FI63950B - Silylkromat innehaollande katalysatorer foer polymerisation avtylen framstaellning och anvaendning av dessa katalysato rre - Google Patents
Silylkromat innehaollande katalysatorer foer polymerisation avtylen framstaellning och anvaendning av dessa katalysato rre Download PDFInfo
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- FI63950B FI63950B FI780140A FI780140A FI63950B FI 63950 B FI63950 B FI 63950B FI 780140 A FI780140 A FI 780140A FI 780140 A FI780140 A FI 780140A FI 63950 B FI63950 B FI 63950B
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- Prior art keywords
- weight
- silica
- catalyst
- calculated
- ethylene
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- 238000006116 polymerization reaction Methods 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 130
- 239000000377 silicon dioxide Substances 0.000 claims description 64
- 239000003054 catalyst Substances 0.000 claims description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 33
- 239000005977 Ethylene Substances 0.000 claims description 33
- CQBWEBXPMRPCSI-UHFFFAOYSA-M O[Cr](O[SiH3])(=O)=O Chemical compound O[Cr](O[SiH3])(=O)=O CQBWEBXPMRPCSI-UHFFFAOYSA-M 0.000 claims description 27
- 239000002685 polymerization catalyst Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 10
- AQLZCGLPNYEIDH-UHFFFAOYSA-N C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Cr](=O)(=O)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical group C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Cr](=O)(=O)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AQLZCGLPNYEIDH-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical group C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 239000002002 slurry Substances 0.000 description 14
- -1 aluminum modified silica Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 150000002222 fluorine compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000012025 fluorinating agent Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BCFRWAJVFIQTTM-UHFFFAOYSA-N [Cr](=O)(=O)(O[Si](C1=C(C=CC=C1)C)(C1=C(C=CC=C1)C)C1=C(C=CC=C1)C)O[Si](C1=C(C=CC=C1)C)(C1=C(C=CC=C1)C)C1=C(C=CC=C1)C.[Cr](=O)(=O)(O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cr](=O)(=O)(O[Si](C1=C(C=CC=C1)C)(C1=C(C=CC=C1)C)C1=C(C=CC=C1)C)O[Si](C1=C(C=CC=C1)C)(C1=C(C=CC=C1)C)C1=C(C=CC=C1)C.[Cr](=O)(=O)(O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 BCFRWAJVFIQTTM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- LAIHYGWCDMKQGB-UHFFFAOYSA-N dioxido(dioxo)chromium silicon(4+) Chemical compound [Cr](=O)(=O)([O-])[O-].[Si+4].[Cr](=O)(=O)([O-])[O-] LAIHYGWCDMKQGB-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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
- C08F10/02—Ethene
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Claims (19)
1. Katalvsator för polymerisering av etvlen ensamt eller kopoly-merisering av etvlen med oi-olefriner som innehAller 3...6 kolatomer, vilken katalysator innehAller en silylkromat med formeln R O R I H I R - Si - 0 - Cr - 0 - Si - R i li I R O R i vilken formel varje P är en kolväterad.ikal som innehAller l...ca 14 kolatomer, kännetecknad därav, att silyl-kromatet är anbringat pA en kiseldioxidbärare med stor yta, vilken bärare oA förhand är värmebehandlad vid 500...1000 °C varvid silyl-kromatmängden är sA stor att den ger 0,05...2,0 vikt-% krom, räknat som krom pA kata^ysatorns totala vikt, och kiseldioxidbäraren inne-hAller ca 0,01...50 vikt-% aluminium, räknat som AI2O3, ca 2...30 vikt-% titan, räknat som Ti02, och 0...10 vikt-% av ett fluorerings-ämne, alla räknade pA kiseldioxidens vikt.
2. Katalysator enligt patentkravet 1, kännetecknad därav, att R är fenyl.
3. Katalysator enligt patentkravet 1, kännetecknad därav, att aluminiummängden är 0,2...1 vikt-%, räknad som AI2O3 oA kiseldioxidens vikt.
