KR940005682A - 올레핀 중합체의 제조방법 - Google Patents

올레핀 중합체의 제조방법 Download PDF

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KR940005682A
KR940005682A KR1019930008716A KR930008716A KR940005682A KR 940005682 A KR940005682 A KR 940005682A KR 1019930008716 A KR1019930008716 A KR 1019930008716A KR 930008716 A KR930008716 A KR 930008716A KR 940005682 A KR940005682 A KR 940005682A
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오또루 야마다
마고또 소네
사이끼 하세가와
아끼히로 야노
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다시로 노조무
도소 가부시기가이샤
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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
    • 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
    • C08F4/65908—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
    • C08F4/6592—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

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

본 발명은 하기 일반식(1)로 표시되는 메탈로센 화합물(A)와 :
[식중, Cp1및 Cp2는 각기 독립적으로 치환 또는 비치환된 시클로펜타디에닐이고, R1은 탄소수 1 내지 20의 알킬렌기, 디알킬실릴렌기, 디알킬게르마닐렌기, 알킬포스피딜기 또는 알킬이미노이고, R1은 Cp1및 Cp2와 가교결합이며; m은 0 또는 1이고; M은 티탄, 지르코늄 또는 하프늄이고; X는 불소, 염소, 브롬, 요드, 알킬기 또는 아릴기이다.]
하기 일반식(2)로 표시되는 유기알루미늄 화합물(B)와 ;
Al(R2)3……(2)
[식중, R2기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이고; R2기중 적어도 하나는 알킬기이다.]
하기 일반식(3)으로 표시되는 이온화합물(C) :
[C] [A] ……(3)
[식 중, [C]는 양이온 이고, [A]는 음이온이다.]을 촉매성분으로 포함하여 이루어지는 올레핀 중합용 촉매계로서, 상기 촉매계가 하기 일반식(4)로 표시되는 붕소화합물(D)을 메탈로센 화합물(A)1몰당 0.01몰 내지 0.8몰의 양으로 더욱 함유하는 올레핀 중합용 촉매계 및
B(R3)3
[식중, R3기는 각기 독립적이고 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이다.]하기 일반식(5)로 표시되는 이온 메탈로센 화합물(a)와 :
(식중, Cp1, Cp2, R1, m 및 M은 상기 일반식(1)에서 정의된 바와 같고, R4는 알킬기 또는 아릴기이고, [A]는 음이온이다.] 하기 일반식(2)로 표시되는 유기알미늄 화합물(b)
Al(R2)3……(2)
[식 중, R2는 상기에서 정의된 바와 같고, R2기중 적어도 하는 알킬기이 다.]을 촉매성분으로 포함하여 이루어지는 올레핀 중합용 촉매로서, 상기 촉매가 하기 일반식(4)로 표시되는 붕소 화합물을 상기 이온 메탈로센 화합물 (a)1몰당 0.01몰 내지 0.8몰의 양으로 더욱 함유하는, 올레핀 중합용 촉매를 제공한다.
B(R2)3……(4)
[식중, R3기는 상기에서 정의된 바와 같다.]
본 발명은 또한 촉매를 사용하여 높은 촉매 활성을 지니면서 높은 효율로 에틸렌 또는 α-올레핀을 중합하는 방법도 제공한다.

Description

올레핀 중합체의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (10)

