KR960029351A - Metallocene supported catalyst and preparation method thereof and preparation method of polymer having double molecular weight distribution using same - Google Patents

Metallocene supported catalyst and preparation method thereof and preparation method of polymer having double molecular weight distribution using same Download PDF

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KR960029351A
KR960029351A KR1019950000710A KR19950000710A KR960029351A KR 960029351 A KR960029351 A KR 960029351A KR 1019950000710 A KR1019950000710 A KR 1019950000710A KR 19950000710 A KR19950000710 A KR 19950000710A KR 960029351 A KR960029351 A KR 960029351A
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carrier
supported
catalyst
metallocene
same
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KR100361890B1 (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
    • 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
    • C08F2500/05—Bimodal or multimodal molecular weight distribution

Abstract

본 발명은 각종 올레핀 및 스티렌계 단량체의 단일중합 또는 공중합에 사용되는 담지 촉매 및 그 제조방법과 이를 이용한 고분자량 성분이 포함된 이중 분자량 분포를 갖는 중합체를 제조하는 방법에 관한 것으로, 본 발명의 담체는 담체의 일부분에 하기 일반식(Ⅰ)로 표시되는 아민기 함유 실란 화합물과 접촉되어 표면 변성이 일어난 담체 또는 변성이 일어난 담체와 변성이 일어나지 아니한 담체의 혼합물에 메탈로센 촉매와 조촉매인 알킬알루미늄 또는 물과 알킬알루미늄의 축합생성물이 담지된 것을 특징으로 한다.The present invention relates to a supported catalyst used for the homopolymerization or copolymerization of various olefins and styrene-based monomers, a method for producing the same, and a method for producing a polymer having a double molecular weight distribution containing a high molecular weight component using the same. Is a metallocene catalyst and a co-catalyst in a mixture of a carrier having surface modification or a carrier having no modification with a amine group-containing silane compound represented by the following general formula (I) on a part of the carrier: It is characterized in that the condensation product of aluminum or water and alkyl aluminum is supported.

(Ⅰ) (Ⅰ)

Description

메탈로센 담지촉매 및 그 제조방법 그리고 이를 이용한 이중 분자량 분포를 갖는 중합체의 제조방법Metallocene supported catalyst and preparation method thereof and preparation method of polymer having double molecular weight distribution using the same

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

Claims (15)

