethoxide), 탈륨 에톡사이드(thallium ethoxide) 등이 있다.The alkali metal compound has an alkyl group or an alkoxy group, and the thallium compound has an alkoxy group. Representative examples thereof include butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, sodium methoxide, sodium ethoxide ( sodium ethoxide) and thallium ethoxide.

주기율표 Ⅳ족의 전이금속 화합물로는 사염화 티타늄(TiCl4), 사염화지르코늄(ZrCl4) 및 사염화하프늄(HfCl4)이 있다.Transition metal compounds of Group IV of the periodic table include titanium tetrachloride (TiCl 4 ), zirconium tetrachloride (ZrCl 4 ) and hafnium tetrachloride (HfCl 4 ).

상기 반쪽 메탈로센 화합물과 반응하는 알코올아민 화합물로는 에탄올아민(ethanolamine), 3-아미노-1-프로판올(3-amino-1-propanol), 1-아미노-2-프로판올(1-amino-2-propanol), 4-아미노-1-부탄올(4-amino-1-butanol), 2-아미노-1-부탄올(2-amino-1-butanol), 2-아미노-2-메틸-1-프로판올(2-amino-2-methyl-1-propanol), 5-아미노-1-펜탄올(5-amino-1-pentanol), 2-아미노-1-펜탄올(2-amino-1-pentanol), 2-아미노-3-메틸-1-부탄올 (2-amino-3-methyl-1-butanol), 6-아미노-1-헥산올(6-amino-1-hexanol), 2-아미노-1-헥산올(2-amino-1-hexanol), 이소루신올(isoleucinol), 루신올(leucinol), 2-아미노시클로헥산올(2-aminocyclohexanol), 3-아미노메틸-3,5,5-트리메틸시클로헥산올 (3-aminomethyl-3,5,5-trimethylcyclohexanol), 2-(2-아미노에톡시)에탄올 (2-2(-aminoethoxy)ethanol), 2-(2-아미노에틸아미노)에탄올 (2-(2-aminoethylamino)ethanol), 1,3-비스(디메틸아미노)-2-프로판올 (1,3-bis(dimethylamino)-2-propanol), 2-(메틸아미노)에탄올 (2-(methylamino)ethanol), 2-(에틸아미노)에탄올 (2-(ethylamino)ethanol), 2-(프로필아미노)에탄올(2-(propylamino)ethanol), 2-(터셔리-부틸아미노)에탄올(2-(tert-butylamino)ethanol), N,N-디메틸에탄올아민(N,N-Dimethylethanolamine), N,N-디에틸에탄올아민(N,N-diethylethanolamine), 2-(디부틸아미노)에탄올(2-(dibutylamino)ethanol), 3-디메닐아미노-1-프로판을(3-dimethylamino-1-propanol), 3-디에틸아미노-1-프로판올(3-diethylamino-1-propanol), 1-디메틸아미노-2-프로판올(1-dimethylamino-2-propanol), 1-디에틸아미노-2-프로판올(1-dimethylamino-2-propanol), 5-디에탄올아미노-2-펜탄올(5-diethylamino-2-pentanol), 디에탄올아민(diethanolamine), 디이소프로판올아민(diisopropanolamine), N-메틸디에탄올아민(N-methyldiethanolamine), N-에틸에탄올아민(N-ethylethanolamine), N-부틸디에탄올아민(N-butyldiethanolamine), 3-(디메틸아미노)-1,2-프로판디올(3-(dimethylamino)-1,2-propanediol), 3-(디에틸아미노)-1,2-프로판디올(3-(diethylamino)-1,2-propanediol), 3-(디이소프로필아미노)-1,2-프로판디올(3-(diisopropylamino)-1,2-propanediol), 3-(터셔리-부틸아미노)-1,2-프로판디올(3-(tert(butylamino)-1,2-propanediol), 세린올(serinol), 2-아미노디에틸-1,3-프로판디올(2-aminodiethyl-1,3-propanediol), 트리에탄올아민(triethanolamine), 1-[N,N-비스(2-히드록시에틸)아미노]-2-프로판올(1-N,N-bis(2-hydroxyethyl)amino]-2-propanol] 트리이소프로판올아민(triisopropanolamine), 및 비스-호모트리스(bis-homotris)가 있다.Alcohol amine compounds that react with the half metallocene compound include ethanolamine, 3-amino-1-propanol, and 1-amino-2-propanol (1-amino-2). -propanol), 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol ( 2-amino-2-methyl-1-propanol), 5-amino-1-pentanol, 2-amino-1-pentanol, 2 -Amino-3-methyl-1-butanol (2-amino-3-methyl-1-butanol), 6-amino-1-hexanol, 2-amino-1-hexanol (2-amino-1-hexanol), isoleucinol, leucinol, 2-aminocyclohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol (3-aminomethyl-3,5,5-trimethylcyclohexanol), 2- (2-aminoethoxy) ethanol (2-2 (-aminoethoxy) ethanol), 2- (2-aminoethylamino) ethanol (2- (2 -aminoethylamino) ethanol), 1,3-bis (dimethylamino) -2-propanol (1,3-bis (d imethylamino) -2-propanol), 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (ethylamino) ethanol, 2- (propylamino) ethanol (propylamino) ethanol), 2- (tert-butylamino) ethanol), N, N-dimethylethanolamine, N, N-diethylethanolamine (N, N-diethylethanolamine), 2- (dibutylamino) ethanol (2- (dibutylamino) ethanol), 3-dimenylamino-1-propane (3-dimethylamino-1-propanol), 3-diethylamino -1-propanol (3-diethylamino-1-propanol), 1-dimethylamino-2-propanol (1-dimethylamino-2-propanol), 1-diethylamino-2-propanol (1-dimethylamino-2-propanol) , 5-diethanolamino-2-pentanol, diethanolamine, diisopropanolamine, N-methyldiethanolamine, N-ethyl N-ethylethanolamine, N-butyldiethanolamine, 3- (dimethyl Mino) -1,2-propanediol (3- (dimethylamino) -1,2-propanediol), 3- (diethylamino) -1,2-propanediol (3- (diethylamino) -1,2-propanediol) , 3- (diisopropylamino) -1,2-propanediol (3- (diisopropylamino) -1,2-propanediol), 3- (tertiary-butylamino) -1,2-propanediol (3- ( tert (butylamino) -1,2-propanediol), serinol, 2-aminodiethyl-1,3-propanediol, triethanolamine, 1- [N, N-bis (2-hydroxyethyl) amino] -2-propanol (1-N, N-bis (2-hydroxyethyl) amino] -2-propanol] triisopropanolamine, and bis-homo There is a bis-homotris.

본 발명의 메탈로센 촉매를 제조하기 위한 다른 방법으로는, Ⅳ족의 전이금속 화합물과 알코올아민 화합물을 반응시켜 생성물을 얻고, 시클로알칸디에닐기 유도체 리간드와 알칼리금속 화합물 또는 탈륨 화합물을 반응시켜 염 상태의 리간드를 얻고, 상기 생성물과 상기 리간드를 반응시켜 메탈로센 촉매를 제조하는 방법이 있다.As another method for preparing the metallocene catalyst of the present invention, a product is obtained by reacting a Group IV transition metal compound with an alcoholamine compound, and a cycloalkanedienyl derivative derivative ligand is reacted with an alkali metal compound or thallium compound to react with a salt. There is a method of obtaining a ligand in a state and reacting the product with the ligand to prepare a metallocene catalyst.

