FI105194B - Polymerisationsförfarande - Google Patents

Polymerisationsförfarande Download PDF

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Publication number
FI105194B
FI105194B FI943996A FI943996A FI105194B FI 105194 B FI105194 B FI 105194B FI 943996 A FI943996 A FI 943996A FI 943996 A FI943996 A FI 943996A FI 105194 B FI105194 B FI 105194B
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FI
Finland
Prior art keywords
component
catalyst
ethylene
process according
group
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Application number
FI943996A
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English (en)
Finnish (fi)
Other versions
FI943996A (sv
FI943996A0 (sv
Inventor
Michael John Doyle
Willem Terlouw
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Shell Int Research
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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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • 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
    • 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
    • C08F4/65908—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
    • C08F4/6592—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

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (12)

1. Förfarande för polymerisering eller sampolymeri-sering av etylen och/eller ett eller flera alfa-olefiner, 5 kännetecknat av, att man kontaktar alfa-ole-fin(-er) med en katalysator sora omfattar en första kom-ponent i form av med en metall ur gruppen IVA bildad bis-(cyklopentadienyl)-förening som innehäller en substituent, vilken förmär reagera med en katjon, och en andra komit) ponent i form av en förening med en skrymmande anjon som innehäller en eller flera boratomer och vilken väsentligen är icke-koordinerande under reaktionsförhällandena och en katjon, varvid man under förfarandet neutraliserar reduktion i katalysator aktivitet genom att tillsätta en ytter- 15 ligare mängd av den första komponenten.
2. Förfarande enligt patentkrav 1, kännetecknat av, att det är ett kontinuerligt förfarande, varvid katalysatorn som är närvarande i produktström-men som lämnar den använda reaktorn deaktiveras före upp- 20 arbetningen av produkten, och den efter upparbetningen av produkten kvarblivna fasta resten ätercirkuleras tili reaktorn som en källa för den andra katalysatorkomponen-ten, vilken kompletteras genom tillsättning av färsk, « · första katalysatorkomponent. « « · 25
3. Förfarande enligt patentkrav 2, k ä n n e - * < « *·.* · t e c k n a t av, att deaktiveringen utförs genom att i • · · • produktströmmen tillsätts vatten i en mängd som är ätmin-stone ekvimolär i förhällande tili närvarande, aktiv kata- • · · « lysator. 30
4. Förfarande enligt patentkrav 2, k ä n n e - .···. t e c k n a t av, att deaktiveringen utförs genom att i • · produktströmmen tillsätts en lägre alkohol i en mängd som är ätminstone ekvimolär i förhällande tili närvarande, aktiv katalysator. 35
5. Förfarande enligt nägot av patentkraven 1-4, kännetecknat av, att den första komponenten är « i > 17 105194 en förening med formeln (Cp)2MR1R2, väri varje grupp Cp, vilka kan vara lika eller olika, betecknar en cyklopenta-dienylgrupp som kan vara eller ej är substituerad med hyd-rokarbylgrupper, M betecknar metallatomen ur gruppen IVA, 5 och R2 och R2, vilka kan vara lika eller olika, vardera betecknar en väteatom eller en substituerad eller osubsti-tuerad hydrokarbylgrupp.
6. Förfarande enligt nägot av patentkraven 1 - 5, kännetecknat av, att metallen ur gruppen IVA 10 är zirkon eller hafnium.
7. Förfarande enligt patentkrav 5 eller 6, kännetecknat av, att varje Cp-grupp betecknar en pentaalkylcyklopentadienylgrupp och Rx och R2 är vardera alkylgrupper. 15
8. Förfarande enligt nägot av patentkraven 1-7, kännetecknat av, att den andra komponenten omfattar en karborananjon som väsentligen icke-koor-dinerande anjon.
9. Förfarande enligt nägot av patentkraven 1-8, 20 kännetecknat av, att den andra komponenten omfattar en protonavgivande katjon.
10. Förfarande enligt patentkrav 9, k ä n n e - . t e c k n a t av, att den andra komponenten är ett tri- *;;; alkylammoniumkarboran, varvid karboranan j onen betecknas I « « 25 genom formeln B11CH12*.
• · *.* ' 11. Förfarande enligt nägot av patentkraven 1 - 10, ·· · ·'.· kännetecknat av, att katalysatorn omfattar den « första komponenten och den andra komponenten i ett molför-hällande i omrädet 0,1 - 20. 30
12. Förfarande enligt nägot av patentkraven 1 - 11, . .··. kännetecknat av, att etylenet sampolymeriseras • · .···, med ett eller flera alfa-olefiner) , varvid förhällandet alfa-olefin(-er) tili etylen ligger i omrädet 50 - 500 mol per mol etylen, och att polymerisationen utföres vid en 35 temperatur i omrädet 50 - 150 °C och vid ett tryck i omrädet 0,5 - 6,0 MPa (5 - 60 bar). I ( \ i · I ·
FI943996A 1992-03-02 1994-08-31 Polymerisationsförfarande FI105194B (sv)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP92200605 1992-03-02
EP92200605 1992-03-02
EP9300469 1993-02-26
PCT/EP1993/000469 WO1993018071A1 (en) 1992-03-02 1993-02-26 Polymerization process

Publications (3)

Publication Number Publication Date
FI943996A FI943996A (sv) 1994-08-31
FI943996A0 FI943996A0 (sv) 1994-08-31
FI105194B true FI105194B (sv) 2000-06-30

