NO752291L - - Google Patents
Info
- Publication number
- NO752291L NO752291L NO752291A NO752291A NO752291L NO 752291 L NO752291 L NO 752291L NO 752291 A NO752291 A NO 752291A NO 752291 A NO752291 A NO 752291A NO 752291 L NO752291 L NO 752291L
- Authority
- NO
- Norway
- Prior art keywords
- halogen
- reaction
- compounds
- carried out
- polymerization
- Prior art date
Links
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- -1 hydride halogen Chemical class 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 4
- 241000036848 Porzana carolina Species 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 229920001195 polyisoprene Polymers 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000000460 chlorine Substances 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- OBUNLFQVPAABFB-UHFFFAOYSA-N ethoxyethane;heptane Chemical compound CCOCC.CCCCCCC OBUNLFQVPAABFB-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
-
- 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
- C08F4/42—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
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)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Meat, Egg Or Seafood Products (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Pc.tymere aluminiumforbinclelseroPc.tymere aluminum connectors
Description
Foreliggende oppfinnelse vedrer er nye alurniniumforbindelser av polyiminnatur, deres fremstilling og illustreres også i forbindelse med anvendelse av disse forbindelser som komponenter av katalytiske systemer som anvendes ved polymerisering av umettede forbindelser„ The present invention relates to new aluminum compounds of a polyimine nature, their preparation and is also illustrated in connection with the use of these compounds as components of catalytic systems used in the polymerization of unsaturated compounds.
Fra det italienske patentskrift S85.567 er dot kjent aluminiumderivater av polyÆminnetur inneholdende halogenatomer bundet til aluminium. From the Italian patent document S85,567, aluminum derivatives of polyÆminnetur containing halogen atoms bonded to aluminum are known.
Det er videre foreslått oligomere N-alkyl-iminoalaner med kjemiske sammensetninger henholdsvis Oligomeric N-alkyl iminoalans with chemical compositions respectively have also been proposed
hvori X og Y er like eller forskjellige og :-etyr hydridhalogen og/eller halogenatomer direkte bundet til nluni liura- n er et helt tall lavere eller lik 10, summen av (x+y) er et helt tall lavere eller lik 10, in which X and Y are the same or different and :-ether hydride halogen and/or halogen atoms directly bonded to nluni liura- n is an integer lower than or equal to 10, the sum of (x+y) is an integer lower than or equal to 10,
y er et helt tall forskjellig fra 0, il er et alifatiskjaromatisk eller cykloalyfatisk hydrokarbon,karakterisert vedén tredimensjonal struktur, og atomforhold X/Al = 1 og N/Al = 1 for (a) og (X .+ Y)/AL>1 og N/Al 1 for (b). y is an integer different from 0, il is an aliphatic-aromatic or cycloaliphatic hydrocarbon, characterized by a three-dimensional structure, and atomic ratios X/Al = 1 and N/Al = 1 for (a) and (X .+ Y)/AL>1 and N/Al 1 for (b).
Noen av disse forbindelser tillater når de anvendes som komponenterSome of these compounds allow when used as components
i katalytiske systemer sammen med overgangsmetallderivater ved polymerisering av konjugerte ciiencr at polymeriseringsreaksjonen kan gjennomføres ved en polymeriseringshastighet h&yere enn dem som kan oppnås med andre katalysatorsystorner og samtidig unngås side-rooksjoner eller ringslutninger cv polyraerkjedene„ Blant annet tillater dette oppnåelse av polymer med lavere forbruk av overgangs- in catalytic systems together with transition metal derivatives when polymerizing conjugated compounds means that the polymerization reaction can be carried out at a polymerization rate higher than that which can be achieved with other catalyst systems and at the same time side reactions or ring closures in the polymer chains are avoided. -
metalIderivater» .metal derivatives" .