본 발명의 메탈로센 촉매는 조촉매와 함께 신디오탁틱 폴리스티렌을 중합하기 위하여 사용된다.The metallocene catalyst of the present invention is used to polymerize syndiotactic polystyrene with a cocatalyst.

조촉매로는 유기금속 화합물을 사용하거나, 비배위 루이스 산(non-coordinated Lewis acid)과 알킬알루미늄(alkyl aluminium)의 혼합물을 함께 사용한다. 여기서 사용될 수 있는 유기금속 화합물로는 알킬알루미늄옥산 또는 유기 알루미늄 화합물이 있다. 상기 알킬알루미늄옥산의 대표적인 예로는 메틸알루미늄옥산(methylaluminoxane; MAO) 및 개질된 메틸알루미늄옥산(modified methylaluminoxane; MMAO)이 있으며, 상기 유기알루미늄 화합물로는 하기 화학식 2a로 표시되는 단위를 가지고 있는 알루미늄옥산이 있으며, 이들은 하기 화학식 2b로 표시되는 사슬상의 알루미늄옥산과 하기 화학식 2c로 표시되는 환상의 알루미늄옥산이 있다:As a promoter, an organometallic compound may be used, or a mixture of non-coordinated Lewis acid and alkyl aluminum may be used together. Organometallic compounds that can be used here include alkylaluminum oxane or organoaluminum compounds. Representative examples of the alkylaluminum oxane include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO). As the organoaluminum compound, aluminum oxane having a unit represented by the following Chemical Formula 2a is These include a chain-shaped aluminum oxane represented by the formula (2b) and a cyclic aluminum oxane represented by the formula (2c):

상기 화학식 2a 내지 2c에서, R은 탄소수 1∼6의 알킬기이고, p는 0∼100의 정수이다.In Formulas 2a to 2c, R is an alkyl group having 1 to 6 carbon atoms, and p is an integer of 0 to 100.

상기의 신규 메탈로센 촉매와 조촉매인 유기금속 화합물을 사용함에 있어서 본 발명의 신규 메탈로센 촉매 성분과 조촉매인 유기금속 화합물의 성분 비율은 보통 유기금속 화합물의 성분중의 알루미늄과 신규 메탈로센 촉매 성분중의 Ⅳ족 전이금속과의 비, 즉 알루미늄 : 전이금속(예; 티탄, 지르코늄, 하프늄)의 몰비를 의미한다. 본 발명에서는 1 : 1 내지 1×106: 1 범위의 몰비로 사용될 수 있으며, 10 : 1 내지 1×104: 1의 범위로 사용되는 것이 바람직하다. 또한 사용되는 비배위 루이스 산(non-coordinated Lewis acid)과 알킬 알루미늄(alkyl aluminium)의 혼합물중 비배위 루이스 산(non-coordinated Lewis acid)은 N,N-디메틸 아닐린 테트라키스(펜타플루오로페닐)보레이트 [N,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate], 트리페닐 카베니움 테트라키스(펜타플루오로페닐)보레이트 [triphenyl carbenium tetrakis(pentafluorophenyl) borate] 또는 페로세리움 테트라키스(펜타플루오로페닐)보레이트 [ferrocerium tetrakis(pentafluorophenyl)borate]를 사용하며, 비배위 루이스산 : 전이금속(예; 티탄, 지르코늄, 하프늄)의 몰비로는 0.1 : 1 ∼ 20 : 1이며, 알킬 알루미늄(alkyl aluminium)은 트리메틸 알루미늄(trimethyl aluminium), 트리이소부틸 알루미늄(triisobutyl aluminium), 트리(n-부틸)알루미늄 (tri(n-butyl)aluminium), 트리(n-프로필)알루미늄(tri(n-propyl)aluminium) 및 트리이소프로필 알루미늄(triisopropyl aluminium) 중의 하나를 사용하며, 알킬알루미늄 : 전이금속(예; 티탄, 지르코늄, 하프늄)의 몰비로는 100 : 1 ∼ 1000 : 1이다. 상기 촉매 및 조촉매를 이용하여 스티렌을 중합하기 위한 중합 온도는 0∼100℃이고, 바람직하게는 30∼80℃이다.In using the organometallic compound which is the catalyst and the novel metallocene catalyst, the component ratio of the novel metallocene catalyst component of the present invention and the organometallic compound which is the promoter is usually aluminum and the new metal in the organometallic compound. The ratio of the group IV transition metal in the Rosene catalyst component, that is, the molar ratio of aluminum to transition metal (eg titanium, zirconium, hafnium). In the present invention, it may be used in a molar ratio of 1: 1 to 1 × 10 6 : 1, and preferably used in a range of 10: 1 to 1 × 10 4 : 1. In addition, the non-coordinated Lewis acid in the mixture of non-coordinated Lewis acid and alkyl aluminum is N, N-dimethyl aniline tetrakis (pentafluorophenyl). Borate [N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate], triphenyl carbenium tetrakis (pentafluorophenyl) borate [triphenyl carbenium tetrakis (pentafluorophenyl) borate] or ferrocerium tetrakis (pentafluorophenyl) Borate [ferrocerium tetrakis (pentafluorophenyl) borate] is used, the molar ratio of non-coordinating Lewis acid: transition metal (e.g. titanium, zirconium, hafnium) is 0.1: 1 to 20: 1, alkyl aluminum is trimethyl Trimethyl aluminum, triisobutyl aluminum, tri (n-butyl) aluminum, tri (n-propyl) aluminium and tree Isopropyl Aluminum using one and an alkyl aluminum in (triisopropyl aluminium): a transition metal; a molar ratio of (for example, titanium, zirconium, hafnium) is 100: 1: 1 to 1,000. The polymerization temperature for polymerizing styrene using the catalyst and the cocatalyst is 0 to 100 ° C, preferably 30 to 80 ° C.

본 발명에서 신디오탁틱 폴리스티렌을 제조하기 위한 모노머는 스티렌 또는 그 유도체이며, 스티렌 유도체로는 알킬스티렌(예; 메틸스티렌, 에틸스티렌, 부틸스티렌, 파라-메틸스티렌 파라-터셔리-부틸스티렌, 디메틸스티렌 등), 할로겐화 스티렌(예; 클로로스티렌, 브로모스티렌, 플로오로스티렌 등), 할로겐치환 알킬스티렌(예; 클로로메틸스티렌, 브로모메틸스티렌, 플로오로메틸스티렌 등), 알콕시스티렌(예; 메톡시스티렌, 에톡시스티렌, 부톡시스티렌 등), 카르복시메틸스티렌, 알킬에스테르스티렌, 알킬실릴스티렌비닐벤젠설폰산 에스테르, 비닐벤질디알콕시포스파이드 등을 들 수 있다.In the present invention, the monomer for preparing syndiotactic polystyrene is styrene or a derivative thereof. Examples of the styrene derivative include alkyl styrene (eg, methyl styrene, ethyl styrene, butyl styrene, para-methyl styrene para-tertiary-butyl styrene, dimethyl). Styrene), halogenated styrenes (e.g. chlorostyrene, bromostyrene, fluorostyrene, etc.), halogen-substituted alkylstyrenes (e.g. chloromethylstyrene, bromomethyl styrene, fluoromethylstyrene, etc.), alkoxy styrenes (e.g .; Methoxy styrene, ethoxy styrene, butoxy styrene), carboxymethyl styrene, alkyl ester styrene, alkyl silyl styrene vinylbenzene sulfonic acid ester, vinyl benzyl dialkoxy phosphide, etc. are mentioned.

