NO159283B - Polymeriseringskatalysator, og fast katalysatorbestanddelfor anvendelse ved fremstilling av katalysatoren. - Google Patents
Polymeriseringskatalysator, og fast katalysatorbestanddelfor anvendelse ved fremstilling av katalysatoren. Download PDFInfo
- Publication number
- NO159283B NO159283B NO812677A NO812677A NO159283B NO 159283 B NO159283 B NO 159283B NO 812677 A NO812677 A NO 812677A NO 812677 A NO812677 A NO 812677A NO 159283 B NO159283 B NO 159283B
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- Prior art keywords
- catalyst
- compound
- component
- dihalide
- solid
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 27
- 239000011949 solid catalyst Substances 0.000 title claims description 9
- 230000000379 polymerizing effect Effects 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 150000003377 silicon compounds Chemical class 0.000 claims description 17
- -1 aluminum compound Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 description 31
- 239000010936 titanium Substances 0.000 description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical group CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- 238000002083 X-ray spectrum Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000012093 Myrtus ugni Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000061461 Tema Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GZDPONITMCBDOX-UHFFFAOYSA-N [ethoxy(diphenyl)silyl] triethyl silicate Chemical compound C=1C=CC=CC=1[Si](OCC)(O[Si](OCC)(OCC)OCC)C1=CC=CC=C1 GZDPONITMCBDOX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 description 1
- LEYKSONZGURWNL-UHFFFAOYSA-N chloro-diethoxy-phenylsilane Chemical compound CCO[Si](Cl)(OCC)C1=CC=CC=C1 LEYKSONZGURWNL-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CNWUDMDXRVLRRB-UHFFFAOYSA-N n-[diethoxy(phenyl)silyl]-n-ethylethanamine Chemical compound CCO[Si](OCC)(N(CC)CC)C1=CC=CC=C1 CNWUDMDXRVLRRB-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- YYPIRAZPRGBECO-UHFFFAOYSA-N triethoxysilyl acetate Chemical compound CCO[Si](OCC)(OCC)OC(C)=O YYPIRAZPRGBECO-UHFFFAOYSA-N 0.000 description 1
- GYTROFMCUJZKNA-UHFFFAOYSA-N triethyl triethoxysilyl silicate Chemical compound CCO[Si](OCC)(OCC)O[Si](OCC)(OCC)OCC GYTROFMCUJZKNA-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- C08F4/02—Carriers therefor
-
- 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
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Description
Foreliggende oppfinnelse vedrører en katalysator som
angitt i krav l's ingress samt en fast katalysatorbestanddel, ifølge krav 2, for anvendelse ved fremstilling av katalysatoren.
De bårede og meget aktive og meget stereospesifikke katalysatorer som til nå har vært anvendt for polymerisering av propylen og høyere olefiner erholdes ved omsetning av en Al-alkyl-forbindelse, delvis kompleksbundet med en elektrondonor-forbindelse (ekstern donor) med en fast forbindelse omfatt-ende en Ti-forbindelse og en elektrondonor-forbindelse (intern donor) båret på et magnesiumhalogenid i aktiv form.
Eksempler på slike katalysatorer er beskrevet bl.a. i brit-isk patent nr. 1.559.194 og belgisk patent nr. 868,682.
De ovenfor bårede katalysatorer trenger anvendelse av en intern donor for erholdelse av polymerer med en høy isotak-tisitetsindeks. Hvis den interne donor er utelatt erholdes polymerer med lav isotaktisk indeks.
Det er nå overraskende funnet at det er mulig å oppnå med høyt utbytte polymerer fra a-olefiner med høy isotaktisk indeks under anvendelse av Ti-inneholdende, magnesiumdi-halogenid-bårede katalysatorer fri fra interne elektron-donorforbindelser, hvis det i stedet anvendes en ekstern donor som er en silisiumforbindelse inneholdende Si-OR bindinger.
Det er også uventet funnet at aktiviteten og stereospesifi-siteten for katalysatorene ytterligere kan forøkes hvis silisiumforbindelsen anvendt som ekstern donor også er tilstede som intern donor også i den Ti-inneholdende Mg-dihalogenid-bårede bestanddel i mengder tilsvarende molforhold mellom silisiumforbindelsen og den bårede halogenerte Ti-forbindelse på 0,1 til 5.
