KR960014164A - 올레핀 중합용 촉매 및 올레핀 중합체의 제조방법 - Google Patents

올레핀 중합용 촉매 및 올레핀 중합체의 제조방법 Download PDF

Info

Publication number
KR960014164A
KR960014164A KR1019950036953A KR19950036953A KR960014164A KR 960014164 A KR960014164 A KR 960014164A KR 1019950036953 A KR1019950036953 A KR 1019950036953A KR 19950036953 A KR19950036953 A KR 19950036953A KR 960014164 A KR960014164 A KR 960014164A
Authority
KR
South Korea
Prior art keywords
compound
metallocene compound
catalyst
group
metallocene
Prior art date
Application number
KR1019950036953A
Other languages
English (en)
Other versions
KR100445364B1 (ko
Inventor
마고또 소네
사이끼 하세가와
사또루 야마다
아끼히로 야노
Original Assignee
다시로 마도까
도소 가부시키가이샤
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 다시로 마도까, 도소 가부시키가이샤 filed Critical 다시로 마도까
Publication of KR960014164A publication Critical patent/KR960014164A/ko
Application granted granted Critical
Publication of KR100445364B1 publication Critical patent/KR100445364B1/ko

Links

Classifications

    • 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
    • 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
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F4/619—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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

본 발명은 특정 치환된 플루오레닐기를 갖는 메탈로센 화합물과, 상기 메탈로센 화합물과 반응하여 양이온성 메탈로센 화합물을 형성할 수 있는 화합물을 포함하여 이루어지는 올레핀 중합용 촉매를 제공한다. 본 촉매를 사용하여 120℃ 이상의 중합온도에서 조성분포와 분자량 분포가 좁은 고분자량 올레핀 중합체를 얻을 수 있다.

Description

올레핀 중합용 촉매 및 올레핀 중합체의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (8)

  1. (a) 하기 일반식 (1)로 표시되는 치환된 플루오레닐 기를 갖는 메탈로센 화합물과, (b) 상기 메탈로센 화합물과 반응하여 양이온성 메탈로센 화합물을 형성하는 화합물로 이루어지는 것을 특징으로 하는 올레핀 중합용 촉매 :
    R1(C5H4)(C4H4－mR2mC5C4H4－nR3n)M1R42(1)
    (상기 식에서, R1은 일반식(1) 화합물의 입체 강성을 향상시키기 위해 C5H4기와 C4H4－mR2mC5C4H4－nR3n기 사이에 브리지를 형성하는 아릴기－함유 탄화수소, 실란디일, 또는 게르만디일기이고; C5H4는 시클로펜타디에닐기이고; C4H4－mR2mC5C4H4－nR3n은 치환된 플루오레닐기이고; R2및 R3는 독립적으로 치환된 플루오레닐기의 벤조링 잔기상에 존재하는 치환체이고, 독립적으로 탄소수 1 내지 20인 아미노기, 탄소수 1 내지 20인 산소－함유 탄화수소기, 또는 할로겐이고; M1은 Ti, Zr 또는 Hf이고; R4는 각각 독립적으로 수소원자, 탄화수소기, 탄소수 1 내지 20인 아미노기, 탄소수 1 내지 20인 산소－함유 탄화수소기, 또는 할로겐이고; m은 0 내지 4의 정수이고; n은 0 내지 4의 정수이고; m 및 n의 합계는 1 이상이다.)
  2. (a) 제1항의 일반식 (1)로 표시되는 치환된 플루오레닐기를 갖는 메탈로센 화합물과, (b) 상기 메탈로센 화합물과 반응하여 양이온성 메탈로센 화합물을 형성하는 화합물 및 (c) 유기금속 화합물로 이루어지는 것을 특징으로 하는 올레핀 중합용 촉매.
  3. 제1항 또는 제2항에 있어서, 상기한 메탈로센 화합물과 반응하여 양이온성 메탈로센 화합물을 형성하는 화합물(b)이 상기 메탈로센에 카운터 음이온을 부여하는, 프로톤산, 루이스 산, 이온화 이온성 화합물 또는 루이스 산 화합물임을 특징으로 하는 촉매.
  4. 제1항 또는 제2항에 있어서, 상기한 메탈로센 화합물과 반응하여 양이온성 메탈로센 화합물을 형성하는 화합물(b)이 알루미녹산임을 특징으로 하는 촉매.
  5. 제2항 또는 제3항에 있어서, 상기한 유기금속 화합물이 유기알루미늄 화합물로 이루어진 것임을 특징으로 하는 촉매.
  6. 제5항에 있어서, 상기한 촉매가, 메탈로센 화합물의 전이금속에 대한 알루미늄의 원자비가 1000 이하인 유기알루미늄 화합물을 함유하는 것임을 특징으로 하는 촉매.
  7. 제4항에 있어서, 상기한 촉매가, 메탈로센 화합물의 전이금속에 대한 알루미늄의 원자비가 1000 이하인 알루미녹산을 함유하는 것임을 특징으로 하는 촉매.
  8. 에틸렌 및/또는 탄소수 3 이상의 α－올레핀 또는 이들의 공중합체를, 제1항 내지 제7항중의 허느 한 항에 기재된 올레핀 중합용 촉매를 사용하여 120℃ 이상의 중합온도에서 중합시키는 것을 특징으로 하는 올레핀 중합체의 제조방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019950036953A 1994-10-25 1995-10-25 올레핀중합용촉매및올레핀중합체의제조방법 KR100445364B1 (ko)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP94-260222 1994-10-25
JP26022294 1994-10-25

