KR960029350A - Metallocene supported catalyst and its manufacturing method - Google Patents

Metallocene supported catalyst and its manufacturing method Download PDF

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Publication number
KR960029350A
KR960029350A KR1019950000709A KR19950000709A KR960029350A KR 960029350 A KR960029350 A KR 960029350A KR 1019950000709 A KR1019950000709 A KR 1019950000709A KR 19950000709 A KR19950000709 A KR 19950000709A KR 960029350 A KR960029350 A KR 960029350A
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metallocene
carrier
metallocene catalyst
supported
promoter
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KR1019950000709A
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KR100361889B1 (en
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박태호
오재승
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성재갑
주식회사 Lg 화학
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    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F4/6592—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
    • C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Abstract

본 발명은 각종 올레핀 및 스티렌 모노머의 단일 중합 또는 공중합에 사용되는 메탈로센 담지촉매 및 그 제조방법에 관한 것으로, 하기 일반식(Ⅰ)로 표시되는 아민기를 포함하고 있는 실란화합물과 접촉되어 표면 변성이 일어난 담체에 전이금속이 리간드 결합한 메탈로센 촉매와 조촉매인 알킬알루미늄 또는 물과 알킬알루미늄의 축합생성물이 담지된 것을 특징으로 한다.The present invention relates to a metallocene supported catalyst used for the single polymerization or copolymerization of various olefins and styrene monomers and a method for preparing the same, and the surface-modified contact with a silane compound containing an amine group represented by the following general formula (I) The resulting carrier is characterized in that a transition metal is ligand-bonded with a metallocene catalyst and an alkylaluminum as a promoter or a condensation product of water and an alkylaluminum.

(Ⅰ) (Ⅰ)

Description

메탈로센 담지촉매 및 그 제조방법Metallocene supported catalyst and its manufacturing method

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

Claims (14)