본 발명의 메탈로센 촉매는 하기의 실시예에 의하여 보다 구체화될 것이며, 하기의 실시예는 본 발명의 예시목적이며 첨부된 특허청구범위의 보호범위를 제한하고자 하는 것은 아니다.The metallocene catalyst of the present invention will be further embodied by the following examples, which are intended to illustrate the present invention and are not intended to limit the scope of the appended claims.

실시예 1∼9: 촉매합성Examples 1-9: Catalytic Synthesis

실시예 1: CpExample 1: Cp ** Ti(OCHTi (OCH 22 CHCH 22 )) 33 N 합성N synthetic

칼륨 126mmol(4.92g)을 플라스크에 무게를 재어 넣은 후, THF(150㎖)를 넣었다. 이후 반응 용기를 0℃로 낮춘 후, Cp*(1,2,3,4,5-펜타메틸시클로펜타디엔) (Cp*(1,2,3,4,5-pentamethyl cyclopentadiene)) 126mmol(17.17g)을 천천히 가한 후, 반응온도를 올려 환류(reflux)시켰다. 반응이 진행되면서 바닥에 녹지않는 흰색의 고체가 가라앉았다. 고체가 가라앉기 시작한 후 약 1시간을 더 환류시킨 후 환류를 멈추고, 다시 온도를 0℃로 낮춘 후, 클로로트리메틸실란 130mmol을 주사기를 이용하여 서서히 가하였다. 이후 2시간 교반후 셀라이트(celite)를 통해 필터(filter)하면, 약간 노란색을 띠는 맑은 용액을 얻을 수 있고, 0.1 torr 정도의 감압하에서 용매(THF)를 제거하여 Cp*(1,2,3,4,5-펜타메틸시클로펜타디엔)에 트리메틸실란이 붙은 화합물을 90%의 수율(yield)로 얻었다. 이 화합물 88.9mmol(18.5g)을 톨루엔 50㎖와 혼합하고, TiCl488.9mmol(16.86g)과 톨루엔 200㎖가 섞여있는 플라스크에 천천히 가하였다. 이 붉은 용액을 2시간동안 교반한 후, 감압하에서 톨루엔을 제거한 후, 펜탄이나 헥산으로 씻어주고, 잘 말려서, 원하는 전형적인 반쪽 메탈로센(half metallocene)의 일종인 Cp*TiCl3가 95%의 수율로 얻었다. 이 화합물 5mmol(1.44g)을 플라스크에 디클로로메탄 20㎖를 넣어 녹였다. 다른 플라스크에 트리에탄올아민 5mmol(0.75g)을 넣고 디클로로메탄 20㎖에 녹인 후, 반응용기를 -78℃로 온도를 낮추었다. 이 용기에 트리에틸아민 15mmol(2.1㎖)를 주사기로 가한 후, 약 30분 동안 그 온도에서 교반한 후, Cp*TiCl3가 디클로로메탄 20㎖에 녹아 있는 용액을 트리에탄올아민과 트리에틸아민이 디클로로메탄 20㎖에 녹아 있는 용액에 서서히 첨가하였다. 첨가가 끝나면 즉시 반응용기의 온도를 상온으로 올렸다. 이후 12시간 정도 상온에서 반응을 시킨 후, 감압하에서 디클로로메탄을 제거하고, 헥산 50㎖을 가하여 30분 동안 교반하고, 셀라이트를 통해 필터하면 매우 맑은 노란색의 용액이 얻어지고, 감압하에서 헥산을 제거하여 Cp*Ti(OCH2CH2)3N 촉매를 75%의 수율로 얻었다.Potassium 126 mmol (4.92 g) was weighed into the flask followed by THF (150 mL). It was lowered to the reaction vessel to 0 ℃, Cp * (1,2,3,4,5- pentamethyl-cyclopentadienyl) (Cp * (1,2,3,4,5-pentamethyl cyclopentadiene)) 126mmol (17.17 After slowly adding g), the reaction temperature was raised to reflux. As the reaction proceeded, an insoluble white solid sank to the bottom. After refluxing, the reflux was stopped for a further 1 hour, the reflux was stopped, the temperature was lowered to 0 ° C., and 130 mmol of chlorotrimethylsilane was slowly added using a syringe. After stirring for 2 hours and then filtered through celite to obtain a slightly yellow clear solution, the solvent (THF) is removed under reduced pressure of about 0.1 torr Cp * (1,2, 3,4,5-pentamethylcyclopentadiene) was obtained in 90% yield with a compound having trimethylsilane. This compound 88.9mmol (18.5g) mixed with toluene 50㎖, which was added to the flask with mixed TiCl 4 88.9mmol (16.86g) and toluene 200㎖ slowly. After stirring this red solution for 2 hours, toluene was removed under reduced pressure, washed with pentane or hexane and dried well, yielding 95% yield of Cp * TiCl 3 , a type of typical half metallocene desired. Got it. 5 mmol (1.44 g) of this compound was dissolved in 20 ml of dichloromethane in a flask. 5 mmol (0.75 g) of triethanolamine was added to another flask, and the resultant was dissolved in 20 ml of dichloromethane, and the reaction vessel was then cooled to -78 ° C. 15 mmol (2.1 ml) of triethylamine was added to the vessel, followed by stirring at that temperature for about 30 minutes. Then, a solution in which Cp * TiCl 3 was dissolved in 20 ml of dichloromethane was dissolved in triethanolamine and triethylamine. It was added slowly to the solution dissolved in 20 ml of methane. Immediately after the addition, the temperature of the reaction vessel was raised to room temperature. After reacting at room temperature for about 12 hours, dichloromethane was removed under reduced pressure, 50 ml of hexane was added thereto, stirred for 30 minutes, filtered through celite to obtain a very clear yellow solution, and hexane was removed under reduced pressure. To give a Cp * Ti (OCH 2 CH 2 ) 3 N catalyst in 75% yield.