4. Katalysator enligt patentkravet 1, kännetecknad __ I 18 63950 därav, att titanmängden är 2...20 vikt-%, räknat som T1O2 pä kiseldioxidens vikt.
5. Katalysator enligt patentkravet lf kännetecknad därav, att fluoreringsämnet föreligger i en mängd οτη 0,2...2 vikt-%, räknat pä kiseldioxidens vikt.
6. Katalysator enligt patentkravet 5, kännetecknad därav, att fluorerinqsämnet är ammonium-hexafluorsilikat.
7. Katalysator enligt patentkravet 1, kännetecknad därav, att kiseldioxidens oorstorlek är 10...45 nm, medelDartikelstorleken är 50...200 /um och ytan är 200...500 m^/g.
8. Katalysator enligt patentkravet 1, kännetecknad därav, att kiseldioxidens porstorlek är 20...30 nm, partikelstorleken är 50...200 yum och vtan är 300...450 m2/g.
9. Förfarande för katalvtisk polvmerisering av etylen ensamt eller kopolymeriserinq av etylen med <*-olefiner med 3...6 kolatomer, varvid man som katalysator använder en katalysator som innehäller en silylkromat med formeln R O R i a I R-Si-O-Cr-O-Si-R I H I R O R i vilken formel varje R är en kolväteradikal som innehäller l...ca 14 kolatomer, kännetecknat därav, att silvl-kromatet är anbringat ph en kiseldioxidbärare med stor yta, vilken bärare ph förhand är värmebehandlad vid 500...1000 °C varvid silyl-kromatmänqden är sh stor att den ger 0,05...2,0 vikt-% krom, räknat som krom pä katalysatorns totala vikt, och kiseidioxidbäraren inne-häller ca 0,01...50 vikt-% aluminium, räknat som AI2O3, ca 2...30 vikt-% titan, räknat som Ti02, och 0...10 vikt-% av ett fluorerings-ämne, alla räknade pä kiseldioxidens vikt. 19 63950
10. Förfarande enligt patentkravet 9, kännetecknat därav, att cX-olefinen är propvlen.
11. Förfarande enliqt patentkravet 9, kännetecknat därav, att c*-olefinen är 1-hexen.
12. Förfarande enligt patentkravet 9, kännetecknat därav, att «X-olefinen är 1-buten.
13. Förfarande enligt patentkravet 9, kännetecknat därav, att aiuminiummängden i katalvsatorn är 0,2...1 vikt-%, räknat som AI2O3 o$ kiseldioxidens vikt.
14. Förfarande enliqt patentkravet 9, kännetecknat därav, att katalvsatorn innehäller 0,2...1 vikt-% aluminium, räknat sora AI2O3, ocb 2...20 vikt-% titan, räknat som T1O2, allt pä kiseldioxidens vikt.
