KR960701907A - METHOD FOR POLYMERISING OR COPOLYMERISING PROPYLENE IN LIQUID PROPYLENE, SOLID CATALYTIC COMPONENT, AND METHOD FOR MAKING SAME - Google Patents

METHOD FOR POLYMERISING OR COPOLYMERISING PROPYLENE IN LIQUID PROPYLENE, SOLID CATALYTIC COMPONENT, AND METHOD FOR MAKING SAME

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KR960701907A
KR960701907A KR1019950704519A KR19950704519A KR960701907A KR 960701907 A KR960701907 A KR 960701907A KR 1019950704519 A KR1019950704519 A KR 1019950704519A KR 19950704519 A KR19950704519 A KR 19950704519A KR 960701907 A KR960701907 A KR 960701907A
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hydrocarbon
range
carbon atoms
silicon
propylene
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KR1019950704519A
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Korean (ko)
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고메-쥬르노 꼬린느
브뤼쏭 쟝-미셸
스삐 로졔
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크리스띠앙 꼴롱비에
아쁘릴 에스.엔.쎄.
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Publication of KR960701907A publication Critical patent/KR960701907A/en

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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C08F4/602—Component covered by group C08F4/60 with an organo-aluminium 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
    • C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612—Pretreating with metals or metal-containing compounds
    • C08F4/614—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6143—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • 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
    • C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612—Pretreating with metals or metal-containing compounds
    • C08F4/616—Pretreating with metals or metal-containing compounds with silicon or compounds thereof

Abstract

본 발명은 공촉매의 존재 및 하기: a. 마그네슘, 할로겐 및 전이금속의 원자를 함유하는 고형 화합물, b. 유기 알루미늄 유도체, c. 식 R1R2Si(OR3)(OR4)의 디알콕시실란[식중, R3및 R4는 1∼12개의 탄소 원자, 바람직하게는 메틸 또는 에틸기를 함유하는 탄화수소기를 나타내고; 및 R1및 R2는 탄화수소기를 나타내며, R1및 R2중의 하나 이상이 3개 이상의 탄소원자를 함유한다.]와 접촉시켜 수득한 고형 촉매 성분의 존재하에서, 액체 프로필렌중 프로필렌의 중합화 또는 공중합화 방법에 관한 것이다.The present invention relates to the presence of a cocatalyst and to: a. Solid compounds containing atoms of magnesium, halogens and transition metals, b. Organoaluminum derivatives, c. Dialkoxysilanes of the formula R 1 R 2 Si (OR 3 ) (OR 4 ) [wherein R 3 and R 4 represent a hydrocarbon group containing 1 to 12 carbon atoms, preferably methyl or ethyl groups; And R 1 and R 2 represent a hydrocarbon group, at least one of R 1 and R 2 containing at least 3 carbon atoms. It is about how to get angry.

본 발명은 또한 올레핀의 중합화를 위한 신규한 고형 촉매 성분 및 그의 제조 방법에 관한 것이다.The present invention also relates to novel solid catalyst components for the polymerization of olefins and processes for their preparation.

Description

액체 프로필렌중 프로필렌의 중합화 또는 공중합화 방법, 고형 촉매성분 및 그의 제조 방법(METHOD FOR POLYMERISING OR COPOLYMERISING PROPYLENE INLIQUID PROPYLENE, SOLID CATALYTIC COMPONENT, AND METHOD FORMAKING SAME)METHOD FOR POLYMERISING OR COPOLYMERISING PROPYLENE INLIQUID PROPYLENE, SOLID CATALYTIC COMPONENT, AND METHOD FORMAKING SAME

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

Claims (19)