실시예 2: CpExample 2: Cp ** Ti(OCHTi (OCH 22 CHCH 22 )) 33 N 합성N synthetic

실시예 1의 Cp*Ti(OCH2CH2)3N 촉매는 다음과 같은 방법으로도 합성되었다. 플라스크에 트리에탄올아민 5mmol(0.75g)을 넣고 디클로로메탄 20㎖에 녹인 후, 반응용기를 -78℃로 온도를 낮추었다. 이 용기에 트리에틸아민 15mmol(2.1㎖)를 주사기로 가한 후, 약 30분 동안 그 온도에서 교반한 후, TiCl45mmol(0.95g)를 천천히 가하면 흰색의 고체가 생긴다. 12시간 더 반응 후, 감압하에서 용매인 디클로로메탄을 제거하고 생긴 고체를 헥산으로 씻어주고, 감압하에서 잘 말린 후, 생성되는 고체와 리튬 펜타메틸시클로펜타디엔니드(lithium pentamethylcyclopentadienide) 5mmol(0.71g)를 플라스크에 섞고 -78℃에서 THF 50㎖를 가한 후, 12시간 동안 반응 후, 감압하에서 THF를 제거하고, 헥산 50㎖를 가하여 30분 동안 교반하고, 셀라이트를 통해 필터하면 매우 맑은 노란색의 용액이 얻어지고, 감압하에서 헥산을 제거하여 Cp*Ti(OCH2CH2)3N 촉매를 60% 수율로 얻을 수 있었다.The Cp * Ti (OCH 2 CH 2 ) 3 N catalyst of Example 1 was also synthesized by the following method. 5 mmol (0.75 g) of triethanolamine was added to the flask and dissolved in 20 mL of dichloromethane. The reaction vessel was then cooled to -78 ° C. 15 mmol (2.1 ml) of triethylamine was added to the vessel, stirred at that temperature for about 30 minutes, and slowly added 5 mmol (0.95 g) of TiCl 4 to give a white solid. After 12 hours of further reaction, dichloromethane as a solvent was removed under reduced pressure, and the resulting solid was washed with hexane. After drying under reduced pressure, 5 mmol (0.71 g) of lithium pentamethylcyclopentadienide was formed. After mixing with the flask and adding 50 ml of THF at -78 ° C, reacting for 12 hours, removing THF under reduced pressure, adding 50 ml of hexane, stirring for 30 minutes, and filtering through Celite to give a very clear yellow solution. Obtained, and hexane was removed under reduced pressure to obtain a Cp * Ti (OCH 2 CH 2 ) 3 N catalyst in 60% yield.

실시예 3: CpExample 3: Cp ** TiCl(OCHTiCl (OCH 22 CHCH 22 )) 22 NCHNCH 33 합성synthesis

트리에탄올아민 대신에 N-메틸디에탄올아민을 사용한 것 외에는 실시예 1과 동일한 방법으로 제조하였다.Preparation was carried out in the same manner as in Example 1 except that N-methyldiethanolamine was used instead of triethanolamine.

실시예 4: CpExample 4: Cp ** TiClTiCl 22 (OCH(OCH 22 CHCH 22 )N(CH) N (CH 33 )) 22 합성synthesis

트리에탄올아민 대신에 N,N-디메틸에탄올아민을 사용한 것 외에는 실시예 1과 동일한 방법으로 제조하였다.Preparation was carried out in the same manner as in Example 1 except that N, N-dimethylethanolamine was used instead of triethanolamine.

실시예 5: CpExample 5: Cp ** Ti[(OCHTi [(OCH 22 CHCH 22 )N(CH) N (CH 33 )) 22 ]] 33 합성synthesis

트리에탄올아민 대신에 N,N-디메틸에탄올아민을 사용한 것 외에는 실시예 1과 동일한 방법으로 제조하였다. 그러나 상기 Cp*Ti(OCH2CH2)3N 촉매 합성시 Cp*TiCl31당량에 대해서 트리에탄올아민 1당량이 반응에 소요되나, Cp*Ti[(OCH2CH2)N(CH3)2]3합성시에는 Cp*TiCl31당량에 대해서 N,N-디메틸에탄올아민 3당량이 소요되었다.Preparation was carried out in the same manner as in Example 1 except that N, N-dimethylethanolamine was used instead of triethanolamine. However, when synthesizing the Cp * Ti (OCH 2 CH 2 ) 3 N catalyst, 1 equivalent of triethanolamine is required for the reaction with respect to 1 equivalent of Cp * TiCl 3 , but Cp * Ti [(OCH 2 CH 2 ) N (CH 3 ) 2 3, 3 equivalents of N, N-dimethylethanolamine were used for 1 equivalent of Cp * TiCl 3 .

실시예 6: CpExample 6: Cp ** TiCl[(OCHTiCl [(OCH 22 CHCH 22 )N(CH) N (CH 33 )) 22 ]] 22 합성synthesis

트리에탄올아민 대신에 N,N-디메틸에탄올아민을 사용한 것 외에는 실시예 1과 동일한 방법으로 제조하였다. 그러나 상기 Cp*Ti(OCH2CH2)3N 촉매 합성시 Cp*TiCl31당량에 대해서 트리에탄올아민 1당량이 반응에 소요되나, Cp*TiCl[(OCH2CH2)N(CH3)2]2합성시에는 Cp*TiCl31당량에 대해서 N,N-디메틸에탄올아민 2당량이 소요되었다.Preparation was carried out in the same manner as in Example 1 except that N, N-dimethylethanolamine was used instead of triethanolamine. However, when synthesizing the Cp * Ti (OCH 2 CH 2 ) 3 N catalyst, 1 equivalent of triethanolamine is required for the reaction with respect to 1 equivalent of Cp * TiCl 3 , but Cp * TiCl [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 2 equivalents of N, N-dimethylethanolamine were used for 1 equivalent of Cp * TiCl 3 .

실시예 7: CpExample 7: Cp ** Ti(OCHTi (OCH 33 )[(OCH) [(OCH 22 CHCH 22 )) 22 NCHNCH 33 ] 합성] synthesis

Cp*TiCl(OCH2CH2)2NCH35mmol(1.68g)을 플라스크에 디클로로메탄 20㎖를 넣어 녹였다. 다른 플라스크에 메탄올 5mmol(0.16g)을 넣고 디클로로메탄 20㎖에 녹인 후, 반응용기를 -78℃로 온도를 낮추었다. 이 용기에 트리에틸아민 5mmol(0.7㎖)를 주사기로 가한 후, 약 30분 동안 그 온도에서 교반한 후, Cp*TiCl[(OCH2CH2)2NCH3]가 디클로로메탄 20㎖에 녹아 있는 용액을 트리에틸아민과 메탄올이 디클로로메탄 20㎖에 녹아 있는 용액에 서서히 첨가하였다. 첨가가 끝나면 즉시 반응용기의 온도를 상온으로 올렸다. 이후 12시간 정도 상온에서 반응을 시킨 후, 감압하에서 디클로로메탄을 제거하고, 헥산 50㎖을 가하여 30분 동안 교반하고, 셀라이트를 통해 필터하면 매우 맑은 노란색의 용액이 얻어지고, 감압하에서 헥산을 제거하여 상기의 Cp*Ti(OCH3)[(OCH2CH2)2NCH3] 촉매를 80%의 수율로 얻었다.5 mmol (1.68 g) of Cp * TiCl (OCH 2 CH 2 ) 2 NCH 3 was dissolved in 20 ml of dichloromethane. Into another flask, 5 mmol (0.16 g) of methanol was dissolved in 20 ml of dichloromethane, and the reaction vessel was then cooled to -78 ° C. 5 mmol (0.7 ml) of triethylamine was added to the vessel, followed by stirring at that temperature for about 30 minutes, after which Cp * TiCl [(OCH 2 CH 2 ) 2 NCH 3 ] was dissolved in 20 ml of dichloromethane. The solution was slowly added to the solution of triethylamine and methanol in 20 ml of dichloromethane. Immediately after the addition, the temperature of the reaction vessel was raised to room temperature. After reacting at room temperature for about 12 hours, dichloromethane was removed under reduced pressure, 50 ml of hexane was added thereto, stirred for 30 minutes, filtered through celite to obtain a very clear yellow solution, and hexane was removed under reduced pressure. To obtain the Cp * Ti (OCH 3 ) [(OCH 2 CH 2 ) 2 NCH 3 ] catalyst in a yield of 80%.

