FI106309B - Förfarande för polymerisering av alfa-olefiner i en gasfas - Google Patents
Förfarande för polymerisering av alfa-olefiner i en gasfas Download PDFInfo
- Publication number
- FI106309B FI106309B FI930404A FI930404A FI106309B FI 106309 B FI106309 B FI 106309B FI 930404 A FI930404 A FI 930404A FI 930404 A FI930404 A FI 930404A FI 106309 B FI106309 B FI 106309B
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- FI
- Finland
- Prior art keywords
- compound
- propylene
- polymers
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- polymerization
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- 238000000034 method Methods 0.000 title claims description 59
- 230000008569 process Effects 0.000 title claims description 42
- 239000004711 α-olefin Substances 0.000 title description 6
- 230000000379 polymerizing effect Effects 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 55
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 31
- -1 aluminum alkyl compound Chemical class 0.000 claims description 27
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- 229910052782 aluminium Inorganic materials 0.000 claims description 21
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- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 239000000203 mixture Substances 0.000 claims description 13
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- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
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- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
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- 239000000600 sorbitol Substances 0.000 claims description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
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- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
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- 150000001993 dienes Chemical class 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 229920001866 very low density polyethylene Polymers 0.000 description 2
- VUQSKJXSSAXICG-UHFFFAOYSA-N 1,3-dimethoxy-5-methylhexane Chemical compound COCCC(OC)CC(C)C VUQSKJXSSAXICG-UHFFFAOYSA-N 0.000 description 1
- ROSQVPGTZCDBOC-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C)(COC)CC(C)C ROSQVPGTZCDBOC-UHFFFAOYSA-N 0.000 description 1
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLNTWVDSQRNWFU-UHFFFAOYSA-N OOOOOOO Chemical compound OOOOOOO JLNTWVDSQRNWFU-UHFFFAOYSA-N 0.000 description 1
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- 244000309493 Soybean severe stunt virus Species 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
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- 238000002083 X-ray spectrum Methods 0.000 description 1
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910000423 chromium oxide Inorganic materials 0.000 description 1
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- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- OFPXSFXSNFPTHF-UHFFFAOYSA-N oxaprozin Chemical compound O1C(CCC(=O)O)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 OFPXSFXSNFPTHF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012289 standard assay Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/18—Assembling together the component parts of electrode systems
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
-
- 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
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
Landscapes
- 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)
- Manufacturing & Machinery (AREA)
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Claims (16)
1. Förfarande för tillverkning av (ko)polymerer av olefiner CH2=CHR, där R är en väteatom eller en alkyl- el-5 ler arylradikal med 1—10 kolatoraer, vilket förfarande om-fattar ätminstone ett (ko) polymeriseringsskede i gasfasen, i vilken en fluidiserad eller omrörd bädd upprätthälles under närvaro av en sädan katalyt som bestär av en produkt ur reaktionen mellan (1) en fast komponent som innehäller en 10 titanförening pä ett magnesiumdihalogenidbärarmaterial i aktiv form som alternativt innehäller en inre elektrondo-nor, samt (2) en aluminiumalkylförening, alternativt under närvaro av en yttre elektrondonor, varvid nämnda förfarande är kännetecknat av att: 15 den nämnda fluidiserade eller omrörda bädden bestär av polymerpartiklar i granulform, av vilka ätminstone 80 % är större än 500 pm och under 10 % är mindre än 200 pm; och en förening (3), med en ked av ätminstone 4 kolato-mer och som innehäller ätminstone 2 grupper, av samma eller 20 olika slag, som förmär reagera med aluminiumalkylföreningen r (2), mätäs i vilket som heist skede av förfarandet en mängd * I < t som är större än 100 ppm av vikten av nämnda (ko)polymer, ,varvid molf örhällandet mellan föreningen (3) och nämnda aluminiumalkylförening (2) är mindre än 1; * * * • *,: 25 varvid nämnda förening (3) förmär vid användning i • · · ·' ett standardprov vid polymerisationen av en blandning av eten och propen förhindra polymerisationen i sädana poly-merpartiklar som är mindre än 850 pm.
·***: 2. Förfarande enligt patentkrav 1, • * · ;·) 30 kännetecknat av att föreningen (3) har valts • · · bland sädana som hör tili nägon av följande grupper: (a) polyalkoholer som innehäller kedar med 4-8 ko- • · ” latomer; « t 30 106309 (b) hydroxiestrar med ätminstone tvä fria hydroxyl-grupper, och vilka erhällits ur karboxylsyror med 8—22 ko-latomer samt ur polyalkoholer; (c) N-alkyldietanolaminer av formeln: CH3(CH2)nCH2-
3. Förfarande enligt patentkrav 2, kännetecknat av att föreningen (3) har valts ur en grupp som omfattar 1,4-butandiol, sorbitol, glycerolmo- 10 nostearat, sorbitanmonooleat, epoxerad linfröolja, epoxerad sojaolja, samt N-alkyldietanolaminer av formeln CH3 (CH) nCH2N- (CH2CH2OH) 2, där n är inom intervallet 6—20.