15. Förfarande enligt patentkravet 14, kännetecknat därav, att silylkromatet är bis-trifenylsilylkromat och föreligger i en mängd som är tillräckliq för att ge ca 0,05...2 vikt-% krom, räknat som krom pä katalysatorns totalvikt,
16. Förfarande för framställninq av en silylkromat innehällande polymerisationskatalvsator för etylen, kännetecknat därav, att man: A) uppvärmer en kiseldioxidbärate med stor yta, som innehäller bäde ca 0,01...50 vikt-% aluminium, räknat som AI2O3, ca 2...30 vikt-% titan, räknat som T1O2, och 0...10 vikt-% av ett fluo-rerinqsämne, alla räknade pä kiseldioxidens vikt tili 500. . .1000 °C., B) avkyler kiseldioxidbäraren, och C) anbringar pä den avkylda kiseldioxidbäraren ett silylkromat med formeln R O R i li I R-qi-Q-Cr-O-Ri-R I II I R O R
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/761,213 US4100105A (en) | 1977-01-21 | 1977-01-21 | Titanium-modified silyl chromate catalysts for ethylene polymerization |
US76121377 | 1977-01-21 |
Publications (3)
Publication Number | Publication Date |
---|---|
FI780140A FI780140A (fi) | 1978-07-22 |
FI63950B true FI63950B (fi) | 1983-05-31 |
FI63950C FI63950C (fi) | 1983-09-12 |
Family
ID=25061518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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FI780140A FI63950C (fi) | 1977-01-21 | 1978-01-16 | Silylkromat innehaollande katalysatorer foer polymerisation avtylen framstaellning och anvaendning av dessa katalysato rre |
Country Status (26)
Country | Link |
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US (2) | US4100105A (sv) |
JP (1) | JPS5391092A (sv) |
AR (1) | AR223142A1 (sv) |
AU (1) | AU524400B2 (sv) |
BE (1) | BE863121A (sv) |
BR (1) | BR7800318A (sv) |
CA (1) | CA1111408A (sv) |
CS (1) | CS203181B2 (sv) |
DE (1) | DE2802517A1 (sv) |
DK (1) | DK152216C (sv) |
EG (1) | EG13129A (sv) |
ES (2) | ES466207A1 (sv) |
FI (1) | FI63950C (sv) |
FR (1) | FR2378048A1 (sv) |
GB (1) | GB1551596A (sv) |
HK (1) | HK37483A (sv) |
IN (1) | IN147022B (sv) |
IT (1) | IT1093202B (sv) |
MX (1) | MX4482E (sv) |
NL (1) | NL177315C (sv) |
NO (1) | NO155140C (sv) |
NZ (1) | NZ186280A (sv) |
PH (1) | PH13673A (sv) |
SE (1) | SE441273B (sv) |
SU (1) | SU1025322A3 (sv) |
ZA (1) | ZA777666B (sv) |
Families Citing this family (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4263422A (en) * | 1979-12-31 | 1981-04-21 | The Dow Chemical Company | Polymerization of olefins with dual, independently supported catalysts |
US4532311A (en) * | 1981-03-26 | 1985-07-30 | Union Carbide Corporation | Process for reducing sheeting during polymerization of alpha-olefins |
US4792592A (en) * | 1981-03-26 | 1988-12-20 | Union Carbide Corporation | Process for reducing sheeting during polymerization of alpha-olefins |
JPS58170957A (ja) * | 1982-03-31 | 1983-10-07 | Aisin Warner Ltd | 車両用自動変速機のアキユムレ−タ |
JPH0725817B2 (ja) * | 1986-04-23 | 1995-03-22 | 日本石油株式会社 | オレフイン重合用触媒 |
JPH072798B2 (ja) * | 1987-10-28 | 1995-01-18 | 住友化学工業株式会社 | オレフィン重合用固体触媒成分 |
EP0594914A1 (en) * | 1992-10-26 | 1994-05-04 | Bp Chemicals S.N.C. | Preparation of a catalyst for the manufacture of polyethylene |
US6720396B2 (en) * | 2000-11-30 | 2004-04-13 | Univation Technologies, Llc | Polymerization process |