실시예 8: CpExample 8: Cp ** Ti(OCHTi (OCH 33 )) 22 [(OCH[(OCH 22 CHCH 22 )N(CH) N (CH 33 )) 22 ] 합성] synthesis

Cp*TiCl(OCH2CH2)2NCH3대신에 Cp*TiCl2(OCH2CH2)N(CH3)2를 사용하는 것 외에는 실시예 7과 동일한 방법으로 제조하였다. 그러나 상기 Cp*Ti(OCH3)[(OCH2CH2)2NCH3]촉매 합성시 Cp*TiCl(OCH2CH2)2NCH31당량에 대해서 메탄올과 트리에틸아민이 각각 1당량 반응에 소요되나, Cp*Ti(OCH3)2[(OCH2CH2)N(CH3)2]합성시에는 Cp*TiCl2(OCH2CH2)N(CH3)21당량에 대해서 메탄올과 트리에틸아민이 각각 2당량 소요되었다.It was prepared in the same manner as in Example 7, except that Cp * TiCl 2 (OCH 2 CH 2 ) N (CH 3 ) 2 was used instead of Cp * TiCl (OCH 2 CH 2 ) 2 NCH 3 . However, methanol and triethylamine were reacted in 1 equivalent reaction with respect to 1 equivalent of Cp * TiCl (OCH 2 CH 2 ) 2 NCH 3 when the Cp * Ti (OCH 3 ) [(OCH 2 CH 2 ) 2 NCH 3 ] catalyst was synthesized. However, when synthesizing Cp * Ti (OCH 3 ) 2 [(OCH 2 CH 2 ) N (CH 3 ) 2 ], Cp * TiCl 2 (OCH 2 CH 2 ) N (CH 3 ) 2 Triethylamine consumed 2 equivalents each.

실시예 9: CpExample 9: Cp ** Ti(OCHTi (OCH 33 )[(OCH) [(OCH 22 CHCH 22 )N(CH) N (CH 33 )) 22 ]] 22 합성synthesis

Cp*TiCl(OCH2CH2)2NCH3대신에 Cp*TiCl[(OCH2CH2)N(CH3)2]2를 사용한 것 외에는 실시예 7과 동일한 방법으로 제조하였다.It was prepared in the same manner as in Example 7, except that Cp * TiCl [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 2 was used instead of Cp * TiCl (OCH 2 CH 2 ) 2 NCH 3 .

실시예 10: 스티렌 중합(용액 중합)Example 10: Styrene Polymerization (Solution Polymerization)

실시예 1∼9에서 제조된 메탈로센 촉매와 종래의 메탈로센 촉매인 펜타메틸시클로펜타디에닐티타늄 트리클로라이드(Cp*TiCl3)를 사용하여 스티렌을 중합하였다. 여기서는 촉매 농도를 4×10-6mol, 스티렌 단량체 20cc, 톨루엔 80cc, [Al]/[Ti]=1000, 온도 70℃에서, 1시간동안 중합하였다. 스티렌 중합은 외부온도 조절장치, 자기교반기 또는 기계교반기 장치를 사용하고, 단량체와 질소를 공급할 수 있는 밸브가 있는 유리 반응기에서 행하였다. 질소 치환된 유리반응기에 톨루엔을 첨가하고, 정제한 스티렌을 첨가하고, 조촉매인 MMAO를 필요량 투입하여 충분히 교반한 후, 필요량의 촉매를 주입하여 중합을 개시시켰다. 일정시간 후 약간의 메탄올을 넣어 중합을 종결시켰다. 얻은 혼합물을 염산이 첨가된 다량의 메탄올에 부어 중합체를 얻고 물과 메탄올로 세척한 다음 진공 건조하였다. 중합하여 얻어진 폴리스티렌의 물성을 표 1에 나타내었다.Styrene was polymerized using the metallocene catalysts prepared in Examples 1-9 and pentamethylcyclopentadienyltitanium trichloride (Cp * TiCl 3 ), which is a conventional metallocene catalyst. Here, the catalyst concentration was polymerized at 4 × 10 −6 mol, 20 cc of styrene monomer, 80 cc of toluene, [Al] / [Ti] = 1000 at a temperature of 70 ° C. for 1 hour. Styrene polymerization was carried out in a glass reactor equipped with a valve capable of supplying monomers and nitrogen, using an external temperature controller, a magnetic stirrer or a mechanical stirrer. Toluene was added to the nitrogen-substituted glass reactor, purified styrene was added, a necessary amount of co-catalyst MMAO was added and stirred sufficiently, and then the required amount of catalyst was injected to initiate polymerization. After some time, a little methanol was added to terminate the polymerization. The resulting mixture was poured into a large amount of methanol added with hydrochloric acid to obtain a polymer, washed with water and methanol and dried in vacuo. Table 1 shows the physical properties of the polystyrene obtained by polymerization.

실시예Example 촉 매catalyst 수율(g)Yield (g) 활성Kg·PS/[Ti][St]hrActive KgPS / [Ti] [St] hr 입체규칙성(%)Stereoregularity (%) 녹는점(℃)Melting Point (℃) -- [Cp*TiCl3][Cp * TiCl 3 ] 2.212.21 3,1653,165 9797 270270 실시예 1-2Example 1-2 Cp*Ti(OCH2CH2)3NCp * Ti (OCH 2 CH 2 ) 3 N 2.322.32 3,3233,323 9898 270270 실시예 3Example 3 Cp*TiCl(OCH2CH2)2NCH3 Cp * TiCl (OCH 2 CH 2 ) 2 NCH 3 3.083.08 4,4114,411 9898 271271 실시예 4Example 4 Cp*TiCl2(OCH2CH2)N(CH3)2 Cp * TiCl 2 (OCH 2 CH 2 ) N (CH 3 ) 2 2.252.25 3,2233,223 9696 269269 실시예 5Example 5 Cp*Ti[(OCH2CH2)N(CH3)2]3 Cp * Ti [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 3 2.312.31 3,3093,309 9797 270270 실시예 6Example 6 Cp*TiCl[(OCH2CH2)N(CH3)2]2 Cp * TiCl [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 2 2.852.85 4,0824,082 9797 271271 실시예 7Example 7 Cp*Ti(OCH3)[(OCH2CH2)2NCH3]Cp * Ti (OCH 3 ) [(OCH 2 CH 2 ) 2 NCH 3 ] 3.543.54 5,0705,070 9898 270270 실시예 8Example 8 Cp*Ti(OCH3)2[(OCH2CH2)N(CH3)2]Cp * Ti (OCH 3 ) 2 [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 3.683.68 5,2715,271 9898 271271 실시예 9Example 9 Cp*Ti(OCH3)[(OCH2CH2)N(CH3)2]2 Cp * Ti (OCH 3 ) [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 2 3.413.41 4,8844,884 9898 270270