Det er nå funnet at de ovennevnte alurniniumforbindelser kan modifiseres ved en reaksjon med et alkalimetall eller jordalkali-metallaiianat, eller med aluminiumhydrid-komplekser til å gi nye aluminiumderivater med en vesentlig polyiminnatur, og ved siden av at de bevarer eller forbedrer de ovennevnte egenskaper ved polymeriseringen av konjugerte diener kan forbindelsene anvendes som komponenter i katalyttiske systemer ved polymerisering av andre umettede forbindelser, spesielt av etylen og monoolefiner. It has now been found that the above aluminum compounds can be modified by reaction with an alkali metal or alkaline earth metal cyanate, or with aluminum hydride complexes to give new aluminum derivatives with a substantial polyimine nature, and in addition to preserving or improving the above properties upon polymerization of conjugated dienes, the compounds can be used as components in catalytic systems in the polymerization of other unsaturated compounds, especially of ethylene and monoolefins.
Aluminiumforbindelsene i henhold til den foreliggende oppfinnelse har den folgende generelle forwol The aluminum compounds according to the present invention have the following general purpose
hvori R er et alifatisk, aromatisk eller cykloalifatisk hydrokarbon-radikal, H er hydriehalogen, Y er halogen? k er fra 2 til 50, h/k^<>>l, (i -i- j)/h<>>l, i / O og j ^ 0o in which R is an aliphatic, aromatic or cycloaliphatic hydrocarbon radical, H is hydriahalogen, Y is halogen? k is from 2 to 50, h/k^<>>l, (i -i- j)/h<>>l, i / O and j ^ 0o
Disse alurniniumforbindelser oppnås ved å omsette de ovenfor angitte polyiminforbindelser med alkalimetall- eller jordalkalimetall-alanater eller med aluminiumhydrid-komplekser. These aluminum compounds are obtained by reacting the above-mentioned polyimine compounds with alkali metal or alkaline earth metal alanates or with aluminum hydride complexes.
Alt etter de anvendte utgangsforbindelser kan hydrogenutvikling finne sted og/eller alkalImetall-halogenidet kan utskilles. Depending on the starting compounds used, hydrogen evolution can take place and/or the alkali metal halide can be separated.
Reaksjonen foregår lett ved temperaturer fra 0 til 70 C og foretrukket ved•trykk tilsvarende damptrykket av det løsningsmiddel hvori operasjonene gjennomfores»ved arbeidstemperaturene The reaction takes place easily at temperatures from 0 to 70 C and preferably at a pressure corresponding to the vapor pressure of the solvent in which the operations are carried out at the working temperatures
Det kan anvendes løsningsmidler som hører til gruppen av etere som f.eks. dimetyletcr, dietyleter, metyletyleter3cykliske etere Solvents belonging to the group of ethers such as e.g. dimethyletcr, diethylether, methylethylether3cyclic ethers
eller blandinger derav med hydrokarboner eller bare hydrokarboner» Som nevnt er forbindelsene nyttige komponenter i katalyttiske systemer for polymerisering av forbindelser ned minst en olefin-umettethet sammen med en overgangsmetallforbindelse» or mixtures thereof with hydrocarbons or only hydrocarbons" As mentioned, the compounds are useful components of catalytic systems for the polymerization of compounds down at least one olefinic unsaturation together with a transition metal compound"
Forbindelsene kan derfor anvendes for fremstilling av katalysatorer mod et bredt anvendelsesområde og med den egenskeip i sammenligning med aluminiumalkyler at de ikke er selvantennelige i neorvær av lUfto The compounds can therefore be used for the production of catalysts for a wide range of applications and with the characteristic, in comparison with aluminum alkyls, that they are not self-igniting in the presence of lUfto
EKSEMPLEREXAMPLES
1) 26 mmol LiAlHA i en eterlosning (1 V-1) ble i løpet av 5 minutter tilsatt til 176 mg atomer polyiminoalan (som Al) opplost i 300 ml eter-heptanblanding (30% som etyleter) med Cl/Al = 0-26., N/Al = 0.97, idet tilsetningen ble gjennomført ved 45°C under omrøring. Disse betingelser ble opprettholdt i 4 timer og blandingen ble sa filtrert på et sintret glasslag. Alle operasjoner ble gjennomfart under en inert og vannfri atmosfære. 1) 26 mmol of LiAlHA in an ether solution (1 V-1) was added over the course of 5 minutes to 176 mg of atoms of polyiminoalane (as Al) dissolved in 300 ml of ether-heptane mixture (30% as ethyl ether) with Cl/Al = 0- 26., N/Al = 0.97, the addition being carried out at 45°C with stirring. These conditions were maintained for 4 hours and the mixture was then filtered on a sintered glass layer. All operations were carried out under an inert and water-free atmosphere.