FR2825357B1 (fr) * | 2001-05-31 | 2004-04-30 | Cit Alcatel | Procede de dopage de la silice par du fluor |
US6989344B2 (en) * | 2002-12-27 | 2006-01-24 | Univation Technologies, Llc | Supported chromium oxide catalyst for the production of broad molecular weight polyethylene |
CA2517269A1 (en) * | 2003-03-28 | 2004-11-04 | Union Carbide Chemicals & Plastics Technology Corporation | Chromium-based catalysts in mineral oil for production of polyethylene |
US6982304B2 (en) * | 2003-12-22 | 2006-01-03 | Union Carbide Chemicals & Plastics Technology Corporation | Blow molding resins with improved ESCR |
US7790826B2 (en) * | 2004-05-06 | 2010-09-07 | DowGlobal Technologies Inc. | Polymer molding compositions |
DE602005020688D1 (de) | 2004-12-17 | 2010-05-27 | Dow Global Technologies Inc | Rheologiemodifizierte polyethylenzusammensetzungen |
US7629422B2 (en) | 2004-12-21 | 2009-12-08 | Univation Technologies, Llc | Process for transitioning between Ziegler-Natta-based and chromium-based catalysts |
CN100436316C (zh) * | 2005-12-16 | 2008-11-26 | 厦门大学 | 一种硅胶载体的制备方法 |
CA2605044C (en) * | 2007-10-01 | 2014-12-02 | Nova Chemicals Corporation | Polymerization process using a mixed catalyst system |
CA2740755C (en) | 2011-05-25 | 2019-01-15 | Nova Chemicals Corporation | Chromium catalysts for olefin polymerization |
CA2783494C (en) | 2012-07-23 | 2019-07-30 | Nova Chemicals Corporation | Adjusting polymer composition |
CA2800056A1 (en) | 2012-12-24 | 2014-06-24 | Nova Chemicals Corporation | Polyethylene blend compositions |
SG10201906006QA (en) | 2013-11-21 | 2019-08-27 | Univation Tech Llc | Method for controlling polyolefin properties during polymerisation |
CA2837591A1 (en) | 2013-12-19 | 2015-06-19 | Nova Chemicals Corporation | Polyethylene composition for extrusion coating |
WO2015181151A1 (en) | 2014-05-27 | 2015-12-03 | Sabic Global Technologies B.V. | Process for transitioning between incompatible catalysts |
JP6674911B2 (ja) | 2014-06-24 | 2020-04-01 | ノヴァ ケミカルズ(アンテルナショナル)ソシエテ アノニム | 攪拌反応器内の局所流体齢の制御 |
CA2857456C (en) | 2014-07-22 | 2022-05-03 | Nova Chemicals Corporation | Improved control over particulate feed |
EP3188834B1 (en) | 2014-09-02 | 2021-02-17 | Univation Technologies, LLC | Polyolefin production with chromium-based catalysts |
SG11201701451UA (en) | 2014-09-02 | 2017-03-30 | Univation Tech Llc | Polyolefin production with chromium-based catalysts |
SG11201701437PA (en) | 2014-09-02 | 2017-03-30 | Univation Tech Llc | Polyolefin production with chromium-based catalysts |
CA2870027C (en) | 2014-11-07 | 2022-04-26 | Matthew Zaki Botros | Blow molding composition and process |
US10266618B2 (en) | 2014-11-24 | 2019-04-23 | Univation Technologies, Llc | Chromium-based catalyst compositions for olefin polymerization |
EP3223943B1 (en) | 2014-11-24 | 2023-09-27 | Univation Technologies, LLC | Composition comprising particles |
CA2891002C (en) | 2015-05-13 | 2022-09-06 | Veronica Rose Zimmerman | Modeling a bed plate and its use |
PL3377421T3 (pl) | 2015-11-19 | 2021-06-14 | Dow Global Technologies Llc | Kompozycje polietylenowe mające właściwości żywego zawiasu |
ES2765241T3 (es) | 2015-12-10 | 2020-06-08 | Dow Global Technologies Llc | Cintas, fibras o monofilamentos de polietileno que comprenden un polímero de etileno/alfa-olefina |
