FI110105B - Polymerisering av eten sampolymerer - Google Patents

Polymerisering av eten sampolymerer Download PDF

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Publication number
FI110105B
FI110105B FI943116A FI943116A FI110105B FI 110105 B FI110105 B FI 110105B FI 943116 A FI943116 A FI 943116A FI 943116 A FI943116 A FI 943116A FI 110105 B FI110105 B FI 110105B
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ethylene
copolymer
process according
catalyst
reactivity
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FI943116A
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English (en)
Finnish (fi)
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FI943116A0 (sv
FI943116A (sv
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Brian W S Kolthammer
Robert S Cardwell
Deepak R Parikh
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Dow Chemical Co
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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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08F4/65908—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

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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)
  • Inorganic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (20)

1. Förfarande för framställning av en etylenpoly-merprodukt, känneteckat av, att man 5 (a) polymeriserar en första homogen etylenpolymer under användande av en första aktiverad katalysatorkompo-sition med begränsad geometri och med sadan första reakti-vitet, att den första polymeren har ett smältindex frän 0,05 tili 50 g/10 minuter, 10 (b) polymeriserar ätminstone en andra homogen ety lenpolymer under användning av en andra katalysatorkompo-sition med begränsad geometri och med sadan andra reakti-vitet, att den andra etylenpolymeren har ett smältindex frän 0,05 tili 50 g/10 minuter, och 15 (c) kombinerar 50 - 95 vikt-% av den första etylen polymeren med 5 - 50 vikt-% av den andra etylenpolymeren för bildande av en etylenpolymerprodukt.
2. Förfarande för framställning av en etylen-a-ole-finsampolymerprodukt, känneteckat av, att man 20 (a) polymeriserar en första homogen etylen-a-ole- finsampolymer under användning av en första aktiverad ka- • · ·!.* talysatorkomposition med begränsad geometri och med sädan *·*'· första reaktivitet, att den första sampolymeren har ett "*! innehäll av 5 - 30 vikt-% sammonomer, ett smältindex frän i’·’: 25 0,05 tili 50 g/10 minuter, och en smältpunkt lägre än ca. ;· 110 °C, (b) polymeriserar ätminstone en andra homogen ety- » len-a-olefin-sampolymer under användning av en andra akti- t. . verad katalysatorkomposition med begränsad geometri och • t > 30 med en andra sädan reaktivitet, att den andra etylen-a- ·;** olef insampolymeren har ett sammonomer innehäll av 2 - 10 : | : vikt-%, ett smältindex frän 0,05 tili 50 g/10 minuter samt en smältpunkt som överstiger ca. 115 °C, och / . (c) kombinerar 50 - 95 vikt-% av den första homoge- * ) 35 na etylen-a-olefin-sampolymeren med 5-50 vikt-% av den » · 42 110105 andra homogena etylen-a-olefin-sampolymeren för bildande av en etylen-a-olefin-sampolymerprodukt.
3. Förfarande enligt patentkrav 1 eller 2, k ä n -neteckat av, att den första katalysatorkomposi- 5 tionen med begränsad geometri omfattar ett titankomplex med begränsad geometri och en aluminiumoxansamkatalysator.
4. Förfarande enligt patentkrav 1 eller 2, k ä n -neteckat av, att den andra aktiverade katalysator-kompositionen med begränsad geometri omfattar ett zirkon- 10 komplex med begränsad geometri och en aluminiumoxansamkatalysator.
5. Förfarande enligt patentkrav 1 eller 2, k ä n -neteckat av, att den andra aktiverade katalysator-kompositionen med begränsad geometri omfattar ett zirkono- 15 cenkomplex med begränsad geometri och en aluminiumoxansamkatalysator .
6. Förfarande enligt patentkrav 2, k ä n neteckat av, att stegen (a) och (b) utföres väsentli-gen samtidigt i en gemensam reaktor. 2 0