실시예 11: 스티렌 중합(괴상 중합)Example 11: Styrene Polymerization (Block Polymerization)

실시예 1∼9에서 제조된 메탈로센 촉매와 종래의 메탈로센 촉매인 펜타메틸시클로펜타디에닐티타늄 트리클로라이드(Cp*TiCl3)를 사용하여 스티렌을 중합하였다. 여기서는 촉매 농도를 5×10-5mol, 스티렌 단량체 200cc, [Al]/[Ti]=400, 온도 70℃에서, 1시간동안 중합하였다. 스티렌 중합은 외부온도 조절장치, 자기교반기 또는 기계교반기 장치를 사용하고, 단량체와 질소를 공급할 수 있는 밸브가 있는 유리 반응기에서 행하였다. 질소 치환된 유리반응기에 정제한 스티렌을 첨가하고 조촉매인 MMAO를 필요량 투입하고 충분히 교반한 후, 필요량의 촉매를 주입하여 중합을 개시시켰다. 일정시간 후 약간의 메탄올을 넣어 중합을 종결시켰다. 얻은 혼합물을 염산이 첨가된 다량의 메탄올에 부어 중합체를 얻고 물과 메탄올로 세척한 다음 진공 건조하였다. 중합하여 얻어진 폴리스티렌의 물성을 표 2에 나타내었다.Styrene was polymerized using the metallocene catalysts prepared in Examples 1-9 and pentamethylcyclopentadienyltitanium trichloride (Cp * TiCl 3 ), which is a conventional metallocene catalyst. In this case, the catalyst concentration was polymerized at 5 × 10 −5 mol, 200 cc of styrene monomer, [Al] / [Ti] = 400 at a temperature of 70 ° C. for 1 hour. Styrene polymerization was carried out in a glass reactor equipped with a valve capable of supplying monomers and nitrogen, using an external temperature controller, a magnetic stirrer or a mechanical stirrer. Purified styrene was added to a nitrogen-substituted glass reactor, MMAO as a cocatalyst was added to the required amount, stirred sufficiently, and then the required amount of catalyst was injected to initiate polymerization. After some time, a little methanol was added to terminate the polymerization. The resulting mixture was poured into a large amount of methanol added with hydrochloric acid to obtain a polymer, washed with water and methanol and dried in vacuo. Table 2 shows the physical properties of the polystyrene obtained by polymerization.

실시예Example 촉 매catalyst 수율(g)Yield (g) 활성Kg·PS/[Ti][St]hrActive KgPS / [Ti] [St] hr 입체규칙성(%)Stereoregularity (%) 녹는점(℃)Melting Point (℃) -- [Cp*TiCl3][Cp * TiCl 3 ] 60.560.5 693693 9696 269269 실시예 1-2Example 1-2 Cp*Ti(OCH2CH2)3NCp * Ti (OCH 2 CH 2 ) 3 N 62.562.5 716716 9797 270270 실시예 3Example 3 Cp*TiCl(OCH2CH2)2NCH3 Cp * TiCl (OCH 2 CH 2 ) 2 NCH 3 68.568.5 785785 9797 270270 실시예 4Example 4 Cp*TiCl2(OCH2CH2)N(CH3)2 Cp * TiCl 2 (OCH 2 CH 2 ) N (CH 3 ) 2 61.561.5 705705 9696 269269 실시예 5Example 5 Cp*Ti[(OCH2CH2)N(CH3)2]3 Cp * Ti [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 3 63.063.0 722722 9696 269269 실시예 6Example 6 Cp*TiCl[(OCH2CH2)N(CH3)2]2 Cp * TiCl [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 2 65.565.5 751751 9797 270270 실시예 7Example 7 Cp*Ti(OCH3)[(OCH2CH2)2NCH3]Cp * Ti (OCH 3 ) [(OCH 2 CH 2 ) 2 NCH 3 ] 72.372.3 828828 9898 270270 실시예 8Example 8 Cp*Ti(OCH3)2[(OCH2CH2)N(CH3)2]Cp * Ti (OCH 3 ) 2 [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 78.678.6 901901 9898 271271 실시예 9Example 9 Cp*Ti(OCH3)[(OCH2CH2)N(CH3)2]2 Cp * Ti (OCH 3 ) [(OCH 2 CH 2 ) N (CH 3 ) 2 ] 2 73.473.4 841841 9898 270270

상기 표 1 및 표 2의 중합에서 얻어진 중합체의 입체규칙성은 얻어진 폴리스티렌의 신디오탁틱 인덱스(S.I.)를 측정하기 위하여 중합체를 메틸에틸케톤으로 추출하였고, 추출 후 남아있는 중합체의 무게를 구하여 백분율로 S.I.를 나타내었다.The stereoregularity of the polymers obtained in the polymerization of Tables 1 and 2 was extracted with methyl ethyl ketone to determine the syndiotactic index (SI) of the obtained polystyrene, and the weight of the remaining polymer after extraction was calculated as SI Indicated.

상기 표 1 및 표 2의 녹는점은 시차열분석기(DSC)로 측정하였으며, 시편을 200℃까지 승온시켜 5분간 방치한 후 냉각, 승온시키면서 측정하였고 승온 속도는 10℃/분로 하였다.The melting point of Table 1 and Table 2 was measured by a differential thermal analyzer (DSC), the specimen was heated to 200 ℃ and left for 5 minutes and then measured while cooling, the temperature was raised to 10 ℃ / min.

본 발명의 메탈로센 촉매는 입체규칙성이 우수하고, 높은 용융온도를 가지며, 분자량 분포가 양호한 신디오탁틱 폴리스티렌을 제조하는 데 사용될 수 있으며 적은 양의 조촉매를 사용하여 신디오탁틱 폴리스티렌을 제조할 수 있는 발명의 효과를 가진다.The metallocene catalyst of the present invention can be used to prepare syndiotactic polystyrene having excellent stereoregularity, high melting temperature, and good molecular weight distribution, and is used to prepare syndiotactic polystyrene using a small amount of promoter. It has the effect of the invention which can be done.

상기 표 1 및 표 2에서 알 수 있듯이 용액중합(solution polymerization) 및 괴상중합(bulk polymerization)시 본 발명의 신규 메탈로센 촉매를 사용하여 스티렌을 중합하는 경우에 전체적으로 그 중합활성이 Cp*TiCl3보다 우수하였으며, 입체규칙성(syndiotactic index; S.I.)은 동등내지 우수한 결과를 보였고, 녹는점은 약 270℃ 정도로 커다란 차이를 보이지 않은 중합체를 제조할 수 있다.As can be seen in Table 1 and Table 2, when the polymerization of styrene using the novel metallocene catalyst of the present invention during solution polymerization and bulk polymerization, the polymerization activity is generally Cp * TiCl 3 It was better, the syndiotactic index (SI) was equal to excellent results, the melting point of about 270 ℃ can be produced a polymer does not show a large difference.

