FI112369B - Katalysator och förfarande för polymerisering av alfa-olefiner - Google Patents
Katalysator och förfarande för polymerisering av alfa-olefiner Download PDFInfo
- 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
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Classifications
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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
- 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
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- 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.
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)
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)
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 |
-
1992
- 1992-09-15 IT ITMI922125A patent/IT1255365B/it active IP Right Grant
-
1993
- 1993-08-20 TW TW082106731A patent/TW259795B/zh active
- 1993-08-23 CA CA002104634A patent/CA2104634A1/en not_active Abandoned
- 1993-08-26 SK SK911-93A patent/SK280679B6/sk not_active IP Right Cessation
- 1993-08-28 DE DE69311657T patent/DE69311657T2/de not_active Expired - Fee Related
- 1993-08-28 AT AT93202524T patent/ATE154618T1/de not_active IP Right Cessation
- 1993-08-28 EP EP93202524A patent/EP0588404B1/en not_active Expired - Lifetime
- 1993-08-28 DK DK93202524.0T patent/DK0588404T3/da active
- 1993-08-28 ES ES93202524T patent/ES2105081T3/es not_active Expired - Lifetime
- 1993-09-03 CZ CZ19931826A patent/CZ288579B6/cs not_active IP Right Cessation
- 1993-09-08 FI FI933923A patent/FI112369B/sv active
- 1993-09-10 JP JP5225913A patent/JPH06184216A/ja active Pending
- 1993-09-14 HU HU9302601A patent/HU212438B/hu not_active IP Right Cessation
- 1993-09-14 RU RU93052696A patent/RU2118329C1/ru not_active IP Right Cessation
- 1993-09-14 MX MX9305641A patent/MX9305641A/es unknown
- 1993-09-14 BR BR9303781A patent/BR9303781A/pt not_active IP Right Cessation
-
1996
- 1996-10-03 US US08/725,696 patent/US6127305A/en not_active Expired - Fee Related
-
1997
- 1997-06-26 GR GR970401542T patent/GR3023895T3/el unknown
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 |
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