  1. 본 발명은 하기 일반식(1)로 표시되는 메탈로센 화합물(A)와 :
    [식중, Cp1및 Cp2는 각기 독립적으로 치환 또는 비치환된 시클로펜타디에닐이고, R1은 탄소수 1 내지 20의 알킬렌기, 디알킬실릴렌기, 디알킬게르마닐렌기, 알킬포스피딜기 또는 알킬이미노이고, R1은 Cp1및 Cp2와 가교결합이며; m은 0 또는 1이고; M은 티탄, 지르코늄 또는 하프늄이고; X는 불소, 염소, 브롬, 요드, 알킬기 또는 아릴기이다.]
    하기 일반식(2)로 표시되는 유기알루미늄 화합물(B)와 ;
    Al(R2)3……(2)
    [식중, R2기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이고; R2기중 적어도 하나는 알킬기이다.]
    하기 일반식(3)으로 표시되는 이온화합물(C) :
    [C] [A] ……(3)
    [식 중, [C]는 양이온 이고, [A]는 음이온이다.]을 촉매성분으로 포함하여 이루어지는 올레핀 중합용 촉매계로서, 상기 촉매계가 하기 일반식(4)로 표시되는 붕소화합물(D)을 메탈로센 화합물(A)1몰당 0.01몰 내지 0.8몰의 양으로 더욱 함유하는 올레핀 중합용 제조 방법.
    B(R3)3
    [식중, R3기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이다.]
  2. 제1항에 있어서, 상기 촉매계가 붕소화합물(D)을 메탈로센 화합물(A)1몰당 0.05몰 내지 0.5몰의 양으로 함유하는 것을 특징으로 하는 올레핀 중합체의 제조방법.
  3. 제1항 또는 제2항에 있어서, 상기 메탈로센 화합물(A) 및 유기알루미늄 화합물(B)을 올레핀과 혼합한 후, 이 혼합물을 붕소화합물(D)을 함유하는 이온 화합물(C)과 접촉반응시키는 것을 특징으로 하는 올레핀 중합체의 제조방법.
  4. 하기 일반식(5)로 표시되는 이온 메탈로센 화합물(a)와 :
    [식중, Cp1및 Cp2는 각기 독립적으로 치환 또는 비치환된 시클로펜타디에닐이고, R1은 탄소수 1 내지 20의 알킬렌기, 디알킬실릴렌기, 디알킬게르마닐렌기, 알킬포스피딜기 또는 알킬이미노이고, R1은 Cp1및 Cp2와 가교결합이며; m은 0 또는 1이고; M은 티탄, 지르코늄 또는 하프늄이고; A는 음이온이다.
    하기 일반식(2)로 표시되는 유기알루미늄 화합물(b)와 ;
    Al(R2)3……(2)
    [식중, R2기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이고; R2기중 적어도 하나는 알킬기이다.]을 촉매성분으로 포함하여 이루어지는 중합촉매계를 사용하여 올레핀 중합체를 제조하는 방법으로서, 상기 촉매계가 하기 일반식(4)로 표시되는 붕소화합물을 상기 이온 메탈로센 화합물(a)1몰당 0.01몰 내지 0.8몰의 양으로 더욱 함유하는 것을 특징으로 하는 올레핀 중합체의 제조방법.
    B(R3)3 ……(4)
    [식중, R3기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이다.]
  5. 제4항에 있어서, 상기 촉매계가 붕소화합물을 이온 메탈로센 화합물(A)1몰당 0.05몰 내지 0.5몰의 양으로 함유하는 것을 특징으로 하는 올레핀 중합체의 제조방법.
  6. 제4항 또는 제5항에 있어서, 상기 이온 메탈로센 화합물(a)을 붕소 화합물에 첨가한후, 이 혼합물을 유기알루미늄 화합물 및 올레핀과 접촉반응시키는 것을 특징으로 하는 올레핀 중합체의 제조방법.
  7. 제1항 내지 제6항중의 어느 한 항에 있어서, 상기 붕소화합물이 트리플루오로보란, 트리크로로보란, 트리브로모보란, 트리페닐보란 및 트리스(펜타플루오로페닐)보란 중에서 선택되는 것을 특징으로 하는 올레핀 중합체의 제조방법.
  8. 제1항 내지 제7항중의 어느 한 항에 있어서, 상기 올레핀이 에틸렌, 프로필렌, 1-부텐, 4-메틸-1-펜텐, 1-헥센 및 1-옥텐 중에서 선택되는 것을 특징으로 하는 올레핀 중합체의 제조방법.
  9. 하기 일반식(1)로 표시되는 메탈로센 화합물(A)와 :
    [식중, Cp1및 Cp2는 각기 독립적으로 치환 또는 비치환된 시클로펜타디에닐이고, R1은 탄소수 1 내지 20의 알킬렌기, 디알킬실릴렌기, 디알킬게르마닐렌기, 알킬포스피딜기 또는 알킬이미노이고, R1은 Cp1및 Cp2와 가교결합이며; m은 0 또는 1이고; M은 티탄, 지르코늄 또는 하프늄이고; X는 불소, 염소, 브롬, 요드, 알킬기 또는 아릴기이다.]
    하기 일반식(2)로 표시되는 유기알루미늄 화합물(B)와 ;
    Al(R2)3……(2)
    [식중, R2기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이고; R2기중 적어도 하나는 알킬기이다.]
    하기 일반식(3)으로 표시되는 이온화합물(C) :
    [C] [A] ……(3)
    [식 중, [C]는 양이온 이고, [A]는 음이온이다.]을 촉매성분으로 포함하여 이루어지는 올레핀 중합용 촉매계로서, 상기 촉매계가 하기 일반식(4)로 표시되는 붕소화합물(D)을 메탈로센 화합물(A)1몰당 0.01몰 내지 0.8몰의 양으로 더욱 함유하는 올레핀 중합용 촉매.
    B(R3)3 ……(4)
    [식중, R3기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이다.]
  10. 하기 일반식(5)로 표시되는 이온 메탈로센 화합물(a)와 :
    [식중, Cp1및 Cp2는 각기 독립적으로 치환 또는 비치환된 시클로펜타디에닐이고, R1은 탄소수 1 내지 20의 알킬렌기, 디알킬실릴렌기, 디알킬게르마닐렌기, 알킬포스피딜기 또는 알킬이미노이고, R1은 Cp1및 Cp2와 가교결합이며; m은 0 또는 1이고; R4는 알킬기 또는 아릴기이고, M은 티탄, 지르코늄 또는 하프늄이고; [A]는 음이온이다.
    하기 일반식(2)로 표시되는 유기알루미늄 화합물(b)와 ;
    Al(R2)3……(2)
    [식중, R2기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이고; R2기중 적어도 하나는 알킬기이다.]을 촉매성분으로 포함하여 이루어지는 올레핀 중합용 촉매로서 상기 촉매계가 하기 일반식(4)로 표시되는 붕소화합물을 상기 이온 메탈로센 화합물(a)1몰당 0.01몰 내지 0.8몰의 양으로 더욱 함유하는 것을 특징으로 하는 올레핀 중합체의 제조방법.
    B(R3)3
    [식중, R3기는 각기 독립적으로 할로겐, 수소, 알킬기, 알콕시기 또는 아릴기이다.]
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019930008716A 1992-05-22 1993-05-21 올레핀 중합체의 제조방법 KR100270838B1 (ko)

Applications Claiming Priority (4)

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JP92-154094 1992-05-22
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