Filtratet ble destillert underrvakuum for å eliminere etyleter og heptan ble tilsatt. The filtrate was distilled under vacuum to eliminate ethyl ethers and heptane was added.
Oppløsningen hadde ved analyse folgende sammensetning On analysis, the solution had the following composition
2) 28 mmol NaAlH^ suspendert i etyleter ble tilsett til 187 mmol polyiminoalan (som Al) opplost i 300 ml av en eter-heksan-blanding (30& som etyleter) med Cl/Al = 0.26 og' N/Al = 0*97, idet tilsetningen ble gjennomfart under omrering og ved en temperatur på 45°C. Hele blandingen ble holdt under disse betingelser i 4 timer og natriurnklorid ble så frafiltrert. 2) 28 mmol of NaAlH^ suspended in ethyl ether was added to 187 mmol of polyiminoalane (as Al) dissolved in 300 ml of an ether-hexane mixture (30& as ethyl ether) with Cl/Al = 0.26 and' N/Al = 0*97 , the addition being carried out under stirring and at a temperature of 45°C. The whole mixture was kept under these conditions for 4 hours and sodium chloride was then filtered off.
Filtratet ble destillert under vakuum for å fjerne etyleter og heptan ble tilsatt» Opplesningen hadde ved analyse følgende sammensetning The filtrate was distilled under vacuum to remove ethyl ether and heptane was added" The reading had the following composition on analysis
Al = 0.724 mol/liter H = 0.864 mol/literAl = 0.724 mol/liter H = 0.864 mol/liter
N = 0.602 mol/liter.N = 0.602 mol/litre.
Cl = 0.95 mol/liter.Cl = 0.95 mol/liter.
Tilsvarende bruttoformelen Corresponding to the gross formula
3) 25 mmol NaH ble under omrøring tilsatt Ved 45°C til 180 mg 3) 25 mmol of NaH were added with stirring at 45°C to 180 mg
atomer polyiminoalan (som Al) opplost i 300 ml av en eter-heptan-v blanding og med Cl/Al = 0.25, M/Al •» 0.86. Hele blandingen ble holdt under disse betingelser i 4 timer og ble så avkjølt og filtrert på et sintret glasslag. atoms of polyiminoalane (as Al) dissolved in 300 ml of an ether-heptane-v mixture and with Cl/Al = 0.25, M/Al •» 0.86. The whole mixture was kept under these conditions for 4 hours and was then cooled and filtered on a sintered glass pad.
Filtratet ble destillert under vakuum for å fjerne etyleterThe filtrate was distilled under vacuum to remove ethyl ethers
og heptan ble tilsatte Den analyserte opplesning hadde folgende sammensetning and heptane were added. The analyzed reading had the following composition
Al = 0.95 mol/literAl = 0.95 mol/litre
N = 0.82 mol/literN = 0.82 mol/litre
Cl = 0.10 mol/literCl = 0.10 mol/liter
H d l.io mol/literH d l.io mol/liter
tilsvarende bruttoformelencorresponding to the gross formula
4) En eterløsning av polyiminoalan, med N/Al molforhold lik 1, uten noe klor og inneholdende 30.78 mg atom aluminium, ble tilsatt en eteroppløsning av vannfri HC1 i slik en mengde at molforholdet Cl/Al =0.165, og det ble så tilsatt 6.05 ml av en eteroppløsning av LiAlmod en konsentrasjon på 0.824 M (4.98 mmol). Hele blandingen ble omrort i 1 time og ble så satt bort i 20 timer. 4) An ether solution of polyiminoalane, with an N/Al molar ratio equal to 1, without any chlorine and containing 30.78 mg of aluminum atoms, was added to an ether solution of anhydrous HC1 in such an amount that the molar ratio Cl/Al = 0.165, and then 6.05 ml of an ether solution of LiAlmod a concentration of 0.824 M (4.98 mmol). The entire mixture was stirred for 1 hour and then set aside for 20 hours.