공촉매의 존재 및 하기: a. 마그네슘, 할로겐 및 전이금속의 원자를 함유하는 고형 화합물 (a), b. 유기알루미늄 유도체(b), c. 식 R1R2Si(OR3)(OR4)의 디알콕시실란(c)[식중, R3및 R4는, 동일하거나 또는 상이할 수 있고, 탄화수소기를 나타내고; 및 R1및 R2는, 동일하거나 또는 상이할 수 있고, 탄화수소기를 나타내며, R1은 포화되고 3개 이상의 탄소원자를 함유한다.]와 접촉시켜 수득한 고형 촉매 성분의 존재하에서, (a), (b) 및 (c)와의 접촉후에 예비 중합화를 수행하고, 고형 촉애 성분에 존재하는 전이금속 M에 대한 공촉매의 몰비가 100∼300의 범위인 것을 특징으로 하는, 액체 프로필렌중 프로필렌의 중합화 또는 액체 프로필렌중 4∼12개의 탄소원자를 함유하는 에틸렌 또는 알파-올레핀과 프로필렌의 공중합화 방법.The presence of a cocatalyst and: a. Solid compounds containing atoms of magnesium, halogens and transition metals (a), b. Organoaluminum derivatives (b), c. Dialkoxysilane (c) of formula R 1 R 2 Si (OR 3 ) (OR 4) [wherein R 3 and R 4 may be the same or different and represent a hydrocarbon group; And R 1 and R 2 , which may be the same or different, represent a hydrocarbon group, and R 1 is saturated and contains at least 3 carbon atoms. (A), prepolymerization is carried out after contact with (b) and (c), and the molar ratio of the cocatalyst to the transition metal M present in the solid catalyst component is in the range of 100 to 300; A process for copolymerizing propylene with ethylene or alpha-olefins containing 4 to 12 carbon atoms in propylene or liquid propylene. 제1항에 있어서, R1의 실리콘에 결합된 탄소원자가 2개의 탄소원자에 결합하는 것을 특징으로 하는 방법.The method of claim 1 wherein the carbon atom bonded to the silicon of R 1 is bonded to two carbon atoms. 제1항 또는 2항에 있어서, R2기가 포화되고 R2의 실리콘에 결합된 탄소원자가 2개의 탄소원자에 결합하는 것을 특징으로 하는 방법.The method of claim 1 or 2, wherein the R 2 group is saturated and a carbon atom bonded to the silicon of R 2 is bonded to two carbon atoms. 제1항 내지 3항 중의 어느 한 항에 있어서, 우선, (b) 및 (c)가 함께 접촉하도록 위치시킨 다음, (a)와 접촉하도록 위치시키는 것을 특징으로 하는 방법.4. A method according to any one of the preceding claims, wherein (b) and (c) are placed in contact with each other and then in contact with (a). 제1항 내지 4항 중의 어느 한 항에 있어서, (a),(b) 및 (c)가 탄화수소에 접촉하도록 위치시키는 것을 특징으로 하는 방법.The method according to any one of claims 1 to 4, wherein (a), (b) and (c) are placed in contact with the hydrocarbon. 제1항 내지 5항 중의 어느 한 항에 있어서, (b) 및 (c)를 우선 탄화수소중 용액과 혼합시킨 다음, 탄화수소중 (a)의 현탄액과 혼합시키는 것을 특징으로 하는 방법.The process according to any one of claims 1 to 5, wherein (b) and (c) are first mixed with a solution in a hydrocarbon and then with a suspension of (a) in a hydrocarbon. 제5항 또는 6항에 있어서, 탄화수소가 포화 지방족 또는 포화 지방족 고리 탄화수소인 것을 특징으로 하는 방법.7. Process according to claim 5 or 6, wherein the hydrocarbon is a saturated aliphatic or saturated aliphatic ring hydrocarbon. 제1항 내지 7항 중의 어느 한 항에 있어서, (a)의 전이금속에 대한 (b)의 알루미늄의 몰비가 0.5∼100의 범위이고, 바람직하게는 1∼50의 범위인 방법으로, (a), (b) 및 (c)를 접촉시키는 것을 특징으로 하는 방법.The method according to any one of claims 1 to 7, wherein the molar ratio of aluminum of (b) to the transition metal of (a) is in the range of 0.5 to 100, preferably in the range of 1 to 50, ), (b) and (c). 제1항 내지 8항 중의 어느 한 항에 있어서, (a)의 전이금속에 대한 (c)의 실리콘의 몰비가 0.5∼20의 범위이고, 바람직하게는 1∼10의 범위인 방법으로, (a), (b) 및 (c)를 접촉시키는 것을 특징으로 하는 방법.The method according to any one of claims 1 to 8, wherein the molar ratio of silicon of (c) to the transition metal of (a) is in the range of 0.5 to 20, preferably in the range of 1 to 10, (a ), (b) and (c). 제1항 내지 9항 중의 어느 한 항에 있어서, 고형 촉매 성분을 포화 지방족 또는 포화 지방족 고리 탄화수소로 세척시키고, 선택적으로 프로필렌의 중합화 또는 공중합화 전에 건조시키는 것을 특징으로 하는 방법.10. The process according to claim 1, wherein the solid catalyst component is washed with saturated aliphatic or saturated aliphatic ring hydrocarbons and optionally dried prior to polymerization or copolymerization of propylene. 제1항 내지 제10항 중의 어느 한 항에 있어서, 공촉매가 식 R1R2R3Al[식중, R1, R2및 R3각각이 동일하거나 또는 상이할 수 있으며, 수소 원자 또는 할로겐 원자중 하나이거나 또는 1∼20개의 탄소원자를 함유하는 알킬기를 나타내고, R1, R2및 R3중 하나 이상이 알킬기를 나타낸다]의 유기 알루미늄 유도체인 것을 특징으로하는 방법.The cocatalyst of claim 1, wherein the cocatalyst is of the formula R 1 R 2 R 3 Al [wherein each of R 1 , R 2 and R 3 may be the same or different, a hydrogen atom or a halogen; Or an alkyl group containing 1 to 20 carbon atoms, and at least one of R 1 , R 2, and R 3 represents an alkyl group. 