De ovenfor nevnte resultater er overraskende når man tar i betraktning at det er kjent katalysatorer som fremstilles ved å anvende både som intern og ekstern donor en silikonforbindelse inneholdende Si-O-C bindinger, men som med hensyn til aktivitet og stereospesifisitet ikke er bedre enn det som erholdes med katalysatorer hvori en ester av benzo-syre anvendes som intern og ekstern donor.
Denne heller dårlige virkning for de kjente katalysatorer skyldes det faktum at Si-inneholdende interne donorer i det vesentlige fjernes fra den Ti-inneholdende bårede komponent som følge av fremstillingen av denne.
Katalysatorene ifølge oppfinnelsen omfatter reaksjonspro-dukter mellom de følgende bestanddeler:
a) en Al-trialkyl-forbindelse.
b) en silisiumforbindelse inneholdende en eller flere
Si-OR-bindinger, hvori R er en hydrokarbongruppe,
c) en fast komponent bestående av en Ti-forbindelse,
og eventuelt en elektrondonor-forbindelse, båret på
et Mg-dihalogenid i aktiv form. Katalysatoren er sær-preget ved det som er angitt i krav 1's karakteriser-ende del.
De aktive vannfrie Mg-dihalogenider som i det vesentlige dan-ner en bærer for komponenten c) er Mg-dihalogenider som i et røntgenpulverspektrum for komponenten c) utviser en spred-ning (a broadening) på minst 30 % av den mest intense diffraksjonslinje som er tilstede i pulverspektret for det tilsvarende dihalogenid med et overflateareale på 1 m 2/g eller er Mg-dihalogenider som utviser et røntgenpulverspek-trum hvori den mest intense diffraksjonslinje er ersattet med en halo hvor intensitetstoppen er forskjøvet i forhold til den interplanare avstand for den mest intense linje og/ eller er Mg-dihalogenider med et overflateareale større enn 3 m2/g.
Måling av overflatearealet for Mg-dihalogenidene gjøres for komponent c) etter behandling med kokende TiCl4 i 2 h. Den funnede verdi betraktes som overflateareal for Mg dihalogenidet.
Meget aktive former av Mg-dihalogenidene er de som viser røntgenpulverspektrum hvori den mest intense diffraksjonslinje som finnes i spektret for det tilsvarende halogenid med et overflateareale på 1 m 2/g har avtatt i relativ intensitet, og er spredd til å gi en halo, eller de hvori den mest intense linje er erstattet av en halo hvis intensitets-topp er forskjøvet med hensyn til den interplanare avstand til den mest intense linje. Generelt er overflatearealet for de mest aktive former større enn 30 - 40 m 2/g og ligger fortrinnsvis i området 100 - 300 m 2/g.
Aktive former er også de som er avledet fra de ovenfor nevnte former ved varmebehandling i inerte hydrokarbonoppløs-ningsmidler og hvis røntgenstrålespektrum viser skarpe diffraksjonslinjer i stedet for halo'er. Den skarpe og mest intense linje for disse former viser en utspredning på minst 30 % i forhold til den tilsvarende linje for Mg-dihalogenidet med et overflateareal på 1 m 2/g. Foretrukne Mg-dihalogenider er Mg-diklorid og Mg-dibromid. Vanninn-holdet i dihalogenidene er generelt mindre enn 1 vekt-%.
For Ti-halogenider eller Ti-halogenalkoholater og estere båret på det aktive Mg-dihalogenid er ment de ovenfor nevnte forbindelser som kan være kjemisk eller fysikalsk bundet til bæreren og som ikke er ekstraherbar fra bestanddel c) ved behandling av denne med kokende 1,2-dikloretan i 2 h. Komponentene a), b) og c) bringes til å reagere med hverandre i en hvilken som helst rekkefølge imidlertid forbland-es bestanddelene a) og b) før de bringes i kontakt med komponent c) .
Forblanding av a) og b) utføres ved en temperatur som van-ligvis ligger mellom romtemperatur og temperaturen som anvendes under polymerisasjonsprosessen.
Forreaksjonen mellom c) og b) kan utføres også ved høyere temperatur. Komponent b) kan også innarbeides eller bringes til å reagere med selve komponent c). Komponent b) bringes til å reagere i et molart forhold i forhold til den halogenerte Ti-forbindelse båret på komponent c) på minst 1 og i et molforhold med hensyn til Al-alkyl-forbindelsen anvendt som komponent a) på mindre enn 2 0 og fortrinnsvis i området 0,05-0,3.