LiCl ble frafiltrert og opplesningen ble gjort fri for oppløsnings-middel ved destillasjon under vakuum. Den faste rost bh tørret sakte under vakuum ved romtemperatur og analysert til A1H33.25% N 14.90% H 14.88 raekv./g LiCl was filtered off and the reading was made free of solvent by distillation under vacuum. The solid roasted bra dried slowly under vacuum at room temperature and analyzed to A1H33.25% N 14.90% H 14.88 raeq./g
tilsvarende bruttoformelencorresponding to the gross formula
Det oppnådde produkt vor opploselig i aromatiske og cyklo-alifatiske hydrokcrbonløsningsrnidler. 5) En eterløsning av AlH^.EtgO (6.2 mmol) ble tilsatt til en eter-heksanoppløsning (30% som etyleter) av polyiminoalan med molforhold W/Al = 0.99, Cl/Al = 0.10 inneholdende 42.7 mg atom aluminium. Blandingen ble holdt kokende under omrøring 1 4 timer og deretter ble losningsmidlet fjernet under vakuum- og helcsan ble erstattet med etyleter. Da oppløsningen var noe uklar ble den filtrert. Analysen viste bruttoformelen The product obtained was soluble in aromatic and cycloaliphatic hydrocarbon solvents. 5) An ether solution of AlH^.EtgO (6.2 mmol) was added to an ether-hexane solution (30% as ethyl ether) of polyiminoalane with molar ratio W/Al = 0.99, Cl/Al = 0.10 containing 42.7 mg of aluminum atoms. The mixture was kept boiling with stirring for 14 hours and then the solvent was removed under vacuum and the helcane was replaced with ethyl ether. When the solution was somewhat cloudy, it was filtered. The analysis showed the gross formula
Polymeriserinqseksem pler: etylen Polymerization examples: ethylene
1) En 5 liters autoklav utstyrt med et anker-roreverk ble tilført 2 liter vannfri og luftfri n-heptan og ble så termostatstyrt ved 90°Co Deretter ble katalysatoren som nå er fremstilt separat tilsatt, og besto av 1.00 g TiCl^ med renhet AA tilsvarende 2.5 mg atom/liter og 1, 7/',' g polyiminoalan (PIAPE) syntetisert, i henhold til et av de fcregående eksempler tilsvarende 7.5 mg at/l H°. 3 atmosfærers hydrogentrykk ble rom molekylvektregulator 1) A 5 liter autoclave equipped with an anchor stirrer was fed with 2 liters of anhydrous and air-free n-heptane and was then thermostatically controlled at 90°Co Then the catalyst that has now been prepared separately was added, and consisted of 1.00 g of TiCl^ with purity AA corresponding to 2.5 mg atom/liter and 1.7/',' g polyiminoalane (PIAPE) synthesized, according to one of the preceding examples corresponding to 7.5 mg at/l H°. 3 atmospheres of hydrogen pressure became room molecular weight regulator
innført og deretter ble etylen innført opp til et totalt trykk på 5 atmosfærer, idet trykket ble holdt ved denne verdi ved forløpet av selve polymerisasjonsreaksjonen. introduced and then ethylene was introduced up to a total pressure of 5 atmospheres, the pressure being maintained at this value during the course of the polymerization reaction itself.
Etter to timers reaksjon ble autoklaven åpnet., suspensjonen ble sentrifugert og polymeren ble tørret under vakuum ved 60°C. After two hours of reaction, the autoclave was opened, the suspension was centrifuged and the polymer was dried under vacuum at 60°C.
Det ble oppnådd 750 g polymer med d = 0.958 og smolteflyte-indeks.SFI = 0.720. 750 g of polymer with d = 0.958 and melt flow index SFI = 0.720 were obtained.
Et polymerisasjorn forsøk gjennomført under de samme. betingelser ved anvendelse avet polyiminoalan med M/AL = 1 tilsvarende italiensk patentskrift 835.567 ga 250 g polymer med SFI = 0.70. 2) Betingelsen i henhold til det foregående eksempel ble etter-fulgt under anvendelse av hydrogentrykk på 5 atmosfærer. A polymerization trial carried out during the same. conditions using polyiminoalane with M/AL = 1 corresponding to Italian patent document 835,567 gave 250 g of polymer with SFI = 0.70. 2) The condition according to the preceding example was followed using a hydrogen pressure of 5 atmospheres.