우선, (b) 및 (c)가 함께 접촉하도록 위치시킨 다음, (a)와 접촉하도록 위치시키는 것을 특징으로 하는, a. 마그네슘, 할로겐 및 전이금속의 원자를 함유하는 고형 화합물 (a), b. 유기 알루미늄 유도체 (b), c. 식 R1R2Si(OR3)(OR4)의 디알콕시실란[식중, R3및 R4는, 동일하거나 또는 상이할 수 있고, 탄화수소기를 나타내고; 및 R1및 R2는, 동일하거나 또는 상이할 수 있고, 탄화수소기를 나타내며, R1은 포화되고 3개 이상의 탄소원자를 함유한다.]와 접촉시켜 수득하는, 마그네슘, 할로겐, 알루미늄, 전이금속 및 실리콘의 원자를 함유하는 고형 촉매 성분의 제조 방법.First, (b) and (c) are placed in contact with each other, and then in contact with (a), a. Solid compounds containing atoms of magnesium, halogens and transition metals (a), b. Organoaluminum derivatives (b), c. Dialkoxysilanes of the formula R 1 R 2 Si (OR 3 ) (OR 4 ) [wherein R 3 and R 4 may be the same or different and represent a hydrocarbon group; And R 1 and R 2 , which may be the same or different, represent a hydrocarbon group and R 1 is saturated and contains at least 3 carbon atoms.], Magnesium, halogen, aluminum, transition metal and silicon A method for producing a solid catalyst component containing an atom of. 제12항에 있어서, (b) 및 (c)를 우선 탄화수소중 용액과 혼합시킨 다음, 탄화수소중 (a)의 현탁액과 혼합시키는 것을 특징으로 하는 방법.13. Process according to claim 12, characterized in that (b) and (c) are first mixed with a solution in hydrocarbon and then with a suspension of (a) in hydrocarbon. 제13항에 있어서, 탄화수소가 포화 지방족 또는 포화 지방족 고리 탄화수소인 것을 특징으로 하는 방법.The method of claim 13 wherein the hydrocarbon is a saturated aliphatic or saturated aliphatic ring hydrocarbon. 제12항 내지 14항 중의 어느 한 항에 있어서, (a)의 전이금속에 대한 (b)의 알루미늄의 몰비가 0.5∼100의 범위이고, 바람직하게는 1∼50의 범위인 방법으로, (a), (b) 및 (c)를 접촉시키는 것을 특징으로 하는 방법.The method according to any one of claims 12 to 14, wherein the molar ratio of aluminum of (b) to the transition metal of (a) is in the range of 0.5 to 100, and preferably in the range of 1 to 50, (a ), (b) and (c). 제12항 내지 15항 중의 어느 한 항에 있어서, (a)의 전이금속에 대한 (c)의 실리콘의 몰비가 0.5∼20의 범위이고, 바람직하게는 1∼10의 범위인 방법으로, (a), (b) 및 (c)을 접촉시키는 것을 특징으로 하는 방법.The method according to any one of claims 12 to 15, wherein the molar ratio of the silicon of (c) to the transition metal of (a) is in the range of 0.5 to 20, preferably in the range of 1 to 10, ), (b) and (c). 제12항 내지 16항 중의 어느 한 항에 있어서, R1의 실리콘에 결합된 탄소원자가 2개의 탄소원자에 결합하는 것을 특징으로 하는 방법.The method according to any one of claims 12 to 16, wherein the carbon atom bonded to the silicon of R 1 is bonded to two carbon atoms. 제12항 내지 17항 중의 어느 한 항에 있어서, R2기가 포화되고 R2의 실리콘에 결합된 탄소원자가 2개의 탄소원자에 결합하는 것을 특징으로 하는 방법.18. The method according to any one of claims 12 to 17, wherein the R 2 group is saturated and the carbon atom bonded to the silicon of R 2 is bonded to two carbon atoms. 제12항 내지 18항 중의 어느 한 항의 방법에 의해 수득될 수 있는 고형 촉매 성분.Solid catalyst component obtainable by the method of any one of claims 12-18. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019950704519A 1994-02-18 1995-02-08 METHOD FOR POLYMERISING OR COPOLYMERISING PROPYLENE IN LIQUID PROPYLENE, SOLID CATALYTIC COMPONENT, AND METHOD FOR MAKING SAME KR960701907A (en)

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FR9401883 1994-02-18
FR9401883 1994-02-18
PCT/FR1995/000147 WO1995022568A1 (en) 1994-02-18 1995-02-08 Method for polymerising or copolymerising propylene in liquid propylene, solid catalytic component, and method for making same

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JPH04272907A (en) * 1991-02-27 1992-09-29 Mitsubishi Petrochem Co Ltd Production of olefin polymer
JP3355657B2 (en) * 1992-08-10 2002-12-09 東ソー株式会社 Method for producing polyolefin

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NO954122L (en) 1995-10-17
CN1123552A (en) 1996-05-29
NO954122D0 (en) 1995-10-17
EP0702701A1 (en) 1996-03-27
FI954937A0 (en) 1995-10-17
WO1995022568A1 (en) 1995-08-24
CA2160806A1 (en) 1995-08-24
FI954937A (en) 1995-10-17

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