FI111376B - Övergångsmetallkatalysator på en kiseldioxidbärare - Google Patents

Övergångsmetallkatalysator på en kiseldioxidbärare Download PDF

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Publication number
FI111376B
FI111376B FI944338A FI944338A FI111376B FI 111376 B FI111376 B FI 111376B FI 944338 A FI944338 A FI 944338A FI 944338 A FI944338 A FI 944338A FI 111376 B FI111376 B FI 111376B
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Finland
Prior art keywords
catalyst
compound
transition metal
vanadium
polymerization
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FI944338A
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English (en)
Finnish (fi)
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FI944338A (sv
FI944338A0 (sv
Inventor
Brian W S Kolthammer
Pak-Wing Steve Chum
Lee Spencer
Jeffrey J Wooster
Miriam P Ripplinger
Jacquelyn Ann Degroot
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Dow Global Technologies Inc
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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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/655—Pretreating with metals or metal-containing compounds with aluminium or compounds thereof
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Claims (8)

1. Förfarande för varierande av den kortkedjade förgreningsfördelningen (SCBD) av etylen-a-olefinsampoly- 5 merer, kännetecknat av att man (I) utsätter etylen och en eller flera α-olefinsammonomerer för lös-ningspolymeriseringsförhällanden i närvaro av en katalysa-torkomposition, vilken omfattar: (A) en uppburen övergängsmetallhaltig katalysator-10 komponent, vilken omfattar den resulterande produkten frän kontaktande de (1) av ett poröstfast oorganiskt oxidbärar- material, valt ur gruppen bestaende av kiseldioxid, alumi- niumoxid eller en kombination av kiseldioxid och alumini- umoxid, varvid nämnda bärarmaterial innehäller högst ca 5 15 millimol hydroxylgrupper per gram bärarmaterial och vilket har en artikelstorlek mindre än 10 pm och en ytarea frän 2 50 tili 800 m /g; (2) en organomagnesiumförening, en kol- vätelöslig organomagnesiumalkoxid eller en kolvätelöslig magnesiumdialkoxid; (3) en titanförening; valfritt (4) en 20 vanadinförening; och (5) en grupp IIIA-metallalkylhalo-genid; och väri komponenterna används i mängder, vilka tillhandahäller följande atomförhällanden: (Si + AI):Mg 1:1 - 30:1; Mg:Ti 0,2:1 - 10:1;
25 Mg:V 0,2:1 - 10:1, när vanadin är närvarande, Mg:IIIA-metall 0,05:1 - 5:1; V:Ti 0,8:1 - 1,2:1, när vanadin är närvarande; och (B) en samkatalysator eller aktivator för kompo-nenten (A); och 30 (II) justerar SCBD:et genom varierande av förhäl- landet Mg:Ti i komponenten (A).
2. Förfarande enligt patentkrav 1, kännetecknat av att (a) nämnda fasta bärarmaterial innehäller högst ca 35 4 millimol hydroxylgrupper per gram bärarmaterial och har 111376 67 en partikelstorlek frän 1 - 8 μιη och en ytarea frän 150 tili 600 m /g; (b) nämnda övergängsmetallkatalysator har ett atomförhällande Si + Ai (frän den oorganiska oxidbäraren) 5 tili Mg frän 2:1 - 40:1; (c) nämnda övergängsmetallkatalysator har ett atomförhällande Mg:Ti frän 0,2:1 - 20:1; (d) nämnda övergängsmetallkatalysator har ett atomförhällande Mg:V, när V är närvarande, frän 0,2:1 - 10 20:1; (e) nämnda övergängsmetallkalysator har ett atomförhällande Mg:IIIA-metall frän 0,05 - 10:1; och (f) nämnda övergängsmetallkatalysator har ett atomförhällande V:Ti, när V är närvarande, av 1:1. 15 3. Förfarande enligt patentkrav 1, k ä n n e- tecknat av att (a) nämnda fasta bärarmaterial innehäller högst 3 millimol hydroxylgrupper per gram bärarmaterial, och har en partikelstorlek frän 2 - 5 pm och en ytarea frän 300 20 tili 500 m /g; (b) nämnda övergängsmetallkatalysator har ett atomförhällande Si + Ai (frän den oorganiska oxidbäraren) tili Mg frän 4:1 - 20:1; (c) nämnda övergängsmetallkatalysator har ett 25 atomförhällande Mg:Ti frän 0,5:1 - 10:1; (d) nämnda övergängsmetallkatalysator har ett atomförhällande Mg:V, när V är närvarande, frän 0,5:1 -10:1; (e) nämnda övergängsmetallkatalysator har ett 30 atomförhällande Mg:IIIA-metall frän 0,1:1 - 5:1; och (f) nämnda övergängsmetallkatalysator har ett atomförhällande V:Ti, när V är närvarande, av 1:1.
4. Förfarande enligt patentkrav 1, 2 eller 3, kännetecknat av att 35 (a) nämnda fasta bärarmaterial är kiseldioxid; 111376 68 (b) nämnda magnesiumförening är en förening med formeln RxMg(OR)y, väri varje R självständigt är en hydro- karbylgrupp med 1-20 kolatomer, x + y = 2, och 0,5 < y < 2; 5 (c) nämnda titanförening är en förening med for meln TiX4_a (OR' ) , väri varje R' s jälvständigt är en alkyl- grupp med 1-20 kolatomer, X är en halogenatom, och a har ett värde 0-4; (d) nämnda vanadinförening, när den är närvarande, 10 är en förening med formeln VX4_a(OR')a, väri varje R’ självständigt är en alkylgrupp med 1-20 kolatomer, X är en halogenatom, och a har ett värde 0-4; (e) nämnda grupp IIIA-metallalkylhalogenid är en förening med formeln R'yMXz, väri M är en metall ur grup- 15 pen IIIA i det periodiska grundämnessystemet, varje R' är självständigt en alkylgrupp med 1-20 kolatomer; X är en halogenatom, y och z har envar s j älvständigt ett värde frän 1 tili ett värde lika med valensen för M minus 1 och y + z har ett värde lika med valensen för M; och 20 (f) nämnda α-olefin innehäller 2-8 kolatomer el- ler nägon kombination av tvä eller flera sädana a-ole-finer.
5. Förfarande enligt patentkrav 1, 2 eller 3, kännetecknat av att 25 (a) komponenten (2) nämnda magnesiumförening är etylmagnesiumetoxid, butylmagnesiumetoxid, oktylmagnesiu-metoxid, butylmagnesiumbutoxid, etylmagnesiumbutoxid, bu-tylmagnesiumoktoxid, s-butylmagnesiumoktoxid eller nägon kombination av sädana föreningar; 30 (b) nämnda titanförening är titantetraklorid, ti- tantetraisopropoxid eller nägon kombination av sädana föreningar; (c) nämnda vanadinförening, när den är närvarande, är vanadintetraklorid, vanadinoxitriklorid eller nägon 35 kombination av sädana föreningar; och 111376 69 (d) nämnda grupp ΙΙΙΆ-metallalkylhalogenid är etylaluminiumdiklorid, isobutylaluminiumdiklorid, etyl-aluminiumseskviklorid eller nägon kombination av sädana föreningar; och 5 (e) nämnda α-olefin är eten, propen, 1-buten, 1-hexen, 1-okten, 1,4-metylpent-l-en eller nägon kombination av tvä eller flera sädana föreningar.
6. Polymer, framställd med förfarandet enligt pa-tentkrav 1, 2 eller 3.
7. Polymer, framställd med förfarandet enligt pa- tentkrav 4.
8. Polymer, framställd med förfarandet enligt pa-tentkrav 5. 15
FI944338A 1992-03-20 1994-09-19 Övergångsmetallkatalysator på en kiseldioxidbärare FI111376B (sv)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US85417592 1992-03-20
US07/854,175 US5231151A (en) 1991-01-18 1992-03-20 Silica supported transition metal catalyst
PCT/US1993/002751 WO1993019105A2 (en) 1992-03-20 1993-03-17 Silica supported transition metal catalyst
US9302751 1993-03-17