4. Förfarande enligt patentkrav 1, kännetecknat av att föreningen (3) mätäs en 15 mängd som är inom intervallet 100—2000 ppm av vikten i för-hällande tili mängden slutlig polymer, varvid molförhällan-det mellan föreningen (3) och aluminiumalkylföreningen är inom intervallet 0,05—0,8.
5. Förfarande enligt patentkrav 1, 20 kännetecknat av att alkan, med 3—5 kolatomer, ..li' är närvarande i gasfasen i en molhalt om 20—90 % i förhäl- lande tili den totala mängden gas.
..|·' 6. Förfarande enligt patentkrav 5, : kännetecknat av att alkanen är propan. • * · J*: 25
7. Förfarande enligt patentkrav 1, kännetecknat av att titanföreningen innehäller ätminstone en halogen-Ti-bindning.
:***; 8. Förfarande enligt patentkrav 1, • · · ·***: kännetecknat av att den fasta komponenten inne- • · · 30 häller en inre elektrondonor och reaktionen utföres under ( 1 1 e närvaro av en yttre elektrondonor. • ·
5 N (CH2CH2OH) 2, där n är större än 2; samt (d) omättade polyepoxidatoljor.
9. Förfarande enligt patentkrav 1, kännetecknat av att den inre elektrondonorföre- • '· ningen är dieter med formeln: 106309 R' CHjOR'" \ / C / \ R" CHjOR,v 5 där R1 och R11, sairana eller olika, är alkyl-, cyklo- alkyl- eller arylradikaler med 1—18 kolatomer.
10. Förfarande enligt patentkrav 8, kännetecknat av att den fasta komponenten (1) uppvisar sfärisk form. 10
11. Förfarande enligt patentkrav 9, kännetecknat av att den fasta komponenten (1) uppvisar sfärisk form.
12. Produkter av förfarandena enligt vilket som heist av patentkraven 1—11.
13. Polymerer i granulform av olefiner, vilka er hällits genom ett förfarande enligt vilket som heist av patentkraven 1-9, kännetecknade av att före-ningen (3) är koncentrerad i sädana polymerpartiklar, vilka är mindre än 700 pm.
14. Sfäriska polymerer av olefiner, vilka har er- hällits genom förfarandet enligt patentkrav 10, I · < * kännetecknade av att föreningen (3) är kon- ' 1 centrerad i sädana polymerpartiklar, vilka är mindre än 700 μ™· • 25 15. (Ko)polymerer av eten, vilka har erhällits ge- nom förfarandet enligt patentkrav 1, kännetecknade av att föreningen (3) är kon- centrerad i sädana polymerpartiklar, vilka är mindre än 700 t · · - ·*·*: pm. • « · ./ 30 16. (Ko)polymerer av propen, vilka har erhällits * «* *... genom förfarandet enligt patentkrav 8 eller 9, '/ kännetecknade av att föreningen (3) är kon- t « centrerad i sädana polymerpartiklar, vilka är mindre än 700 ' ' pm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI920191 | 1992-01-31 | ||
| ITMI920191A IT1262933B (it) | 1992-01-31 | 1992-01-31 | Processo per la polimerizzazione in fase gas di alfa-olefine |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| FI930404A0 FI930404A0 (fi) | 1993-01-29 |
| FI930404A FI930404A (fi) | 1993-08-01 |
| FI106309B true FI106309B (sv) | 2001-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI930404A FI106309B (sv) | 1992-01-31 | 1993-01-29 | Förfarande för polymerisering av alfa-olefiner i en gasfas |
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| US (1) | US5410002A (sv) |
| EP (1) | EP0560035B1 (sv) |
| KR (1) | KR100262204B1 (sv) |
| CN (1) | CN1041833C (sv) |
| AR (1) | AR246070A1 (sv) |
| AT (1) | ATE159732T1 (sv) |
| AU (1) | AU653885B2 (sv) |
| BR (1) | BR9300452A (sv) |
| CA (1) | CA2088524C (sv) |
| DE (1) | DE69314826T2 (sv) |
| DK (1) | DK0560035T3 (sv) |
| ES (1) | ES2110529T3 (sv) |
| FI (1) | FI106309B (sv) |
| GR (1) | GR3025520T3 (sv) |
| IL (1) | IL104560A (sv) |
| IT (1) | IT1262933B (sv) |
| MX (1) | MX9300541A (sv) |