I komponent c) ligger molforholdet mellom Mg-dihalogenidet og den halogenerte Ti-forbindelse som er båret derpå i området 1 - 500 og molforholdet mellom den halogenerte Ti-for-bindelse og elektrondonoren båret på Mg-dihalogenidet i området 0,1 - 50. Silikonforbindelsen som inngår i b) innbefatter forbindelser med. den generelle formel:
hvori:
R er en alkyl-, alkenyl-, aryl-, arylalkyl- ellerrcykloalkyl-
gruppe med 1-20 karbonatomer,
Y er -OR' hvori R' enten er lik eller for-
skjellig fra R og har den samme betydning som R,
X er enten halogen eller hydrogen eller en OCOR", -NR2"
gruppe hvori R" enten er lik eller forskjellig fra R<1>
og har samme betydning som R',
m, n og p er tall som henholdsvis betyr:
m = 0 - 3, n=l-4ogp=0-l med det forbehold at m+n+p = 4.
Andre silisiumforbindelser som kan anvendes er forbindelser hvori 2 eller flere silisiumatomer er bundet til hverandre via oksygen- eller nitrogenatomer.
Eksempler på disse forbindelser er heksaetoksydisiloksan, symmetrisk difenyltetraetoksydisiloksan
Foretrukne silisiumforbindelser er fenylalkoksysilaner så som fenyltrietoksy- eller trimetoksysilan, difenyldimetoksy-, og dietoksysilan, monoklorfenyldietoksysilan, alkylalkoksy-silaner så som etyltriétoksysilan, etyltriisopropoksy-silan.
Eksempler på egnede andre forbindelser er klortrietoksy-silan, acetoksytrietoksysilan, vinyltrietoksysilan, butyl-trietoksysilan, trifenylmonoetoksysilan, fenyltricykloetoksy-silan, fenyldietoksydietylaminosilan, tetrafenoksysilan eller tetralkoksysilaner som tetrametoksysilan.
Silisiumforbindelsen kan også dannes in situ ved eksempelvis omsetning av en halogenert silisiumforbindelse så som SiCl^ med en alkohol eller et alkoholat av Mg eller Al.
I katalysatoren i henhold til oppfinnelsen er silisiumforbindelsen tilstede i en kombinert form i det faste produkt av reaksjonen mellom de forskjellige katalysatordannende komponenter idet molforholdet mellom silisiumforbindelsen og den halogenerte Ti-forbindelse er større enn 0,05 og ligger generelt i området 0,1 - 5.
Som indikert er Al-alkylforbindelser hvori Al-atomene er forbundet via grupper så som SO^ eller SO^ også egnet.
Al-alkylforbindelsene kan anvendes i blanding med Al-alkyl-halogenider så som AlEt2Cl.
Komponent c) fremstilles i henhold til forskjellige fremgangsmåter hvorav en som også er foretrukket, omfatter sammaling av Mg-dihalogenidet, Ti-halogenidet
og silisiumforbindelsen, når denne anvendes, inntil tilsynekomst i røntgenspekteret for det malte produkt av de ovenfor angitte modifikasjoner for spekteret av Mg-dihalogenidet og varmebehandling av det malte produkt i suspensjonen i en halogenert hydrokarbon så som 1,2-dikloretan, separasjon av det faste produkt og vasking med heptan eller lignende hydrokarbonoppløsningsmiddel. Behand-lingstiden ligger generelt i mellom 1-4 h og er avhengig av behandlingstemperaturen.
I henhold til en annen fremgangsmåte omsettes adduktet mellom Mg-dihalogenidet og en alkohol med TiCl^- Denne omsetning er beskrevet i belgisk patent nr. 868,682 og i tysk patent nr. 3.022.728.
I henhold til de ovenfor gitte metoder vil sluttproduktet inneholde et Mg-dihalogenid tilstede i aktiv form som angitt ovenfor.
