FI112369B - Katalysator och förfarande för polymerisering av alfa-olefiner - Google Patents

Katalysator och förfarande för polymerisering av alfa-olefiner Download PDF

Info

Publication number
FI112369B
FI112369B FI933923A FI933923A FI112369B FI 112369 B FI112369 B FI 112369B FI 933923 A FI933923 A FI 933923A FI 933923 A FI933923 A FI 933923A FI 112369 B FI112369 B FI 112369B
Authority
FI
Finland
Prior art keywords
catalyst
cyclopentadienyl
tin
range
magnesium
Prior art date
Application number
FI933923A
Other languages
English (en)
Finnish (fi)
Other versions
FI933923A (fi
FI933923A0 (fi
Inventor
Luciano Luciani
Federico Milani
Antonio Labianco
Bruno Pivotti
Original Assignee
Enichem Spa
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 Enichem Spa filed Critical Enichem Spa
Publication of FI933923A0 publication Critical patent/FI933923A0/fi
Publication of FI933923A publication Critical patent/FI933923A/fi
Application granted granted Critical
Publication of FI112369B publication Critical patent/FI112369B/sv

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
    • 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
    • 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
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • 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
    • C08F4/65916—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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (11)

1. Förfarande för framställning av en katalysator inne-hallande.· ett cyklopentadienylskt derivat av en metall fran grundämnenas periodiskt sydtem gruppen IVB, pä en fast bära-re, kanne tecknat därav (i) i ett inert organiskt lösningsmedel upplöses ett dial-kylmagnesium eller en alkylmagnesiumhalid med en tennhalid, varvid atomförhallande av tenn i tenn-haliden tili magnesium i dialkylmagnesium eller alkyl-magnesiumhalid, ligger i omradet o, 1:1 - 13:1, och reaktanterna hälles i ömsesidig kontakt ända tills en fast granulformad substans utfaller ur lösningen; (ii) nämnda granulformade substansensuspenderas i ett inert organiskt lösningsmedel och bringas i kontakt med en förening som kan definieras genom formeln: C R \/ M (I) 3 Λ ·' ; CP R • \ · d ä r : • ’t' M avser en metall fran gruppen IVB i grundämnenas : : ; · periodiska systemet; envart R avser pberoende av var- andra· en halogenatom, en antingen linjär eller för-grenad alkylgraupp med 1-10 kolatomer eller en alkyl-grupp; och envarrt oberoende av varandra avser en cyklopentadieny1- indenyl- eller fluorenylgrupp, =’ ‘ eyentuellt med en eller flera C^-C^ alky 1-substi- tuenter, och nämnda grupper (^kan dessutom vara bundna vid varandra med hjälp av en sammanlänkande brygg-, strukturav kolatomer eller en alkylsilan-struktur, varvid atomförhallandet av magnesium, tillfört under 24 112369 steget (i), till metall i grupp 1VB i foreningen (1), i omradet 1:1 - 10; varvid man arbetar vid en tempera-tur i omradet 0° - 100°C och under en tid av minst 0,5 timmar, för att bilda en granulformad fast kata-lysator; och (ii) den fasta katalysatorn utuinnes ur den erhallna suspension som innehaller den.
2. Förfarande enligt patentkravet 1, känneteck-n a t, därav, att nämnda dialkylmagnesium kan represen-teras genom formeln MgR’R’ ’ där envart R’ och R’’, som kan vara lika eller skilda varandra, oberoende fran varandra avser en linjär eller förgrgrenad alkylgrupp med 1-10 kolatomer.