본 발명의 단순한 변형 또는 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 이용될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or variations of the present invention can be readily used by those skilled in the art, and all such modifications or changes can be regarded as being included in the scope of the present invention.

Claims (11)

하기 화학식 1a, 1b, 1c, 1d 또는 1e의 구조식을 갖고, 신디오탁틱 폴리스티렌을 제조하기 위한 메탈로센 촉매:A metallocene catalyst having the structural formula of Formula 1a, 1b, 1c, 1d or 1e, for preparing syndiotactic polystyrene: 화학식 1aFormula 1a 화학식 1bFormula 1b 화학식 1cFormula 1c 화학식 1dFormula 1d 화학식 1eFormula 1e 상기 화학식 1a 내지 1e에서, L1, L2, L3, L4및 L5는 주기율표 Ⅳ족의 전이금속 M과 η5결합을 생성하는 각각 시클로펜타디에닐기, 인데닐기, 플로오레닐기 또는 그것의 유도체중의 하나로서, 이들은 하기 구조식(Ⅰ), (Ⅱ) 또는 (Ⅲ)으로 표시되며:In Formulas 1a to 1e, L 1 , L 2 , L 3 , L 4, and L 5 each represent a cyclopentadienyl group, indenyl group, fluorenyl group, or the like to form a η 5 bond with a transition metal M of Group IV of the periodic table. As one of derivatives of these, they are represented by the following structural formulas (I), (II) or (III): (상기식 Ⅰ 내지 Ⅲ에서 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12및 R13은 각각 독립적으로 수소원자, 탄소수 1 내지 20의 알킬기, 시클로알킬기, 알콕시기, 아실옥시기, 알킬실릴기, 탄소수 6 내지 20의 아릴기, 알킬아릴기 또는 아릴알킬기이며, 상기 실릴기는 -Sir1r2r3으로 나타낼 수 있으며, 여기서 r1, r2및 r3은 독립적으로 수소원자, 탄소수 1 내지 10의 알킬기, 또는 탄소수 6 내지 20의 아릴기임),(In Formulas I to III, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, an acyloxy group, an alkylsilyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and the silyl group is represented by -Sir 1 r 2 r 3 Wherein r 1 , r 2 and r 3 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, A1, A2, A3, A4, A5, A6, A7, A8, A9, A10및 A11은 독립적으로 산소원자이고, B1, B2, B3, B4, B5, B6, B7, B8, B9, B10및 B11은 각각 독립적으로 탄소수 1 내지 20의 알킬기 또는 시클로알킬기이고, C1, C2, C3, C4및 C6은 각각 질소원자, -NR1', -NR2'R3', -NR4'R5', 또는 -NR6'R7'로 표현할 수 있으며, C5, C7및 C8은 각각 독립적으로 -NR8'R9' 또는 -CR10'R11'R12'로 나타낼 수 있고, 상기에서 R1', R2', R3', R4', R5', R6', R7', R8', R9', R10', R11' 및 R12'은 각각 독립적으로 수소원자 또는 탄소수 1 내지 10의 알킬기이고, X1, X2, X3및 X4는 각각 독립적으로 할로겐 원자, 탄소수 1 내지 10의 알킬기, 시클로알킬기, 알콕시, 아실옥시기, 탄소수 6 내지 20의 아릴기, 알킬아릴기 또는 아릴알킬기임.A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 and A 11 are independently oxygen atoms, B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 , B 8 , B 9 , B 10 and B 11 are each independently an alkyl or cycloalkyl group having 1 to 20 carbon atoms, and C 1 , C 2 , C 3 , C 4 and C 6 Are each represented by a nitrogen atom, -NR 1 ', -NR 2 ' R 3 ', -NR 4 ' R 5 ', or -NR 6 ' R 7 ', and C 5 , C 7 and C 8 are each independently As -NR 8 'R 9 ' or -CR 10 'R 11 ' R 12 ', wherein R 1 ', R 2 ', R 3 ', R 4 ', R 5 ', R 6 ', R 7 ′, R 8 ′, R 9 ′, R 10 ′, R 11 ′ and R 12 ′ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X 1 , X 2 , X 3 and X 4 are Each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkoxy, acyloxy group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group. 시클로알칸디에닐기 유도체 리간드를 알칼리금속 화합물 또는 탈륨 화합물과 반응시켜 알칼리금속 또는 탈륨 양이온을 함유하는 염(salt) 상태의 리간드를 제조하고;Reacting the cycloalkanedienyl group derivative ligand with an alkali metal compound or thallium compound to prepare a ligand in a salt state containing an alkali metal or thallium cation; 상기 리간드에 산에 잘 떨어져 나가는 화합물을 도입시키고;Introducing a compound that falls off well into acid to the ligand; 상기 생성물에 Ⅳ족의 전이금속 화합물을 반응시켜 반쪽 메탈로센 화합물을 제조하고; 그리고Reacting the product with a Group IV transition metal compound to produce a half metallocene compound; And 상기 반쪽 메탈로센(half metallocene) 화합물에 알코올아민 화합물을 반응시키는;Reacting an alcohol amine compound with the half metallocene compound; 단계로 이루어지는 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.Method for producing a metallocene catalyst for styrene polymerization, characterized in that consisting of steps. 제2항에 있어서, 상기 시클로알칸디에닐기는 시클로펜타디에닐기, 치환된 시클로펜타디에닐기, 인데닐기, 치환된 인데닐기, 플루오레닐기 및 치환된 플루오레닐기로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.The method of claim 2, wherein the cycloalkanedienyl group is selected from the group consisting of a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, and a substituted fluorenyl group. Method for producing a metallocene catalyst for styrene polymerization. 제2항에 있어서, 상기 알칼리금속화합물은 알킬기 또는 알콕시기를 가지며, 부틸리튬, 세크-부틸리튬, 터셔리-부틸리튬, 메틸리튬, 나트륨 메톡사이드, 및 나트륨 에톡사이드로 이루어진 군으로부터 선택되는 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.The method of claim 2, wherein the alkali metal compound has an alkyl group or an alkoxy group, characterized in that selected from the group consisting of butyllithium, sec-butyllithium, tertiary-butyllithium, methyllithium, sodium methoxide, and sodium ethoxide. The manufacturing method of the metallocene catalyst for styrene superposition | polymerization made into. 제2항에 있어서, 상기 탈륨 화합물은 탈륨 에톡사이드인 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.3. The method of claim 2, wherein the thallium compound is thallium ethoxide. 4. 제2항에 있어서, 상기 Ⅳ족의 전이금속 화합물은 사염화 티타늄(TiCl4), 사염화지르코늄(ZrCl4) 및 사염화하프늄(HfCl4)로 이루어진 군으로부터 선택되는 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.The metallocene for styrene polymerization according to claim 2, wherein the transition metal compound of Group IV is selected from the group consisting of titanium tetrachloride (TiCl 4 ), zirconium tetrachloride (ZrCl 4 ) and hafnium tetrachloride (HfCl 4 ). Method for preparing a catalyst. 