MX2018007480A (es) | 2015-12-21 | 2018-08-01 | Dow Global Technologies Llc | Formulaciones de polietileno con barrera mejorada y dureza para aplicaciones de moldeo. |
US11492467B2 (en) | 2015-12-21 | 2022-11-08 | Dow Global Technologies Llc | Polyethylene formulations with improved barrier and environmental stress crack resistance |
EP3408314B1 (en) | 2016-01-29 | 2020-12-23 | Univation Technologies, LLC | Polyolefin film with improved toughness |
JP6971252B2 (ja) | 2016-04-20 | 2021-11-24 | ユニベーション・テクノロジーズ・エルエルシー | ポリマーフローインデックス調整剤 |
CN109983035B (zh) | 2016-12-15 | 2022-02-11 | 尤尼威蒂恩技术有限责任公司 | 对聚合工艺进行评定 |
US11161924B2 (en) | 2017-10-27 | 2021-11-02 | Univation Technologies, Llc | Polyethylene copolymer resins and films |
CA3079202A1 (en) | 2017-10-27 | 2019-05-02 | Univation Technologies, Llc | Selectively transitioning polymerization processes |
US10738182B2 (en) | 2018-04-23 | 2020-08-11 | Dow Global Technologies Llc | Molded articles and methods thereof |
US20210070902A1 (en) | 2018-05-24 | 2021-03-11 | Univation Technologies, Llc | Unimodal polyethylene copolymer and film thereof |
EP3830145A1 (en) | 2018-07-31 | 2021-06-09 | Univation Technologies, LLC | Unimodal polyethylene copolymer and film thereof |
CN112585177A (zh) | 2018-07-31 | 2021-03-30 | 尤尼威蒂恩技术有限责任公司 | 单峰聚乙烯共聚物和其膜 |
CN112673032B (zh) | 2018-09-24 | 2024-03-15 | 切弗朗菲利浦化学公司 | 制备具有增强的聚合活性的负载型铬催化剂的方法 |
CA3142138A1 (en) | 2019-06-10 | 2020-12-17 | Univation Technologies, Llc | Polyethylene blend |
WO2021205333A1 (en) | 2020-04-07 | 2021-10-14 | Nova Chemicals (International) S.A. | High density polyethylene for rigid articles |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1545098C3 (de) * | 1963-09-05 | 1980-11-06 | Union Carbide Corp., New York, N.Y. (V.St.A.) | Verfahren zur Polymerisation von Äthylen |
NL128841C (sv) | 1963-06-21 | |||
NL135065C (sv) * | 1965-05-14 | |||
US3445367A (en) * | 1965-11-22 | 1969-05-20 | Phillips Petroleum Co | Catalyst and process for making olefin polymers of narrow molecular weight distribution |
US3622521A (en) * | 1967-08-21 | 1971-11-23 | Phillips Petroleum Co | Olefin polymerization with chromium and titanium-containing compounds |
US3704287A (en) * | 1970-09-17 | 1972-11-28 | Union Carbide Corp | High temperature reduced catalyst and process |
US3974101A (en) * | 1970-10-08 | 1976-08-10 | Phillips Petroleum Company | Olefin polymerization catalyst |
US3887494A (en) * | 1970-11-12 | 1975-06-03 | Phillips Petroleum Co | Olefin polymerization catalyst |
US3798202A (en) * | 1971-10-12 | 1974-03-19 | Phillips Petroleum Co | Polyolefin production |
US3870656A (en) * | 1972-05-25 | 1975-03-11 | Phillips Petroleum Co | Preparation of silica-containing compositions |
GB1429174A (en) * | 1972-06-12 | 1976-03-24 | Bp Chem Int Ltd | Polymerisation process and catalyst |
US3884832A (en) * | 1974-02-04 | 1975-05-20 | Chemplex Co | Organotin chromate polymerization catalyst |
US3941761A (en) * | 1974-02-04 | 1976-03-02 | Chemplex Company | Method of polymerizing olefins |
GB1495547A (en) * | 1974-03-22 | 1977-12-21 | British Petroleum Co | Polymerisation catalyst |
US3959178A (en) * | 1974-03-28 | 1976-05-25 | Phillips Petroleum Company | Mixed hydrocarbyloxide treated catalyst activated at different temperatures |