3. Förfarande enligt patentkrvet 2, känneteck-nat därav, att nämnda dialkylmagnesium valts fran di-etylmagnesium, etylbutylmagnesium, dihexylmagnesium, butyloktylmagnesium och dioktylmagnesium. » I · It « :\! 4. förfarande enligt patentkravet 1, k ä n n e t e c k - n a t därav, att nämnda tennhalid valts fran tennklorid och -bromid. • 1 * » · # 1 5,- · Förfarande'enligt patentkrvet4, k ä n n e t e c k-n a t därav·, att nämnda tennhalid är tenntetraklor id.
6. Förfarande enligt patentkravet 1, känneteck- n a t därav, att i nämnda steg (i) utförs förfarandet i en lösning i ett alifatiskt kolväte-lösningsmedel, i ett atomförhallahde tenn till magnesiumii omradet 0,5: 1 -10:1, vid en temperatur i omradet 30 - 70°C, företrädesvis 60 - 70°C, och under en tid av 0,5 - 5 timmar, företrädesvis 1 timme. 25 112569
7. Förfarande enligt patentkravet 1, kännetecknat -därav, att i nämnda formel (I) näranda metall M valts f ran titan, ziiconium och hafnium, företrädesvis zirconium och hafnium, envart R är en kloratom eller en alkylgrupp med 1-8 kolato- . mer, och envart Cp har vplts frän cyklopentadienyl-fiiindapyl-. öchyfluorenylgrupRer, vilka antingen kan kan vara osubstitue-rade eller ha en eller. flera C^-C^ alkyl-substituenter, och bägge grupperna kan vara kopplade genom en rak eller för- grenad alkylenkedjebrygga med 1-4 kolatmer, eller genom en . dialkylsilyl-halvdel.
8. Förfarande enligt patentkravet 7, k a n n e t e c k n a t därav, a.tt nämnd.a förening (I) valts fran bis(cyklopentadienyl )-zirkoriiumdiklorid, bis(cyklopentadienyl)-hafniumdiklorid, bis-(cyklopentadienyl)-zirkoniumoktylklorid, bis(cyklopentadienyl)-zirkoniumdimetyl, etylen-Tbis(indenyl)zirkoniumdiklorid , etylen-bis(ind.enyl)hafniumdiklorid och isopropyl(cyklopentadienyl-•£luorenyl)hafniumdiklorid. c
9. Förfarande enligt patentkravet 1, kännetecknat därayatt I· nämnda stegn.(ii) förfarandet utförs i ett alifa- tiskt kolvätelösningsmedel med ett förhällande av magnesium tili i nämnda grupp IVB-metail i omrädet 5:1 - 5000:1, vid en tempera- .:tur i omrädet 20 - 90°C och under en tid av 0,5 - 5 timmar, före-* * * * . trädesvis 1' - 2,5 timmar. i t ♦ 9 « * t i t · : ’ 10·.. Katalytiskt system för polymerisationen av olefiner, be- > * stäende av den enligt patentkravet 1 erhällna katalysa- torn, och en aluminoxan-ko-katalysator, med ett atomförhallande : av aluminium i nämnda ko-katalysator tili grupp IVB-metallen i i 8 den fasta katalysatorn i omrädet 10:1 - 10 :1, företrädesvis 2-4 10 :1·- .10 :,1. 11..· Förfarande för polymerisationen avolefiner, kanne-t e c k n.a r därav, att det katalytiska systemet enligt patentkravet 10 användes.
FI933923A 1992-09-15 1993-09-08 Katalysator och förfarande för polymerisering av alfa-olefiner FI112369B (sv)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI922125A IT1255365B (it) 1992-09-15 1992-09-15 Catalizzatore e procedimento per la polimerizzazione di alfa-olefine
ITMI922125 1992-09-15

Publications (3)

Publication Number Publication Date
FI933923A0 FI933923A0 (fi) 1993-09-08
FI933923A FI933923A (fi) 1994-03-16
FI112369B true FI112369B (sv) 2003-11-28

Family

ID=11363949

Family Applications (1)

Application Number Title Priority Date Filing Date
FI933923A FI112369B (sv) 1992-09-15 1993-09-08 Katalysator och förfarande för polymerisering av alfa-olefiner

Country Status (18)