제2항에 있어서, 상기 알코올아민 화합물은 에탄올아민, 3-아미노-1-프로판올, 1-아미노-2-프로판올, 4-아미노-1-부탄올, 2-아미노-1-부탄올, 2-아미노-2-메틸-1-프로판올, 5-아미노-1-펜탄올, 2-아미노-1-펜탄올, 2-아미노-3-메틸-1-부탄올, 6-아미노-1-헥산올, 2-아미노-1-헥산올, 이소루신올, 루신올, 2-아미노시클로헥산올, 3-아미노메틸-3,5,5-트리메틸시클로헥산올, 2-(2-아미노에톡시)에탄올, 2-(2-아미노에틸아미노)에탄올, 1,3-비스(디메틸아미노)-2-프로판올, 2-(메틸아미노)에탄올, 2-(에틸아미노)에탄올, 2-(프로필아미노)에탄올, 2-(터셔리-부틸아미노)에탄올, N,N-디메틸에탄올아민, N,N-디에틸에탄올아민, 2-(디부틸아미노)에탄올, 3-디메닐아미노-1-프로판을, 3-디에틸아미노-1-프로판올, 1-디메틸아미노-2-프로판올, 1-디에틸아미노-2-프로판올, 5-디에탄올아미노-2-펜탄올, 디에탄올아민, 디이소프로판올아민, N-메틸디에탄올아민, N-에틸에탄올아민, N-부틸디에탄올아민, 3-(디메틸아미노)-1,2-프로판디올, 3-(디에틸아미노)-1,2-프로판디올, 3-(디이소프로필아미노)-1,2-프로판디올, 3-(터셔리-부틸아미노)-1,2-프로판디올, 세린올, 2-아미노디에틸-1,3-프로판디올, 트리에탄올아민, 1-[N,N-비스(2-히드록시에틸)아미노]-2-프로판올, 트리이소프로판올아민 및 비스-호모트리스(bis-homotris)로 이루어진 군으로부터 선택되는 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.The method of claim 2, wherein the alcohol amine compound is ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino- 2-methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2-amino-3-methyl-1-butanol, 6-amino-1-hexanol, 2-amino -1-hexanol, isoleucine, leucine, 2-aminocyclohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2- (2-aminoethoxy) ethanol, 2- ( 2-aminoethylamino) ethanol, 1,3-bis (dimethylamino) -2-propanol, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (propylamino) ethanol, 2- (ter Sheryl-butylamino) ethanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, 2- (dibutylamino) ethanol, 3-dimenylamino-1-propane, 3-diethylamino- 1-propanol, 1-dimethylamino-2-propanol, 1-diethylamino-2-propanol, 5-diethanolamino-2-pentanol, Diethanolamine, diisopropanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-butyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3- (diethylamino)- 1,2-propanediol, 3- (diisopropylamino) -1,2-propanediol, 3- (tertiary-butylamino) -1,2-propanediol, serineol, 2-aminodiethyl-1 , 3-propanediol, triethanolamine, 1- [N, N-bis (2-hydroxyethyl) amino] -2-propanol, triisopropanolamine and bis-homotris Method for producing a metallocene catalyst for styrene polymerization, characterized in that. Ⅳ족의 전이금속 화합물과 알코올아민 화합물을 반응시켜 생성물을 얻고;Reacting the transition metal compound of Group IV with an alcoholamine compound to obtain a product; 시클로알칸디에닐기 유도체 리간드와 알칼리금속 화합물 또는 탈륨 화합물을 반응시켜 염상태의 리간드를 얻고; 그리고Reacting the cycloalkanedienyl group derivative ligand with an alkali metal compound or thallium compound to obtain a salt ligand; And 상기 생성물과 상기 리간드를 반응시키는;Reacting the product with the ligand; 단계로 이루어지는 것을 특징으로 하는 스티렌 중합용 메탈로센 촉매의 제조방법.Method for producing a metallocene catalyst for styrene polymerization, characterized in that consisting of steps. 스티렌을 제1항의 메탈로센 촉매와 조촉매로써 중합시켜 신디오탁틱 폴리스티렌을 제조하기 위한 방법.A method for producing syndiotactic polystyrene by polymerizing styrene with a cocatalyst of the metallocene catalyst of claim 1. 제9항에 있어서, 상기 조촉매는 알킬알루미늄옥산, 유기 알루미늄 화합물, 또는 비배위 루이스 산(non-coordinated Lewis acid)과 알킬알루미늄(alkyl aluminium)의 혼합물인 것을 특징으로 하는 신디오탁틱 폴리스티렌의 제조방법.10. The preparation of syndiotactic polystyrene according to claim 9, wherein the promoter is an alkylaluminum oxane, an organoaluminum compound, or a mixture of non-coordinated Lewis acid and alkylaluminum. Way. 제10항에 있어서, 상기 메탈로센 촉매가 실리카, 알루미나, 염화마그네슘, 제올라이트, 인산알루미늄 및 지르코니아로 이루어진 군으로부터 선택되는 지지체에 담지되는 것을 특징으로 하는 신디오탁틱 폴리스티렌의 제조방법.The method for producing syndiotactic polystyrene according to claim 10, wherein the metallocene catalyst is supported on a support selected from the group consisting of silica, alumina, magnesium chloride, zeolite, aluminum phosphate, and zirconia.
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KR100497172B1 (en) * 2002-11-11 2005-06-28 주식회사 엘지화학 Multinuclear half metallocene catalyst having sandwitch type metallocene derivatives as ligands for styrene polymerization and polymerization process using the metallocene catalyst
KR100503359B1 (en) * 2002-10-16 2005-07-26 주식회사 엘지화학 Metallocene catalyst for styrene polymerization and polymerization process using the same
EP1777239A1 (en) * 2005-10-19 2007-04-25 LG Chem Ltd. Half-metallocene catalyst and process for preparing syndiotactic styrene polymer using the same
KR100771351B1 (en) * 2004-08-12 2007-10-29 주식회사 엘지화학 Novel Half Metallocene Catalysts and Method for Preparing Syndiotactic Polystyrenes

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KR100440482B1 (en) * 2001-07-11 2004-07-14 주식회사 엘지화학 New multinuclear half metallocene catalyst for styrene polymerization
US7592404B2 (en) 2005-11-08 2009-09-22 Lg Chem, Ltd. Half metallocene catalyst and process for preparing syndiotactic styren polymer using the same

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KR100503359B1 (en) * 2002-10-16 2005-07-26 주식회사 엘지화학 Metallocene catalyst for styrene polymerization and polymerization process using the same
KR100497172B1 (en) * 2002-11-11 2005-06-28 주식회사 엘지화학 Multinuclear half metallocene catalyst having sandwitch type metallocene derivatives as ligands for styrene polymerization and polymerization process using the metallocene catalyst
KR100771351B1 (en) * 2004-08-12 2007-10-29 주식회사 엘지화학 Novel Half Metallocene Catalysts and Method for Preparing Syndiotactic Polystyrenes
EP1777239A1 (en) * 2005-10-19 2007-04-25 LG Chem Ltd. Half-metallocene catalyst and process for preparing syndiotactic styrene polymer using the same

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