Publications (2)

Publication Number Publication Date
KR960014164A true KR960014164A (ko) 1996-05-22
KR100445364B1 KR100445364B1 (ko) 2004-11-17

Family

ID=17345052

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019950036953A KR100445364B1 (ko) 1994-10-25 1995-10-25 올레핀중합용촉매및올레핀중합체의제조방법

Country Status (3)

Country Link
US (1) US6121396A (ko)
EP (1) EP0709393A3 (ko)
KR (1) KR100445364B1 (ko)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69720823T2 (de) * 1996-01-25 2004-01-22 Tosoh Corp., Shinnanyo Verfahren zur Olefinpolymerisierung unter Verwendung eines Übergangsmetallkatalysators.
US6174974B1 (en) * 1996-07-05 2001-01-16 Bayer Aktiengesellschaft Method for producing thermoplastic elastomers
KR100472591B1 (ko) * 1996-07-05 2005-05-16 바이엘 악티엔게젤샤프트 고융점폴리올레핀의제조방법
US5760262A (en) * 1996-09-17 1998-06-02 Albemarle Corporation Enhanced production of bridged hafnocenes
DE19719517A1 (de) 1997-05-09 1998-11-12 Basf Ag Katalysatorlösung zur Polymerisation von alpha-Olefinen
US5905162A (en) * 1997-08-12 1999-05-18 Albemarle Corporation Enhanced production of bridged hafnocenes
DE19737306A1 (de) 1997-08-27 1999-03-04 Basf Ag Katalysatorzubereitung für die (Co)polymerisation von Alk-l-enen
US6495484B1 (en) * 2000-08-28 2002-12-17 Univation Technologies, Llc Catalyst system and its use in a polymerization process
US7923593B2 (en) 2008-07-31 2011-04-12 Chevron U.S.A. Inc. Process for producing a middle distillate
AU2014253506B2 (en) * 2008-07-31 2014-12-18 Chevron U.S.A. Inc. Process for producing a low volatility gasoline blending component and a middle distillate
US7923594B2 (en) * 2008-07-31 2011-04-12 Chevron U.S.A. Inc. Process for producing middle distillate by alkylating C5+ isoparaffin and C5+ olefin
US7919663B2 (en) * 2008-07-31 2011-04-05 Chevron U.S.A. Inc. Process for producing a low volatility gasoline blending component and a middle distillate
US7919664B2 (en) * 2008-07-31 2011-04-05 Chevron U.S.A. Inc. Process for producing a jet fuel
WO2012134700A2 (en) 2011-03-28 2012-10-04 Dow Global Technologies Llc Process to produce enhanced melt strength ethylene/alpha-olefin copolymers and articles thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0500944B1 (en) * 1990-07-24 1998-10-07 Mitsui Chemicals, Inc. Catalyst for alpha-olefin polymerization and production of poly-alpha-olefin therewith
US5571880A (en) * 1991-05-09 1996-11-05 Phillips Petroleum Company Organometallic fluorenyl compounds and use thereof in an alpha-olefin polymerization process
ES2082274T3 (es) * 1991-05-27 1996-03-16 Hoechst Ag Procedimiento para la preparacion de poliolefinas sindiotacticas con amplia distribucion de masas moleculares.
NL9101502A (nl) * 1991-09-06 1993-04-01 Dsm Nv Werkwijze voor het bereiden van een gebrugde metalloceenverbinding alsmede een katalysatorcomponent en een werkwijze voor de polymerisatie van een olefinen.
US5710222A (en) * 1992-06-22 1998-01-20 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
US6313240B1 (en) * 1993-02-22 2001-11-06 Tosoh Corporation Process for producing ethylene/α-olefin copolymer
KR100311244B1 (ko) * 1993-02-22 2001-12-15 가지와라 야스시 에틸렌/α-올레핀공중합체의제조방법