Country Link
US (1) US6127305A (sv)
EP (1) EP0588404B1 (sv)
JP (1) JPH06184216A (sv)
AT (1) ATE154618T1 (sv)
BR (1) BR9303781A (sv)
CA (1) CA2104634A1 (sv)
CZ (1) CZ288579B6 (sv)
DE (1) DE69311657T2 (sv)
DK (1) DK0588404T3 (sv)
ES (1) ES2105081T3 (sv)
FI (1) FI112369B (sv)
GR (1) GR3023895T3 (sv)
HU (1) HU212438B (sv)
IT (1) IT1255365B (sv)
MX (1) MX9305641A (sv)
RU (1) RU2118329C1 (sv)
SK (1) SK280679B6 (sv)
TW (1) TW259795B (sv)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1269837B (it) * 1994-05-26 1997-04-15 Spherilene Srl Componenti e catalizzatori per la polimerizzazione delle olefine
CN1044609C (zh) * 1994-11-07 1999-08-11 中国科学院化学研究所 乙烯聚合载体锆茂催化剂体系及其制法和用途
US6399533B2 (en) * 1995-05-25 2002-06-04 Basell Technology Company Bv Compounds and catalysts for the polymerization of olefins
IT1282364B1 (it) * 1996-01-16 1998-03-20 Enichem Spa Catalizzatore metallocenico supportato per la (co) polimerizzazione delle alfa-olefine
IT1282635B1 (it) * 1996-02-16 1998-03-31 Enichem Elastomers Componente catalitico al vanadio e suo utilizzo nella preparazione di ep(d)m
US6180736B1 (en) 1996-12-20 2001-01-30 Exxon Chemical Patents Inc High activity metallocene polymerization process
WO1999021898A1 (en) * 1997-10-28 1999-05-06 Exxon Chemical Patents Inc. Magnesium halide based metallocene catalyst system
SG96700A1 (en) * 2001-09-27 2003-06-16 Sumitomo Chemical Co Catalyst component for addition polymerization, process for producing catalyst for addition polymerization and process for producing addition polymer
EP1403288A1 (en) * 2002-09-27 2004-03-31 ATOFINA Research Dual site catalyst system comprising a hafnocene component for the production of bimodal polyolefins
BRPI0705994A2 (pt) * 2007-10-19 2009-10-06 Braskem Sa processo de preparação de suporte catalìtico e catalisadores bimetálicos suportados para a produção de homopolìmeros e copolìmeros de etileno com alfa-olefinas de alto e ultra alto peso molecular e com ampla distribuição de peso molecular em processos em lama, massa e fase gás e os produtos assim obtidos
KR102616697B1 (ko) * 2019-10-11 2023-12-21 주식회사 엘지화학 폴리에틸렌 및 이의 제조방법
KR102668044B1 (ko) * 2020-05-28 2024-05-23 한화솔루션 주식회사 혼성 촉매 조성물, 이를 포함하는 촉매 및 이들의 제조방법

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR480434A (fr) * 1915-01-19 1916-08-03 Edmond Roquette Appareil à mouton pour le moulage de métal, destiné aux dentistes, orfèvres, etc.
FR2252355B1 (sv) * 1973-11-22 1976-10-01 Solvay
US4330646A (en) * 1979-08-13 1982-05-18 Asahi Kasei Kogyo Kabushiki Kaisha Polymerization of an α-olefin
US4471066A (en) * 1981-02-16 1984-09-11 Asahi Kasei Kogyo Kabushiki Kaisha Polymerization of olefins
US4808561A (en) * 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
IL84798A (en) * 1986-12-15 1991-09-16 Montedison Spa Production of crystalline vinyl aromatic polymers having mainly a syndiotactic structure
DE3855519T2 (de) * 1987-03-19 1997-04-17 Idemitsu Kosan Co Olefinpolymere und Verfahren zu deren Herstellung
JPS646004A (en) * 1987-06-30 1989-01-10 Mitsui Petrochemical Ind Solid catalyst component for olefin polymerization
JPS646005A (en) * 1987-06-30 1989-01-10 Mitsui Petrochemical Ind Solid catalyst component for olefin polymerization
US5120696A (en) * 1989-12-29 1992-06-09 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for the polymerization of olefins
DE69130320T2 (de) * 1990-07-24 1999-04-08 Mitsui Chemicals Inc Katalysator für alpha-olefinpolymerisation und herstellung von poly(alpha)olefinen damit
IT1243829B (it) * 1990-10-11 1994-06-28 Enimont Anic Srl Componente solido di catalizzatore per la omo-e la co-polimerizzazione di etilene.
DE69224463T2 (de) * 1991-11-28 1998-07-09 Showa Denko Kk Neues Metallocen und Verfahren zur Herstellung von Polyolefinen unter Verwendung desselben

