KR960034231A - 다리걸친 형의 비스-플루오레닐 메탈로센, 그것의 제조 방법 및 올레핀 중합용 촉매로 사용되는 그것의 용도 - Google Patents

다리걸친 형의 비스-플루오레닐 메탈로센, 그것의 제조 방법 및 올레핀 중합용 촉매로 사용되는 그것의 용도 Download PDF

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KR960034231A
KR960034231A KR1019960005498A KR19960005498A KR960034231A KR 960034231 A KR960034231 A KR 960034231A KR 1019960005498 A KR1019960005498 A KR 1019960005498A KR 19960005498 A KR19960005498 A KR 19960005498A KR 960034231 A KR960034231 A KR 960034231A
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레스코니 루이지
엘.존스 로버트
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제프리 에이치.갠디
몬텔 테크놀로지 캄파니 비브이
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    • 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
    • C08F4/65927—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 bridged
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
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    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 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
    • C08F4/61927—Component covered by group C08F4/60 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 bridged
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

적어도 총 4개의 탄소원자들이 포함된 2개의 치환기가 있는 실리콘원자 또는 게르마늄 원자 하나에 의하여 다리 걸쳐진 2개의 플루오레닐 리간드를 가지는 메타로센 화합물은 올레핀 중합용의 촉매 성분으로서 유용하다. 특히, 알려져 있는 촉매들에 대하여는 개선된 수율로 고분자량의 동일배열 중합체를 제조하는 것이 가능하다.

Description

다리걸친 형의 비스-플루오레닐 메탈로센, 그것의 제조 방법 및 올레핀 중합용 촉매로 사용되는 그것의 용도
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (13)