| MY (1) | MY109770A (sv) |
| NO (1) | NO301124B1 (sv) |
| RU (1) | RU2124026C1 (sv) |
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| DE3833444A1 (de) * | 1988-10-01 | 1990-04-05 | Basf Ag | Vermeidung von farbigen verunreinigungen bei der herstellung von ultrahochmolekularen ethylenpolymerisaten mittels eines titan enthaltenden katalysatorsystems |
| DE3833445A1 (de) * | 1988-10-01 | 1990-04-05 | Basf Ag | Vermeidung von farbigen verunreinigungen bei der herstellung von ultrahochmolekularen ethylenpolymerisaten mittels eines titan enthaltenden katalysatorsystems |
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| US5036480A (en) * | 1990-03-12 | 1991-07-30 | Honeywell Inc. | Method and apparatus for simulating microburst windshears |
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-
1992
- 1992-01-31 IT ITMI920191A patent/IT1262933B/it active IP Right Grant
-
1993
- 1993-01-28 EP EP93101285A patent/EP0560035B1/en not_active Expired - Lifetime
- 1993-01-28 AT AT93101285T patent/ATE159732T1/de not_active IP Right Cessation
- 1993-01-28 ES ES93101285T patent/ES2110529T3/es not_active Expired - Lifetime
- 1993-01-28 DE DE69314826T patent/DE69314826T2/de not_active Expired - Lifetime
- 1993-01-28 DK DK93101285.0T patent/DK0560035T3/da active
- 1993-01-29 RU RU93004487/04A patent/RU2124026C1/ru not_active IP Right Cessation
- 1993-01-29 IL IL10456093A patent/IL104560A/en not_active IP Right Cessation
- 1993-01-29 US US08/010,749 patent/US5410002A/en not_active Expired - Lifetime
- 1993-01-29 FI FI930404A patent/FI106309B/sv active
- 1993-01-29 ZA ZA93666A patent/ZA93666B/xx unknown
- 1993-01-30 CN CN93102676A patent/CN1041833C/zh not_active Expired - Fee Related
- 1993-01-30 MY MYPI93000151A patent/MY109770A/en unknown
- 1993-01-30 TW TW082100593A patent/TW229216B/zh active
- 1993-01-30 KR KR1019930001255A patent/KR100262204B1/ko not_active IP Right Cessation
- 1993-02-01 BR BR9300452A patent/BR9300452A/pt not_active IP Right Cessation
- 1993-02-01 MX MX9300541A patent/MX9300541A/es unknown
- 1993-02-01 NO NO930347A patent/NO301124B1/no not_active IP Right Cessation
- 1993-02-01 AU AU32159/93A patent/AU653885B2/en not_active Ceased
- 1993-02-01 CA CA002088524A patent/CA2088524C/en not_active Expired - Fee Related
- 1993-02-02 AR AR93324216A patent/AR246070A1/es active
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|---|---|
| AU653885B2 (en) | 1994-10-13 |
| CA2088524C (en) | 2006-07-18 |
| CN1041833C (zh) | 1999-01-27 |
| TW229216B (sv) | 1994-09-01 |
| ZA93666B (en) | 1993-09-02 |
| CN1075484A (zh) | 1993-08-25 |
| NO930347D0 (no) | 1993-02-01 |
| DE69314826T2 (de) | 1998-04-30 |
| US5410002A (en) | 1995-04-25 |
| KR930016447A (ko) | 1993-08-26 |
| GR3025520T3 (en) | 1998-02-27 |
| MX9300541A (es) | 1993-07-01 |
| DE69314826D1 (de) | 1997-12-04 |
| MY109770A (en) | 1997-06-30 |
| ITMI920191A0 (it) | 1992-01-31 |
| EP0560035B1 (en) | 1997-10-29 |
| DK0560035T3 (da) | 1997-12-01 |
| NO301124B1 (no) | 1997-09-15 |
| ITMI920191A1 (it) | 1993-07-31 |
| RU2124026C1 (ru) | 1998-12-27 |
| CA2088524A1 (en) | 1993-08-01 |
| IT1262933B (it) | 1996-07-22 |
| KR100262204B1 (ko) | 2000-07-15 |
| FI930404A (fi) | 1993-08-01 |
| NO930347L (no) | 1993-08-02 |
| AU3215993A (en) | 1993-08-05 |
| AR246070A1 (es) | 1994-03-30 |
| BR9300452A (pt) | 1993-08-03 |
| FI930404A0 (fi) | 1993-01-29 |
| EP0560035A1 (en) | 1993-09-15 |
| IL104560A (en) | 1995-08-31 |
| ATE159732T1 (de) | 1997-11-15 |
| ES2110529T3 (es) | 1998-02-16 |
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