담체의 일부분에 하기 일반식(Ⅰ)로 표시되는 아민기 함유 실란 화합물과 접촉되어 표면 변성이 일어난 담체에 전이금속이 리간드 결합한 메탈로센 촉매와 조촉매인 알킬알루미늄 또는 물과 알킬알루미늄의 축합생성물이 담지된 것을 특징으로 하는 메탈로센 담지촉매.A condensation product of alkylaluminum, which is a metallocene catalyst and a cocatalyst of a transition metal to a carrier having surface modification, in contact with an amine group-containing silane compound represented by the general formula (I) The supported metallocene catalyst, characterized in that supported. (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- type. 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. 상기 일반식(Ⅰ)로 표시되는 아민기를 함유 실란 화합물과 접촉되어 표면 변성이 일어난 담체와 표면 변성이 일어나지 아니한 담체의 혼합물에 전이금속이 리간드 결합된 메탈로센 촉매와 조촉매인 알킬알루미늄 또는 물과 알킬알루미늄 축합생성물이 담지된 것을 특징으로 하는 메탈로센 담지 촉매.Alkyl aluminum or water, which is a covalent catalyst and a metallocene catalyst having a transition metal ligand bonded to a mixture of a carrier in which surface modification is made by contact with a silane compound containing an amine group represented by the general formula (I) and a carrier in which surface modification has not occurred And an alkyl aluminum condensation product supported thereon. 제1항 또는 제2항에 있어서, 메탈로센 촉매는 티타늄, 지로코늄, 하프늄 등의 전이금속에 사이클로펜타디에닐, 치환기가 있는 사이클로펜타디에닐, 변형 사이클로펜타디에닐, 인데틸, 치환기가 있는 인데닐, 플로레닐, 치환기가 있는 플로레닐 중 선택된 1종이 하기 방법 중 하나의 방법으로 결합되어 있는 것을 특징으로 하는 메탈로센 담지 촉매, (1) 1종 이상의 리간드가 전이금속에 π-결합, (2) 동일하거나 서로 다른 두 종류의 리간드가 하이드로카본, 실란, 황, 아민, 인 등의 화합물에 의하여 연결되어 있는 2 결합 리간드 화합물이 전이금속에 π-결합, (3) 1종의 리간드에 실란, 황, 아민, 인 등이 치환되어 있는 2 결합 리간드 화합물이 전이금속에 π-결합과 σ-결합.The metallocene catalyst of claim 1 or 2, wherein the metallocene catalyst has a cyclopentadienyl, a cyclopentadienyl having a substituent, a modified cyclopentadienyl, an intyl, a substituent on a transition metal such as titanium, zirconium, hafnium, or the like. Metallocene supported catalyst, characterized in that one selected from indenyl, florenyl, and florenyl having a substituent is bonded by one of the following methods, (1) at least one ligand is? -Bonded to the transition metal. (2) a bivalent ligand compound in which two or more of the same or different ligands are linked by a compound such as hydrocarbon, silane, sulfur, amine, phosphorus, π-bond to the transition metal, (3) one ligand The two-bond ligand compound in which silane, sulfur, amine, phosphorus and the like are substituted is a? -Bond and a? -Bond to the transition metal. 제3항에 있어서, 메탈로센 촉매는 동일하거나 상이한 2종이상의 할라이드, 알콕시, 알킬 중 선택된 1종이 전이금속에 치환되어 있는 것을 특징으로 하는 메탈로센 담지 촉매.The supported metallocene catalyst according to claim 3, wherein the metallocene catalyst is selected from the same or different two or more kinds of halides, alkoxy, and alkyls substituted with transition metals. 제1항 또는 제2항에 있어서, 전이금속과 알루미늄의 몰비는 1:10 내지 1:1000이며, 전이금속과 알루미늄의 총 무게는 담체의 30% 이하인 것을 특징으로 하는 메탈로센 담지 촉매.The supported metallocene catalyst according to claim 1 or 2, wherein the molar ratio of the transition metal to aluminum is 1:10 to 1: 1000, and the total weight of the transition metal and aluminum is 30% or less of the carrier. 제1항 또는 제2항에 있어서, 담체는 입자의 표면 및 내부가 다공성인 유기물, 무기물, 비활성 고체 중 선택된 1종 또는 2종 이상인 것을 특징으로 하는 메칼로센 담지 촉매.3. The mecarlocene supported catalyst according to claim 1 or 2, wherein the carrier is one or two or more selected from organic, inorganic and inert solids having a porous surface and inside. 제1항에 있어서, 담체 표면의 반응기가 아민기를 포함하는 실란화합물로 5~90% 변형된 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The method for preparing a metallocene supported catalyst according to claim 1, wherein the reactor on the carrier surface is 5 to 90% modified with a silane compound containing an amine group. 제1항 또는 제2항에 기재된 담체 또는 담체혼합물에 조촉매를 우선 접촉시킨 후 메탈로센 촉매를 담지시킴을 특징으로 하는 메탈로센 담지촉매의 제조방법.A method for producing a supported metallocene catalyst, characterized in that the cocatalyst is first contacted with the carrier or the carrier mixture according to any one of claims 1 to 5, and then the metallocene catalyst is supported. 제1항 또는 제2항에 기재된 담체 또는 담체혼합물에 메탈로센 촉매를 우선 담지시킨 후 조촉매를 접촉시킴을 특징으로 하는 메탈로센 담지 촉매의 제조방법.A method for producing a metallocene-supported catalyst characterized by first supporting a metallocene catalyst on a carrier or a carrier mixture according to any one of claims 1 to 7, followed by contacting a promoter. 메탈로센 촉매와 조촉매를 우선 접촉시켜 활성화시킨 후 또는 동시에 제1항 또는 제2항에 기재된 담체 또는 담체혼합물과 접촉시켜 담지시킴을 특징으로 하는 메탈로센 담지 촉매의 제조방법.A method for preparing a metallocene supported catalyst, which is activated by first contacting a metallocene catalyst with a cocatalyst, or at the same time by contacting with a carrier or a carrier mixture according to claim 1 or 2. 제8항 내지 제10항 중의 어느 한 항에 있어서, 담체의 표면을 변형할 때 사용하는 실란 화합물로는 3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 아미노 페녹시 트리메톡시 실란, (아미노에틸아미노메틸) 페닐 트리메톡시 실란 중 선택된 1종을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The silane compound according to any one of claims 8 to 10, wherein the silane compound used when modifying the surface of the carrier is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, amino phenoxy trimeth. A method for producing a metallocene supported catalyst, characterized by using one selected from oxysilane and (aminoethylaminomethyl) phenyl trimethoxy silane. 제8항 내지 제10항 중의 어느 한 항에 있어서, 담체로 폴리올레핀, 또는 반응 성기를 포함한 폴리올레핀 공중합체를 사용하는 것을 특징으로 하는 메탈로센 담지 촉매의 제조방법.The method for producing a metallocene supported catalyst according to any one of claims 8 to 10, wherein a polyolefin or a polyolefin copolymer including a reactive group is used as a carrier. 제8항 내지 제10항 중의 어느 한 항에 있어서, 조촉매로 트리메틸알루미늄, 트리에틸알루미늄, 트리프로필알루미늄, 트리이소프로필알루미늄, 트리부틸알루미늄, 트리이소부틸알루미늄, 디메틸클로로알루미늄, 디에틸클로로알루미늄 또는 물과 알킬알루미늄 화합물의 축합 생성물 중 선택된 1종 또는 2종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.The trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, dimethylchloroaluminum, diethylchloroaluminum according to any one of claims 8 to 10 as a promoter. Or a one or two or more selected from condensation products of water and alkylaluminum compounds. 제1항 또는 제2항의 담지 촉매를 사용하여 고분자량과 저분자량을 동시에 함유하는 중합체를 제조함을 특징으로 하는 이중 분자량 분포를 갖는 중합체의 제조방법.A method for producing a polymer having a double molecular weight distribution, comprising producing a polymer containing both a high molecular weight and a low molecular weight at the same time using the supported catalyst of claim 1. 상기 일반식(Ⅰ)로 표시되는 아민기 함유 실란 화합물과 접촉되어 표면 변성이 일어난 담체에 메탈로센 촉매와 조촉매가 담지된 담지촉매와, 변형하지 않은 담체에 메탈로센 촉매와 조촉매가 담지된 담지촉매를 중합시 혼합하여 중합촉매로 사용함을 특징으로 하는 이중 분자량 분포를 갖는 중합체의 제조방법.The supported catalyst in which the metallocene catalyst and the promoter are supported on a carrier in which surface modification occurs by contact with the amine group-containing silane compound represented by the general formula (I), and the metallocene catalyst and the promoter in the unmodified carrier A method for producing a polymer having a double molecular weight distribution, characterized in that the supported supported catalyst is mixed during polymerization and used as a polymerization catalyst. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
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