  1. 다음의 식(I)를 갖는 메탈로센 화합물:
    [여기서 R1은 각각, 같거나 다른 것으로서, 수소원자, C1-C20알킬 라디칼, C3-C20시클로알킬 라디칼, C2-C20알케닐 라디칼, C6-C20알릴 라디칼, C7-C20알킬아릴 라디칼, 또는 C7-C20아릴알킬 라디칼이며, 경우에 따라서는 인접한 2개의 R1치환기들이 탄소원자 갯수 5 내지 8의 고리를 형성할 수가 있고, 더욱이 그 R1치환기들은 Si원자 또는 Ge원자를 함유할 수가 있으며;R2다리 원자단(기)은〉SiR3 2기 또는 〉GeR3 2기(여기서 R3는 각각, 같거나 다른 것으로서, 경우에 따라서는 헤테로 원자들을 함유하는, C1-C20알킬 라디칼, C3-C20시크로알킬 라디칼, C2-C20알케닐 라디칼, C6-C20아릴 라디칼, C7-C20알킬아릴 라디칼 또는 C7-C20아릴알칼 라디칼 이며, 또는 그 2개의 R3치환기들이 연결되어 원자 갯수 8이하의 고리를 형성할 수가 있고, 이때 적어도 총4개의 탄소 원자들은 그 2개의 R3치환기들이 연결되어 원자 갯수 8이하의 고리를 형성할 수가 있고, 이때 적어도 총4개의 탄소 원자들은 그 2개의 R3치환기들에 포함됨)에서 선택된 것이며; M은 원소의 주기율표(IUPAC판)의 제3족, 제4족이나 제5족 또는 란탄족이나 악티늄족에 속하는 전이금속의 원자이고; X는 각각, 같거나 다른 것으로서, 할로겐 원자, -OH기,-SH기,R4기,-OR4기,-SR4기,-NR4 2기 또는 PR4 2기 (여기서 R4는 R1가 같이 정의됨)이다].
  2. 제1항에 있어서, 치환기들 R1은 수소 원자인 것을 특징으로 하는 메탈로센 화합물.
  3. 제1항 또는 제2항에 있어서, R2다리 원자단을 비스(n-부틸)실란디일기인 것을 특징으로 하는 메탈로센 화합물.
  4. 제1항 또는 제2항에 있어서, 치환기들 R2는 염소원자 또는 메틸기인 것을특징으로 하는 메탈로센 화합물.
  5. 제1항에서 청구된 바의 식(I)을 갖는 메탈로센 화합물의 제조 방법으로서, 다음의 단계들을 포함하는 것을 특징으로 하는 방법: (a) 식 (Ⅱ):
    (여기서 치환기들 R1은, 서로 같거나 다른 것을서, 제1항에서 정의된 바와 같음)의 화합물을 음이온형의 식 (Ⅲ):
    을 형성할 수 있는 화합물과 반응시키고, 그다음에는 식 R2Y2(여기서 R2는 제1항에서 정의된 바과 같고, 치환기들 Y는, 서로 같거나 다른 것으로서, 할로겐 원자들임)의 화합물과 반응시켜, 식(Ⅳ):
    의 화합물을 얻는 단계 (b) 이어서, 단계(a)에서 얻어진 식(Ⅳ)의 화합물을 2음이온형의 식(Ⅴ):
    를 형성할 수 있는 화합물과 반응시키고, 그 다음에 식 MX`4(여기서 M은 제1항에서 3정의된 바와 같으며 치환기들 X`는 할로겐 원자들임)의 화합물과 반응시켜, 식(Ⅵ):
    의 화합물을 얻는 단계 그리고 마지막으로, (c) 제조하고자 하는 식 (I)의 메탈로센에서 적어도 하나의 X가 할로겐이 아닌 다른 것인 경우에는, 식(Ⅳ)의 화합물에서 적어도 하나의 치환기 X`를 할로겐이 아닌 다른 적어도 하나의 X로 치환시키는 단계.
  6. 제5항에 있어서, 식 MX`4의 화합물은 지르코늄 테트라클로리드인 것을 특징으로 하는 방법.
  7. 다음의 식(Ⅳ)을 갖는 화합물:
    (여기서 치환기들 R1그리고 R2다리 원자단은 제1항에서 정의된 바와 같다.)
  8. 제7항에 있어서, 화합물은 디에틸비스(플루오레닐)실란, 디(n-프로필)비스(플루오레닐)실란, 디(n-부틸)비스(플루오레닐)실란, 메틸(n-헥실)비스(플루오레닐)실란, 메틸(n-옥틸)비스(플루오레닐)실란, 메틸(2-비시크로헵틸)비스(플루오레닐)실란, 메틸(3,3,3-트리플루오로프로필)비스(플루오레닐)실란, 디에틸비스(플루오레닐)게르마늄, 디에틸비스(1-메틸플루오레닐)실란에서 선택되는 것을 특징으로 하는 화합물.
  9. 다음의 화합물간의 반응의 생서물을 함유하는 것을 특징으로 하는 올레핀 중합용 촉매: (A) 제1항에서 청구된 바의 식(I)의 메탈로센 화합물 [경우에 따라서는 식 AIR5 3또는 AI2R5 6(여기서 치환기들 R5는, 서로 같거나 다른 것으로서, R1과 같이 정의되는 것이나 또는 할로겐 원자들임)의 알루미늄 유기-금속 화합물과의 반응 생성물의 형태로서]과 (B) 알루목산[경우에 따라서는 식 AIR5 3또는 AI2R5 6(여기서 치환기들 R5는, 서로 같거나 다른 것으로서, 위에서 정의된 바와 같음)의 알루미늄 유기-금속 화합물과 혼합된 것이거나 또는 메탈로센 알킬 양이온을 줄 수 있는 하나 이상의 화합물들과 혼합된 것].
  10. 제9항에 있어서, 디(n-부틸)실란디일비스(플루오레닐)지르코늄디클로리다와 메틸알루목산간의 반응의 생성물을 함유하는 것을 특징으로 하는 촉매.
  11. 제9항 또는 제10항에 청구된 바의 촉매의 존재하에 올레핀 단량체의 중합반응을 포함하는 것을 특징으로 하는 올레핀 중합 방법.
  12. 제11항에 있어서, 올레핀 단량체는 프로필렌인 것을 특징으로 하는 방법.
  13. 제3항에 있어서, 치환기들 R2는 염소원자 또는 메틸기인 것을 특징으로 하는 메탈로센 화합물.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960005498A 1995-03-03 1996-03-02 다리걸친 형의 비스-플루오레닐 메탈로센, 그것의 제조 방법 및 올레핀 중합용 촉매로 사용되는 그것의 용도 KR960034231A (ko)

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IT95MI000410A IT1275856B1 (it) 1995-03-03 1995-03-03 Composti metallocenici bis-fluorenilici, procedimento per la loro preparazione e loro utilizzo in catalizzatori per la polimerizzazione
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US8692009B2 (en) 2009-07-31 2014-04-08 Lg Chem, Ltd. Metallocene compound, catalyst composition comprising the same, and an olefinic polymer produced using the same

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IT1275856B1 (it) * 1995-03-03 1997-10-24 Spherilene Srl Composti metallocenici bis-fluorenilici, procedimento per la loro preparazione e loro utilizzo in catalizzatori per la polimerizzazione
US6291695B1 (en) 1996-02-20 2001-09-18 Northwestern University Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon
US6274752B1 (en) 1996-02-20 2001-08-14 Northwestern University Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations
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ES2181816T3 (es) 2003-03-01
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CA2170928A1 (en) 1996-09-04
ITMI950410A0 (it) 1995-03-03
EP0729968B1 (en) 2002-09-25
IT1275856B1 (it) 1997-10-24
US6180733B1 (en) 2001-01-30
DE69623833T2 (de) 2003-07-31
JPH08259583A (ja) 1996-10-08
DE69623833D1 (de) 2002-10-31
US6054404A (en) 2000-04-25
ITMI950410A1 (it) 1996-09-03
CN1147522A (zh) 1997-04-16
US6365764B1 (en) 2002-04-02

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