Family

ID=8210462

Family Applications (1)

Application Number Title Priority Date Filing Date
FI943996A FI105194B (sv) 1992-03-02 1994-08-31 Polymerisationsförfarande

Country Status (16)

Country Link
US (1) US5387660A (sv)
EP (1) EP0629215B2 (sv)
JP (1) JP3109742B2 (sv)
KR (1) KR100244676B1 (sv)
CN (1) CN1033813C (sv)
AU (1) AU665623B2 (sv)
BR (1) BR9306003A (sv)
CA (1) CA2131298C (sv)
CZ (1) CZ281974B6 (sv)
DE (1) DE69300366T3 (sv)
DK (1) DK0629215T4 (sv)
FI (1) FI105194B (sv)
NO (1) NO301238B1 (sv)
NZ (1) NZ249485A (sv)
TW (1) TW254950B (sv)
WO (1) WO1993018071A1 (sv)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2101217T3 (es) * 1992-10-23 1997-07-01 Shell Int Research Composicion catalitica para oligomerizacion y co-oligomerizacion de alquenos.
TW404956B (en) * 1996-05-21 2000-09-11 Mitsui Petrochemical Ind A method of diminishing the source of odor from polyolefin obtained by use of metallocene compound
US6242545B1 (en) * 1997-12-08 2001-06-05 Univation Technologies Polymerization catalyst systems comprising substituted hafinocenes
US20060293470A1 (en) * 2005-06-28 2006-12-28 Cao Phuong A Polymerization process using spray-dried catalyst
US8497330B2 (en) * 1997-12-08 2013-07-30 Univation Technologies, Llc Methods for polymerization using spray dried and slurried catalyst
BR0211286B1 (pt) * 2001-07-19 2012-10-02 filmes com propriedades fìsicas aperfeiçoadas.
US6936675B2 (en) * 2001-07-19 2005-08-30 Univation Technologies, Llc High tear films from hafnocene catalyzed polyethylenes
US7053157B2 (en) * 2001-07-20 2006-05-30 University Of Maryland, College Park Method for production of multimodal polyolefins of tunable composition, molecular weight, and polydispersity
US7041759B2 (en) * 2002-11-20 2006-05-09 The University Of Maryland, College Park Method for the preparation of well-defined metal acetamidinate-based catalysts on solid supports
US7683140B2 (en) * 2004-05-20 2010-03-23 Univation Technologies, Llc Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring
US7754830B2 (en) 2004-05-20 2010-07-13 Univation Technologies, Llc Polymerization reaction monitoring with determination of induced condensing agent concentration for preventing discontinuity events
US7078467B1 (en) * 2005-06-14 2006-07-18 Univation Technologies, Llc Single catalyst low, medium and high density polyethylenes
EP2059537B8 (en) * 2006-09-07 2017-02-22 Univation Technologies, LLC Methods for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring
RU2448981C2 (ru) * 2006-09-07 2012-04-27 Юнивейшн Текнолоджиз, Ллк Способы определения в режиме реального времени степени липкости смолы с использованием модели снижения температуры начала плавления
WO2009061499A1 (en) * 2007-11-09 2009-05-14 University Of Maryland, College Park Process for preparation of polyolefins via living coordinative chain transfer polymerization
SG11202003755XA (en) * 2017-10-31 2020-05-28 Dow Global Technologies Llc Catalyst systems comprising carborane cocatalysts

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
IL85097A (en) * 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
PL276385A1 (en) * 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
US5155080A (en) * 1988-07-15 1992-10-13 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
ATE186918T1 (de) * 1990-01-02 1999-12-15 Exxon Chemical Patents Inc Ionische metallocenkatalysatoren auf träger für olefinpolymerisation
GB9004014D0 (en) * 1990-02-22 1990-04-18 Shell Int Research Co-oligomerization process
GB9116297D0 (en) * 1991-07-29 1991-09-11 Shell Int Research Co-oligomerisation process

Also Published As

Publication number Publication date
US5387660A (en) 1995-02-07
DK0629215T3 (da) 1995-09-25
CZ212294A3 (en) 1994-12-15
NO943221D0 (no) 1994-08-31
CA2131298C (en) 1998-06-16
EP0629215B2 (en) 1999-05-12
NO301238B1 (no) 1997-09-29
KR100244676B1 (ko) 2000-02-15
EP0629215B1 (en) 1995-08-09
FI943996A (sv) 1994-08-31
JP3109742B2 (ja) 2000-11-20
DE69300366D1 (de) 1995-09-14
DE69300366T2 (de) 1996-03-21
AU3629993A (en) 1993-10-05
CA2131298A1 (en) 1993-09-16
CN1033813C (zh) 1997-01-15
WO1993018071A1 (en) 1993-09-16
AU665623B2 (en) 1996-01-11
CN1075971A (zh) 1993-09-08
DK0629215T4 (da) 1999-11-01
JPH07504225A (ja) 1995-05-11
DE69300366T3 (de) 1999-10-28
TW254950B (sv) 1995-08-21
NZ249485A (en) 1996-05-28
NO943221L (no) 1994-08-31
BR9306003A (pt) 1997-10-21
FI943996A0 (sv) 1994-08-31
CZ281974B6 (cs) 1997-04-16
KR950700335A (ko) 1995-01-16
EP0629215A1 (en) 1994-12-21

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