US3950316A (en) * | 1974-05-03 | 1976-04-13 | Phillips Petroleum Company | Catalyst support formed by adding acidic material to silica containing titanium |
GB1447605A (en) | 1974-05-08 | 1976-08-25 | Phillips Petroleum Co | Olefin polymerization catalyst peparation |
GB1505994A (en) * | 1974-06-11 | 1978-04-05 | British Petroleum Co | Polymerisation process |
US3976632A (en) * | 1974-12-04 | 1976-08-24 | Phillips Petroleum Company | Reactivation of organochromium olefin polymerization catalyst in presence of oxygen |
US4001196A (en) * | 1974-12-04 | 1977-01-04 | Phillips Petroleum Company | Reactivation of organochromium olefin polymerization catalyst in presence of oxygen |
US4011382A (en) * | 1975-03-10 | 1977-03-08 | Union Carbide Corporation | Preparation of low and medium density ethylene polymer in fluid bed reactor |
US4049896A (en) * | 1975-03-14 | 1977-09-20 | National Petro Chemicals Corporation | Olefin polymerization catalyst |
US3984351A (en) * | 1975-03-14 | 1976-10-05 | National Petro Chemicals Corporation | Olefin polymerization catalyst |
US4016343A (en) * | 1975-08-22 | 1977-04-05 | Chemplex Company | Tetravalent chromium alkoxide polymerization catalyst and method |
US4053437A (en) * | 1976-03-04 | 1977-10-11 | Chemplex Company | Polyolefin catalyst and method for its preparation |
US4065612A (en) * | 1976-03-30 | 1977-12-27 | Union Carbide Corporation | Phenol modified polymerization catalyst and polymerization process |
-
1977
- 1977-01-21 US US05/761,213 patent/US4100105A/en not_active Expired - Lifetime
- 1977-12-28 ZA ZA00777666A patent/ZA777666B/xx unknown
-
1978
- 1978-01-12 CA CA294,855A patent/CA1111408A/en not_active Expired
- 1978-01-16 FI FI780140A patent/FI63950C/fi not_active IP Right Cessation
- 1978-01-18 AU AU32514/78A patent/AU524400B2/en not_active Expired
- 1978-01-19 BR BR7800318A patent/BR7800318A/pt unknown
- 1978-01-20 SE SE7800738A patent/SE441273B/sv not_active IP Right Cessation
- 1978-01-20 NO NO780227A patent/NO155140C/no unknown
- 1978-01-20 PH PH20695A patent/PH13673A/en unknown
- 1978-01-20 DE DE19782802517 patent/DE2802517A1/de active Granted
- 1978-01-20 IT IT19503/78A patent/IT1093202B/it active
- 1978-01-20 BE BE184483A patent/BE863121A/xx not_active IP Right Cessation
- 1978-01-20 NZ NZ186280A patent/NZ186280A/xx unknown
- 1978-01-20 GB GB2471/78A patent/GB1551596A/en not_active Expired
- 1978-01-20 NL NLAANVRAGE7800749,A patent/NL177315C/xx not_active IP Right Cessation
- 1978-01-20 AR AR270782A patent/AR223142A1/es active
- 1978-01-20 DK DK029778A patent/DK152216C/da not_active IP Right Cessation
- 1978-01-20 JP JP441278A patent/JPS5391092A/ja active Granted
- 1978-01-20 ES ES466207A patent/ES466207A1/es not_active Expired
- 1978-01-20 MX MX78100707U patent/MX4482E/es unknown
- 1978-01-20 SU SU782568008A patent/SU1025322A3/ru active
- 1978-01-20 CS CS78410A patent/CS203181B2/cs unknown
- 1978-01-20 FR FR7801618A patent/FR2378048A1/fr active Granted
- 1978-01-20 IN IN82/CAL/78A patent/IN147022B/en unknown
- 1978-01-21 EG EG34/78A patent/EG13129A/xx active
- 1978-03-07 ES ES467604A patent/ES467604A1/es not_active Expired
- 1978-04-12 US US05/895,662 patent/US4152502A/en not_active Expired - Lifetime
-
1983
- 1983-09-29 HK HK374/83A patent/HK37483A/xx unknown
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