Det ble oppnådd 550 g polymer med SFI = 3.60. 550 g of polymer with SFI = 3.60 were obtained.
Polymeriserinqseksempel; isoprenPolymerization example; isoprene
1) 90 ml vannfri og luftfri hekcan, lo82»10~<3>mol TiCl^ og PIAPE i slike mengder nt Al/T;l~f or hol det var 0.95, 1, 1.05, 1.1 og 1.2 ble innfart i en rekke glassflasker. Disse ble lukket og katalysatoren tilsatt og deretter ble det tilsatt 30 ml vannfri nydestillert isopren. Flaskene ble lukket med vanlige crov/n-korker og anbragt i en termostat ved 30°C. Alle operasjoner ble gjennomført under inert atmosfesreo 1) 90 ml of anhydrous and air-free hecan, lo82»10~<3>mol TiCl^ and PIAPE in such amounts nt Al/T;l~f or hol it was 0.95, 1, 1.05, 1.1 and 1.2 were entered in a series glass bottles. These were closed and the catalyst added and then 30 ml of anhydrous freshly distilled isoprene was added. The bottles were closed with standard crov/n caps and placed in a thermostat at 30°C. All operations were carried out under inert atmosphere
Etter to timers polymerisering ble reaksjonen stanset ved tilsetning av etylalkohol og det ble gjennomført en etylalkohol-koagulering. After two hours of polymerization, the reaction was stopped by the addition of ethyl alcohol and an ethyl alcohol coagulation was carried out.
Etter tørring ble det oppnådd folgende omdannelsersAfter drying, the following conversions were obtained
En sammenlignende rekka polymeriseringer, gjennomført pa nytt ved anvendelse av PIA i henhold til italiensk patentskrift 885.567, ga følgende resultaters A comparative series of polymerizations, carried out again using PIA according to Italian patent document 885,567, gave the following results
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24661/74A IT1019677B (en) | 1974-07-01 | 1974-07-01 | POLYMER COMPOUNDS OF ALUMINUM OF POLYIMINIC NATURE PROCEDURE FOR THEIR PREPARATION AND THEIR USE AS COMPONENTS OF CATALYTIC SYSTEMS FOR THE POLY MERIZATION OF UNSATURATED COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO752291L true NO752291L (en) | 1976-01-05 |
Family
ID=11214294
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO752291A NO752291L (en) | 1974-07-01 | 1975-06-25 | |
| NO774148A NO774148L (en) | 1974-07-01 | 1977-12-05 | PROCEDURES FOR POLYMERIZATION OF UNSaturated Compounds |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO774148A NO774148L (en) | 1974-07-01 | 1977-12-05 | PROCEDURES FOR POLYMERIZATION OF UNSaturated Compounds |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS5544099B2 (en) |
| BE (1) | BE830812A (en) |
| CA (1) | CA1049028A (en) |
| CH (1) | CH604885A5 (en) |
| CS (1) | CS205002B2 (en) |
| DD (2) | DD121794A5 (en) |
| DE (1) | DE2529318C3 (en) |
| DK (1) | DK146474C (en) |
| FR (1) | FR2277113A1 (en) |
| GB (1) | GB1508048A (en) |
| HU (1) | HU172081B (en) |
| IL (1) | IL47773A (en) |
| IT (1) | IT1019677B (en) |
| LU (1) | LU72856A1 (en) |
| NL (1) | NL7507771A (en) |
| NO (2) | NO752291L (en) |
| SE (1) | SE425492B (en) |
| SU (1) | SU549087A3 (en) |
| YU (1) | YU37353B (en) |