Andre kjente metoder som fører til dannelse av Mg-dihalogenidet i aktiv form eller til Ti-inneholdende Mg-dihalogenid-bårede komponenter hvori dihalogenidet er tilstede i aktiv form er basert på de følgende reaksjoner: - omsetning av et Grignard-reagens eller Mg forbindelse
(R er en hydrokarbylgruppe) eller komplekser av Mg R2 forbindelser • med Al-trialkyler, med halogeneringsmidler så som AIX^ eller Al RmXn forbindelser (X er halogen, R er
en hydrokarbylgruppe, m+n = 3), SiCl4 eller HSiCl^*
- ved omsetning av et Grignard-reagens med en silanol eller polysiloksan, E^ O eller med en alkohol og ytterligere omsetning med et halogeneringsmiddel eller med TiCl^, - ved omsetning av Mg med en alkohol og en halogenhydrogen-syre eller Mg med et hydrokarbylhalogenid og en alkohol,
- ved omsetning av MgO med Cl2 eller AlCl^,
- ved omsetning av MgX2«nH20 (X = halogen) med et halogeneringsmiddel eller TiCl^, - eller ved omsetning av Mg mono- eller dialkoholater eller Mg-karboksylater med et halogeneringsmiddel.
Ti-halogenidene innbefatter særlig Ti-tetrahalogenider. Foretrukne forbindelser er : TiCl4 eller TiBr4.
Foretrukne katalysatorer er de hvori komponent c) er erholdt fra MgCl2f TiCl^ en silisiumforbindelse valgt fra gruppene av fenyl- eller etyltrietoksysilan eller difenyldimetoksy-eller dietoksysilan.
Komponent a) er en Al-trialkyl så som Al-trietyl eller Al-triisobutyl.
En av de foretrukne fremgangsmåter ved fremstilling av komponenten c) omfatter sammaling av MgCl2» TiCl4 og silisiumforbindelsen og behandle det malte produkt med en halogenert hydrokarbon som er 1,2-dikloretan.
Katalysatoren i henhold til oppfinnelsen anvendes for polymerisering av a-olefiner i henhold til kjente metoder, dvs. ved utføring av polymerisasjonen i væskefase, enten i nær-vær eller i fravær av et inert hydrokarbonoppløsningsmiddel, eller i gassfase eller eksempelvis kombinering av væskefase-polymerisasjonstrinn etterfulgt av et gassfasepolymerisa-sjonstrinn.
Generelt ligger temperaturen i området 40° - 160°C, fortrinnsvis i området 60° - 90°C idet det arbeides ved atmos-færetrykk eller høyere.
Som molekylvektregulerende bestanddel kan hydrogen eller andre kjente regulatorer anvendes.
Katalysatoren er spesielt egnet ved polymerisering av propylen, buten-1, styren, 4-metylpenten. Katalysatoren kan også anvendes i henhold til kjente metoder for polymerisering av blandinger av propylen og etylen til å gi modifiser-te polypropylener med bedre sjokkmotstandsevne ved lavere temperaturer (såkalte blokkopolymerer av propylen og etylen) eller for erholdelse av tilfeldige krystallinske kopolymer-er av propylen med mindre andeler av etylen.
De følgende eksempler illustrerer oppfinnelsen nærmere.
EKSEMPEL 1
Til en "inox" med et volum på 2 1, forsynt med magnetisk rører og termometer, varmestabilisert ved 60°C og holdt under et trykk ved hjelp av en nitrogenatmosfære ble det innført 5 m mol trietylaluminium, 1,5 m mol fenyltrietoksysilan, den faste katalysatorbestanddel erholdt ved omsetning av~ TiCl^ med MgCl.j.2.3 C2HJ-OH fremstilt under betingelsene beskrevet i eksempel 1 i belgisk patent nr. 868,682 og 700 ml avgasset og vannfri n-heptan, samtidig som propylen også ble innmatet. Den således fremstilte katalysatorbestanddel viste et røntgenstrålespektrum hvori den mest intense dif^i: fraksjonslinje som er tilstede i spekteret for MgCl„ med et overflateareal på 1 m 2/g hadde avtatt i relativ intensitet og utspredd seg til å danne en halo.
Deretter ble inf ørt 0,2 kp/cm 2hydrogen hvoretter det hele ble raskt oppvarmet til 7 0°C under samtidig innføring av ytterligere propylen til et totaltrykk på 7 kp/cm 2.