7. Förfarande enligt patentkrav 6, k ä n ne teckat av, att det ytterligare omfattar steg, vid • · vilka man ’·"· (d) blandar den första och andra katalysatorkompo- ‘•"ί sitionen för bildande av en katalysatorblandning och : **: 25 (e) insprutar katalysatorblandningen i den gemen- ··· samma reaktorn. • · * ·
8. Förfarande enligt patentkrav 2, k ä n ne teckat av, att stegen (a) och (b) utföres separat i . . ätminstone tvä reaktorer. 3 0
9. Förfarande enligt patentkrav 8, k ä n n e - *;·* t e c k a t av, att de tvä reaktorerna omfattar ätminsto- : : : ne en första reaktor och en andra reaktor och att de tvä reaktorerna drivs i serie.
. 10. Förfarande enligt patentkrav 8, k ä n n e - ’ ; 35 t e c k a t av, att de tvä reaktorerna drivs parallellt. 110105
11. Förfarande enligt patentkrav 2, känne-t e c k a t av, att den i steget (a) producerade homogena etylen-a-olefin-sampolymeren har en smältpunkt frän 70 tili 110 °C och att den i steget (b) producerade homogena 5 etylen-a-olefin-sampolymeren har en smältpunkt frän 115 tili 130 °C.
12. Förfarande enligt patentkrav 2, kanne-t e c k a t av, att ett av α-olefinerna är ett C2_18-a-ole-fin. 10
13. Förfarande enligt patentkrav 12, känne- t e c k a t av, att ätminstone ett α-olefin valts bland etylen, 1-propen, isobutylen, 1-buten, 1-hexen, 4-metyl-l-penten och 1-okten.
14. Förfarande enligt patentkrav 13, känne- 15. e c k a t av, att den första och anra etylen-a-olefin- sampolymeren vardera omfattar en sampolymer av etylen och 1-okten.
15. Förfarande enligt patentkrav 2, känne-t e c k a t av, att antingen den första eller den andra 20 aktiverade katalysatorkompositionen med begränsad geomet-ri, eller vardera, valts bland katalysatorkomponenter med • · • f.‘ begränsad geometri, vilka valts bland titan, vanadin, haf- '“‘i nium och zirkon.
16. Sampolymerprodukt som erhällits med förfarandet 25 enligt patentkrav 2, känneteckad av, att den · första homogena etylen-a-olef in-sampolymeren och den andra ♦ I " · homogena etylen-a-olef in-sampolymeren kombineras i mäng-der, vilka förmär avge en sampolymerprodukt som har en . kristallisationsbegynnelsetemperatur av ätminstone 5 °C * · « 30 högre än kristallisationsbegynnelsetemperaturen hos sampo- * · ·;* lymeren som producerats av den aktiverade katalysatorkom- positionen med begränsad geometri och högre reaktivitet.
17. Sampolymerprodukt enligt patentkrav 2, k ä n - , netecknad av, att den första homogena etylen-a- t t ♦ ’ ; 35 olefin-sampolymeren och den andra homogena etylen-a-ole- tilli 110105 44 fin-sampolymeren kombineras i mängder som avger en kris-tallisationsbegynnelsetemperatur av ätminstone 110 °C.
18. Sampolymerprodukt enligt patentkrav 2, k ä n -netecknad av, att den första och andra etylen-a- 5 olefin-sampolymeren vardera omfattar en sampolymer av ety- len och 1-okten.
19. Fabricerad artikel som framställts av sampoly-merprodukten enligt patentkrav 16.
20. Fabricerad artikel enligt patentkrav 19 och 10 vald bland filmer, formade artiklar och fibrer. * 1 • · • · · · * · · • · · • Ml • · • 1 · • « • · · • · · • · « » • · · • · • · #
FI943116A 1991-12-30 1994-06-29 Polymerisering av eten sampolymerer FI110105B (sv)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US81571691A 1991-12-30 1991-12-30
US81571691 1991-12-30
US9211269 1992-12-29
PCT/US1992/011269 WO1993013143A1 (en) 1991-12-30 1992-12-29 Ethylene interpolymer polymerizations

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FI943116A0 FI943116A0 (sv) 1994-06-29
FI943116A FI943116A (sv) 1994-06-29
FI110105B true FI110105B (sv) 2002-11-29

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US (4) US6538070B1 (sv)
EP (1) EP0619827B1 (sv)
JP (1) JP3157163B2 (sv)
KR (1) KR100253826B1 (sv)
CA (1) CA2125780C (sv)
DE (1) DE69211569T2 (sv)
ES (1) ES2095037T3 (sv)
FI (1) FI110105B (sv)
WO (1) WO1993013143A1 (sv)

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US20030166784A1 (en) 2003-09-04
US6566446B1 (en) 2003-05-20
FI943116A (sv) 1994-06-29
JPH07502771A (ja) 1995-03-23
US6916883B2 (en) 2005-07-12
ES2095037T3 (es) 1997-02-01
DE69211569D1 (de) 1996-07-18
KR100253826B1 (ko) 2000-04-15

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