하기 일반식(Ⅰ)로 표시되는 아민기를 포함하고 있는 실란화합물과 접촉되어 표면 변성이 일어난 담체에 전이금속이 리간드 결합한 메탈로센 촉매와 조촉매인 알킬알루미늄 또는 물과 알킬알루미늄의 축합생성물이 담지된 것을 특징으로 하는 메탈로센 담지촉매.The condensation product of alkyl aluminum or water and alkyl aluminum, which is a metallocene catalyst and a cocatalyst having a transition metal ligand, and a promoter, is brought into contact with a silane compound containing an amine group represented by formula (I) Metallocene supported catalyst, characterized in that. (Ⅰ) (Ⅰ) 상기의 (Ⅰ)식에서, A, B 및 C는 서로 동일하거나 상이한 그룹으로, A, B 및 C 중 최소 1종 이상은 R1HN-(R2)x-형태이고, 나머지는 H(R2)x-형태이다.In the above formula (I), A, B and C are the same or different groups from each other, at least one of A, B and C is in the form of R 1 HN- (R 2 ) x- , and the rest is H (R 2 ) x- form. 여기에서, R1=수소, 탄소수 1~8개의 알킬, 또는 탄소수 6~20개의 아릴 중에서 선택된 1종, R2=탄소수 20개 이하인 알킬, 또는 탄소수 6~20개의 아릴, 또는 N, O, S, P, Si원자를 1종 또는 2종 이상 포함하고 있는 탄소수 1~10개의 이성 알킬 및 탄소수 6~20개의 이성아릴 중에서 선택된 1종 또는 2종 이상 x=0~15이고 x개가 모두 동일하거나 상이, y=0~10이고 y개가 모두 동일하거나 상이, z=0~3이고 z개가 모두 동일하거나 상이, D=할로겐으로 (3-z)개가 모두 동일하거나 상이.Here, R 1 = hydrogen, alkyl having 1 to 8 carbon atoms, or one selected from aryl having 6 to 20 carbon atoms, R 2 = alkyl having 20 or less carbon atoms, or aryl having 6 to 20 carbon atoms, or N, O, S One or two or more selected from the group consisting of one or two or more P, Si atoms, or two or more heteroalkyls having 1 to 10 carbon atoms and six or twenty heteroisomers having x = 0 to 15, all of which are the same or different. , y = 0-10 and y are all the same or different, z = 0-3 and z are all the same or different, and D = halogen is the same or different. 제1항에 있어서, 알킬 알루미늄의 양은 담체 1g당 0.05~400mmol인 것을 특징으로 하는 메탈로센 담지촉매.The supported metallocene catalyst according to claim 1, wherein the amount of alkyl aluminum is 0.05 to 400 mmol per gram of carrier. 제1항에 있어서, 메탈로센 촉매의 전이금속과 알킬 알루미늄의 몰비는 1:10 내지 1:1000인 것을 특징으로 하는 메탈로센 담지촉매.The supported metallocene catalyst according to claim 1, wherein the molar ratio of the transition metal to the alkyl aluminum of the metallocene catalyst is 1:10 to 1: 1000. 제1항에 있어서, 메탈로센 촉매의 전이금속과 알킬 알루미늄의 총무게는 300% 이하인 것을 특징으로 하는 메탈로센 담지촉매.The supported metallocene catalyst according to claim 1, wherein the total weight of the transition metal of the metallocene catalyst and the alkyl aluminum is 300% or less. 제1항에 있어서, 담체는 실리타, 알루미나, 실리카-알루미나, 마그네시아,티타니아,지르코니아,활석, 지올라이트 중 선택된 1종 또는 2종 이상인 것을 특징으로 하는 메탈로센 담지촉매.The supported metallocene catalyst according to claim 1, wherein the carrier is one or two or more selected from silica, alumina, silica-alumina, magnesia, titania, zirconia, talc, and zeolite. 상기 일반식(Ⅰ)로 표시되는 아민기를 포함하고 있는 실란화합물을 담체와 직접 접촉시키거나 비활성 용매하에서 접촉시켜 담체의 표면을 변형한 후, 담체에 메탈로센 촉매와 조촉매를 담지시키는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.After modifying the surface of the carrier by directly contacting the silane compound containing the amine group represented by the general formula (I) or under an inert solvent, the carrier is supported with a metallocene catalyst and a promoter Method for producing a metallocene supported catalyst. 제6항에 있어서, 담체에 메탈로센 촉매와 조촉매를 담지시키는 방법은 담체에 조촉매를 우선 접촉시킨 후 메탈로센 촉매를 담지시키는 방법인 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method for preparing a metallocene supported catalyst according to claim 6, wherein the method for supporting the metallocene catalyst and the promoter on the carrier is a method of firstly contacting the promoter on the carrier and then supporting the metallocene catalyst. . 제6항에 있어서, 담체에 메탈로센 촉매와 조촉매를 담지시키는 방법은 담체에 메탈로센 촉매를 우선 담지시킨 후 조촉매를 접촉시키는 방법인 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method for preparing a metallocene supported catalyst according to claim 6, wherein the method of supporting the metallocene catalyst and the promoter on the carrier is a method of firstly supporting the metallocene catalyst on the carrier and then contacting the promoter. . 제6항에 있어서, 담체에 메탈로센 촉매와 조촉매를 담지시키는 방법은 메탈로센 촉매와 조촉매를 우선 접촉시켜 활성화시킨 후 또는 한꺼번에 담체와 접촉시켜 담지시키는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.7. The method of claim 6, wherein the method of supporting the metallocene catalyst and the promoter on the support is activated by first contacting the metallocene catalyst and the promoter or by contacting the carrier at a time to support the metallocene catalyst. Method for preparing a catalyst. 제6항에 있어서, 담체의 표면을 변형할 때 사용하는 실란화합물로는 3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 아미노페녹시트리메톡시실란, (아미노에틸아미노메틸) 페닐트리메톡시실란 중 선택된 1종을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The silane compound used in modifying the surface of the carrier is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminophenoxytrimethoxysilane, (aminoethylaminomethyl ) A method for producing a metallocene supported catalyst, characterized in that one selected from phenyltrimethoxysilane is used. 제6항에 있어서, 담체는 실리카, 알루미나, 실리카-알루미나, 마그네시아, 티타니아, 지르코니아, 활석, 지올라이트 중 선택된 1종 또는 2종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method of claim 6, wherein the carrier is one or more selected from silica, alumina, silica-alumina, magnesia, titania, zirconia, talc, and zeolite. 제6항에 있어서, 조촉매로는 트리메틸알루미늄, 트리에틸알루미늄, 트리프로필알루미늄, 트리이소프로필알루미늄, 트리부틸알루미늄, 트리이소부틸알루미늄, 디메틸클로로알루미늄, 디에틸클로로알루미늄 또는 물과 알킬알루미늄 화합물의 축합 생성물 중 선택된 1종 이상을 사용함을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method of claim 6, wherein the promoter is trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, dimethylchloroaluminum, diethylchloroaluminum or water and an alkylaluminum compound. A method for producing a metallocene supported catalyst, characterized in that at least one selected from condensation products is used. 제6항에 있어서, 담체는 하이드록시기가 유리된 것임을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method for preparing a metallocene supported catalyst according to claim 6, wherein the carrier is a free hydroxy group. 제6항 또는 제13항에 있어서, 담체는 진공 또는 비활성 기체의 존재하에서 100~1000℃의 온도에서 2~48 시간 유지된 것임을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method for producing a supported metallocene catalyst according to claim 6 or 13, wherein the carrier is maintained at a temperature of 100 to 1000 ° C. for 2 to 48 hours in the presence of a vacuum or an inert gas. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019950000709A 1995-01-18 1995-01-18 Supported metallocene catalyst and method for producing the same KR100361889B1 (en)

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