Publications (3)

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FI944338A0 FI944338A0 (sv) 1994-09-19
FI944338A FI944338A (sv) 1994-11-18
FI111376B true FI111376B (sv) 2003-07-15

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US (3) US5231151A (sv)
EP (1) EP0705282B1 (sv)
JP (3) JP3306663B2 (sv)
KR (1) KR100256460B1 (sv)
AT (1) ATE169034T1 (sv)
AU (2) AU677184B2 (sv)
CA (1) CA2132447C (sv)
DE (1) DE69320070T2 (sv)
ES (1) ES2118952T3 (sv)
FI (1) FI111376B (sv)
TW (1) TW327177B (sv)
WO (1) WO1993019105A2 (sv)

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US5231151A (en) 1993-07-27
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US5487938A (en) 1996-01-30
AU1994097A (en) 1997-08-21
KR100256460B1 (ko) 2000-05-15
US5487938B1 (en) 1997-11-18
ES2118952T3 (es) 1998-10-01
WO1993019105A3 (en) 1993-11-11
FI944338A (sv) 1994-11-18
DE69320070D1 (de) 1998-09-03
DE69320070T2 (de) 1998-12-10
FI944338A0 (sv) 1994-09-19
US5420090A (en) 1995-05-30
ATE169034T1 (de) 1998-08-15
CA2132447A1 (en) 1993-09-30
AU3933293A (en) 1993-10-21
WO1993019105A2 (en) 1993-09-30
JP3306663B2 (ja) 2002-07-24
JPH07507819A (ja) 1995-08-31
AU677184B2 (en) 1997-04-17
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