Det sistnevnte trykk ble holdt konstant under hele polymerisasjonen ved innføring av monomeren. Etter 4 h ble poly-meriseringen avbrutt, og polymeren isolert ved filtrering og deretter tørket. Mengden av tilstedeværende polymer oppløst i filtratet ble deretter isolert, veiet og addert til polymeren oppløselig i kokende n-heptan for beregning av isotaktisitetsindeksen. Mengden av den anvendte katalysatorbestanddel og mengden av den nevnte Ti-bestanddel, utbytte av polymeren med hensyn til tilstedeværende Ti og isotaktisitetsindeksen (I.I.) og grenseviskositeten ble be-stemt i tetralin ved 35°C er alle gjengitt i tabell I.
EKSEMPEL 2
Eksempel 1 ble gjentatt men det ble anvendt en fast katalysatorbestanddel fremstilt på følgende måte: Vannfritt MgC^, f enyltrietoksysilan i molforholdet Mg/Si på 6 og TiCl^ i molforholdet 1:1 med hensyn til fenyltri-etoksylan ble sammalt i en vibrasjonsmølle av typen "VTBRATOM" (N.V. TEMA<1>S, Gravenhage (Holland)) med et total-volum på 1 1 og inneholdende 3 kg rustfrie stålkuler med en
diameter på 16 mm. Malingen ble utført under anvendelse av en fyllingskoeffisient lik 100 g/l av det totale volum (vakuum) ved en indre temperatur i møllen på 25°C og med en maletid på 72 h.
Innføringen i møllen av materialet som skulle males, malingen og utføringen av produktet av sammalingen fra møllen fant sted under en nitrogenatmosfære. 10 g av det sammalte produkt ble brakt i kontakt med 100 ml 1,2 dikloretan ved 80°C i 2 h.
Etter denne periode ble 1,2-dikloretanet fjernet ved filtrering ved 8 0°C og det gjenværende faste produkt gjentatte ganger vasket med n-heptan ved romtemperatur til klorioner ikke kunne påvises i filtratet og deretter oppbevart i en heptansuspensjon.
De således fremstilte katalysatorbestanddeler viste et rønt-genpulverspektrum hvori den mest intense diffraksjonslinje som er tilstede i spekteret for MgCl0 med et overflateareal på 2 in /g hadde avtatt i relativ intensitet og utbredt seg til å danne en halo.
Egenskapene for den faste katalysatorbestanddel og resultat-ene av polymerisasjonsforsøkene er gjengitt i tabell I.
SAMMENLIGNINGSEKSEMPEL 3
62 g MgCl2 og 12,5 g TiCl^ ble innført i møllen beskrevet i eksempel 2 og sammalt i 60 h ved romtemperatur. Innholdet av titan var 3,9 vekt-%. 10 g av det sammalte produkt ble brakt i kontakt med 100 ml 1,2-dikloretan ved 80 C i 2 h. Faststoffet ble separert ved filtrering og deretter vasket med heptan ved den nevnte temperatur inntil klorioner ikke kunne påvises i filtratet. Røntgenpulverspekteret var det samme for den i henhold til katalysatorbestanddelen ifølge eksempel 1.
Den erholdte faste katalysatorbestanddel ble anvendt ved polymerisering av propylen under de samme betingelser som beskrevet i eksempel 1.
Resultatene av polymerisasjonen er gjengitt i tabell I.
SAMMENLIGNINGSEKSEMPEL 4
4 0 g MgCl2 ble malt i møllen beskrevet i eksempel 2 i 200 h ved romtemperatur.
10 g av det malte produkt ble behandlet med 150 ml TiCl^ i
2 h ved 135°C. Etter filtrering i varm tilstand ble be-handlingen med TiCl, gjentatt. Etter vasking med heptan ved 80 oC og tørking ble det tørre faststoff anvendt under de samme polymerisasjonsbetingelser som beskrevet i eksempel 1.
Katalysatorbestanddelen viste et røntgenpulverspektrum tilsvarende det for katalysatorbestanddelen ifølge eksempel 1.
Resultatene av polymerisasjonen er gjengitt i tabell I.
SAMMENLIGNINGSEKSEMPEL 1
200 mg av den faste katalysatorbestanddel fremstilt i henhold til eksempel 4 ble anvendt ved polymerisering av propylen under de samme betingelser som beskrevet i eksempel 1 men i stedet for PES ble det anvendt etyl-p-toluat. Re-sultatene av polymerisasjonen er rapportert i tabell I.