Also Published As

Publication number Publication date
CZ288579B6 (cs) 2001-07-11
JPH06184216A (ja) 1994-07-05
ITMI922125A0 (it) 1992-09-15
EP0588404A3 (en) 1994-08-24
DE69311657D1 (de) 1997-07-24
GR3023895T3 (en) 1997-09-30
HUT66777A (en) 1994-12-28
US6127305A (en) 2000-10-03
ATE154618T1 (de) 1997-07-15
ITMI922125A1 (it) 1994-03-15
SK91193A3 (en) 1994-07-06
EP0588404B1 (en) 1997-06-18
ES2105081T3 (es) 1997-10-16
IT1255365B (it) 1995-10-31
TW259795B (sv) 1995-10-11
RU2118329C1 (ru) 1998-08-27
DE69311657T2 (de) 1997-12-18
FI933923A (fi) 1994-03-16
EP0588404A2 (en) 1994-03-23
HU9302601D0 (en) 1993-11-29
FI933923A0 (fi) 1993-09-08
BR9303781A (pt) 1994-06-14
CA2104634A1 (en) 1994-03-16
SK280679B6 (sk) 2000-06-12
CZ182693A3 (en) 1994-04-13
MX9305641A (es) 1995-01-31
DK0588404T3 (da) 1997-10-13
HU212438B (en) 1996-06-28

Similar Documents

Publication Publication Date Title
EP0586168B1 (en) Catalyst compositions and process for preparing polyolefins
US6316562B1 (en) Catalyst systems for (co-)polymerization reactions, metallocene amide halogenides, the production and use thereof
EP0628577B2 (en) Silyl bridged metallocenes and use thereof
JP2540174B2 (ja) １−オレフイン−ステレオブロック重合体およびその製造方法
US6262195B1 (en) Multi-stage process for the polymerization of olefins
US8569194B2 (en) Catalyst composition for polymerization of olefins, polymerization process using the same, and method for its preparation
US5886202A (en) Bridged fluorenyl/indenyl metallocenes and the use thereof
EP3421506B1 (en) Metallocene supported catalyst and method for producing polypropylene using same
US6111046A (en) Atactic copolymers of propylene with ethylene
CA2113601A1 (en) Catalyst compositions and process for preparing polyolefins
NO301332B1 (no) Katalysatorsammensetning, fremgangsmåte for fremstilling derav og polymerisering av olefiner
US5202398A (en) Process for the preparation of a 1-olefin polymer
FI112369B (sv) Katalysator och förfarande för polymerisering av alfa-olefiner
JP2006182778A (ja) アルファオレフィンの重合及び共重合用触媒組成物
EP1417031B1 (en) Amine elimination process for making single-site catalysts
EP0595390B1 (en) Catalyst and process for (co)polymerizing alpha-olefins
CN111556878B (zh) 负载型茂金属催化剂和使用该催化剂制备聚丙烯的方法
JP3850048B2 (ja) 有機遷移金属化合物およびそれを用いたポリオレフィンの製造方法
US5670436A (en) Metallocene compound
JPH10502406A (ja) エチレンの重合のための触媒系
EP3455231B1 (en) Unsymmetrical metallocene catalysts and uses thereof
RU2156253C2 (ru) Каталитическая композиция, металлоценовый комплекс и способ полимеризации олефинов
US6927262B2 (en) Bridged biphospholes and metallocenes prepared therefrom
JP3427488B2 (ja) 新規有機遷移金属化合物およびそれを用いたポリオレフィンの製造方法
JPH11171916A (ja) 高シンジオタクチック性ポリスチレン製造用の触媒組成物および該触媒組成物を利用した重合法