Also Published As

Publication number Publication date
KR100445364B1 (ko) 2004-11-17
EP0709393A2 (en) 1996-05-01
US6121396A (en) 2000-09-19
EP0709393A3 (en) 2003-04-16

Similar Documents

Publication Publication Date Title
JP2669833B2 (ja) オレフインの重合及びオレフインの共重合のための触媒系
US4975403A (en) Catalyst systems for producing polyolefins having a broad molecular weight distribution
KR950008154B1 (ko) 올레핀 중합용 하프늄 메탈로센 촉매
US5710224A (en) Method for producing polymer of ethylene
JP2999000B2 (ja) Ｃ２−ｃ１０アルケン−１重合体用の可溶性触媒組成物
KR960014164A (ko) 올레핀 중합용 촉매 및 올레핀 중합체의 제조방법
KR920021595A (ko) 분자량 분포도가 넓은 신디오택틱 폴리올레핀의 제조 방법
KR950008543A (ko) 에틸렌 중합체의 제조방법 및 이 방법으로 부터 수득한 생성물
JP3076619B2 (ja) ブロック共重合体の製造方法
KR940014464A (ko) 불규칙 배열의 폴리 프로필렌
CA2345628A1 (en) Bridged metallocenes for olefin copolymerization
KR950014129A (ko) 메탈로센, 이의 제조방법 및 촉매로서의 이의 용도
KR960035724A (ko) 폴리올레핀 제조에 사용되는 신규의 촉매
KR930002361A (ko) 플루오레닐 함유 메탈로센 제조 방법
KR910007971A (ko) 신디오택틱 중합체의 제조방법 및 이에 사용되는 촉매
KR900701859A (ko) 올레핀의 고압 중합용의 지지된 메탈로센-알룸옥산 촉매. 그의 제조방법 및 그의 사용방법
KR900009719A (ko) 신규 에틸렌-프로필렌 공중합체
KR970074795A (ko) 에틸렌 중합체의 제조방법
CA2010065C (en) Process for the preparation of a random propylene copolymer
Jalali et al. Effect of metal type on the metallocene‐catalyzed oligomerization of 1‐hexene and 1‐octene to produce polyα‐olefin‐based synthetic lubricants
WO2001016192B1 (en) Metallocene catalyst compositions, processes for making polyolefin resins using such catalyst compositions, and products produced thereby
KR960022548A (ko) 메탈로센 화합물 및 촉매 성분으로의 이의 용도
HUP9801341A2 (hu) Polimerizációs katalizátorok és eljárás előállításukra
KR940005677A (ko) 올레핀중합용 촉매 및 올레핀의 중합방법
KR900014444A (ko) 스티렌계 중합체의 제조방법

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20110630

Year of fee payment: 8

FPAY Annual fee payment

Payment date: 20120724

Year of fee payment: 9

LAPS Lapse due to unpaid annual fee