SAMMENLIGNINGSEKSEMPEL 2
Sammenligningseksempel 1 ble gjentatt men det ble anvendt en fast katalysatorbestanddel fremstilt i henhold til eksempel 3.
Resultatene av polymerisasjonsforsøkene er gjengitt i tabell
I.
Claims (2)
1. Katalysator for polymerisasjon av £-olefiner, og som består av et reaksjonsprodukt av a) en trialkylaluminiumforbindelse, b) en Si-forbindelse som inneholder en eller flere Si-OR-bindinger hvor R er en hydrokarbongruppe, og c) en fast komponent bestående av en Ti-forbindelse, og eventuelt en elektrondonorforbindelse, båret på et Mg-dihalogenid i aktiv form, karakterisert ved at komponent (c) er et fast produkt bestående av som hovedkomponent minst et vannfritt Mg-dihalogenid i aktiv form som bærer og båret på dihalogenidet et Ti-tetra-halogenid og en silisiumforbindelse inneholdende en eller flere Si-OR-bindinger (R er som ovenfor angitt) hvorved for-holdet mellom den bårede silisiumforbindelse og den bårede Ti-forbindelse er 0,1 til 5 mol silisiumforbindelse pr. mol av Ti-forbindelsen.
2. Fast katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren ifølge krav 1, karakterisert ved. at den består av den faste komponent c) i krav 1, hvor Mg-dihalogenidet er Mg-diklorid eller Mg-dibromid, og silisiumforbindelsen er fenyl-di- eller trialkoksysilan eller et alkyl-di- eller trialkoksysilan.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT8024141A IT1209255B (it) | 1980-08-13 | 1980-08-13 | Catalizzatori per la polimerizzazione di olefine. |
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| Publication Number | Publication Date |
|---|---|
| NO812677L NO812677L (no) | 1982-02-15 |
| NO159283B true NO159283B (no) | 1988-09-05 |
| NO159283C NO159283C (no) | 1988-12-14 |
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| NO812676A NO160303C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, katalysatorbestanddel for fremstilling av katalysatoren og anvendelse av katalysatoren. |
| NO812675A NO159282C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, og katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren. |
| NO812677A NO159283C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, og fast katalysatorbestanddelfor anvendelse ved fremstilling av katalysatoren. |
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| Application Number | Title | Priority Date | Filing Date |
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| NO812676A NO160303C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, katalysatorbestanddel for fremstilling av katalysatoren og anvendelse av katalysatoren. |
| NO812675A NO159282C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, og katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren. |
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| EP (4) | EP0045976B2 (no) |
| JP (11) | JPS5763312A (no) |
| KR (3) | KR840000802B1 (no) |
| AR (1) | AR244254A1 (no) |
| AT (4) | ATE42311T1 (no) |
| AU (3) | AU557334B2 (no) |
| BR (3) | BR8105185A (no) |
| CA (3) | CA1174225A (no) |
| CS (2) | CS226437B2 (no) |
| DE (4) | DE3177124D1 (no) |
| DK (3) | DK160256C (no) |
| ES (3) | ES8300795A1 (no) |
| FI (3) | FI70030C (no) |
| HU (3) | HU186399B (no) |
| IN (3) | IN155867B (no) |
| IT (1) | IT1209255B (no) |
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| NO (3) | NO160303C (no) |
| PH (3) | PH17763A (no) |
| PL (3) | PL140238B1 (no) |
| PT (3) | PT73501A (no) |
| RU (1) | RU2111975C1 (no) |
| SG (1) | SG33087G (no) |
| SU (2) | SU1457813A3 (no) |
| YU (3) | YU42579B (no) |
| ZA (3) | ZA815487B (no) |
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-
1980
- 1980-08-13 IT IT8024141A patent/IT1209255B/it active
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1981
- 1981-08-06 NO NO812676A patent/NO160303C/no unknown
- 1981-08-06 NO NO812675A patent/NO159282C/no unknown
- 1981-08-06 FI FI812442A patent/FI70030C/fi not_active IP Right Cessation
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- 1981-08-12 ES ES504715A patent/ES504715A0/es active Granted
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- 1981-08-12 SU SU813450787A patent/SU1568890A3/ru active
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- 1981-08-12 CA CA000383747A patent/CA1185960A/en not_active Expired
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1987
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1990
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1991
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1994
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1995
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1996
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