| ZA (1) | ZA754119B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1064496B (en) * | 1976-11-22 | 1985-02-18 | Snam Progetti | PROCESS FOR THE POLYMERIZATION OF MONO AND DIOLEFINIC COMPOUNDS |
| US5229468A (en) * | 1992-02-13 | 1993-07-20 | Hercules Incorporated | Polymer precursor for silicon carbide/aluminum nitride ceramics |
-
1974
- 1974-07-01 IT IT24661/74A patent/IT1019677B/en active
-
1975
- 1975-06-19 GB GB26213/75A patent/GB1508048A/en not_active Expired
- 1975-06-25 NO NO752291A patent/NO752291L/no unknown
- 1975-06-26 CH CH831475A patent/CH604885A5/xx not_active IP Right Cessation
- 1975-06-26 FR FR7520159A patent/FR2277113A1/en active Granted
- 1975-06-26 YU YU1645/75A patent/YU37353B/en unknown
- 1975-06-27 ZA ZA00754119A patent/ZA754119B/en unknown
- 1975-06-30 HU HU75SA00002812A patent/HU172081B/en unknown
- 1975-06-30 JP JP8014975A patent/JPS5544099B2/ja not_active Expired
- 1975-06-30 BE BE157821A patent/BE830812A/en not_active IP Right Cessation
- 1975-06-30 SU SU2149356A patent/SU549087A3/en active
- 1975-06-30 DD DD186974A patent/DD121794A5/xx unknown
- 1975-06-30 NL NL7507771A patent/NL7507771A/en not_active Application Discontinuation
- 1975-06-30 CA CA75230439A patent/CA1049028A/en not_active Expired
- 1975-06-30 LU LU72856A patent/LU72856A1/xx unknown
- 1975-06-30 DK DK295875A patent/DK146474C/en not_active IP Right Cessation
- 1975-06-30 CS CS754608A patent/CS205002B2/en unknown
- 1975-06-30 DD DD192567A patent/DD125804A5/xx unknown
- 1975-07-01 DE DE2529318A patent/DE2529318C3/en not_active Expired
- 1975-07-01 SE SE7507563A patent/SE425492B/en unknown
- 1975-07-23 IL IL47773A patent/IL47773A/en unknown
-
1977
- 1977-12-05 NO NO774148A patent/NO774148L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HU172081B (en) | 1978-05-28 |
| NO774148L (en) | 1976-01-05 |
| YU37353B (en) | 1984-08-31 |
| AU8212275A (en) | 1976-12-16 |
| IT1019677B (en) | 1977-11-30 |
| FR2277113A1 (en) | 1976-01-30 |
| IL47773A (en) | 1979-05-31 |
| DE2529318A1 (en) | 1976-01-22 |
| JPS5544099B2 (en) | 1980-11-10 |
| ZA754119B (en) | 1976-06-30 |
| DK146474B (en) | 1983-10-17 |
| SE425492B (en) | 1982-10-04 |
| YU164575A (en) | 1983-04-27 |
| CA1049028A (en) | 1979-02-20 |
| DK146474C (en) | 1984-03-26 |
| FR2277113B1 (en) | 1980-05-30 |
| LU72856A1 (en) | 1975-10-08 |
| GB1508048A (en) | 1978-04-19 |
| DD121794A5 (en) | 1976-08-20 |
| SE7507563L (en) | 1976-01-02 |
| DE2529318C3 (en) | 1979-01-18 |
| CS205002B2 (en) | 1981-04-30 |
| DK295875A (en) | 1976-01-02 |
| DE2529318B2 (en) | 1978-04-27 |
| JPS5176399A (en) | 1976-07-01 |
| BE830812A (en) | 1975-10-16 |
| SU549087A3 (en) | 1977-02-28 |
| DD125804A5 (en) | 1977-05-18 |
| IL47773A0 (en) | 1976-11-30 |
| NL7507771A (en) | 1976-01-05 |
| CH604885A5 (en) | 1978-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5659101A (en) | Catalytic system and process for the production of polydiolefins | |
| CA1076544A (en) | Catalysts for the polymerization of olefins | |
| NO142350B (en) | PROCEDURE FOR POLYMERIZATION OF ALFA OLEFINES, AND CATALYTIC PREPARATION FOR USE IN THE PROCEDURE | |
| NO152789B (en) | HYDROCARBON SOLUTION OF DIORGANOMAGNESIUM MIXTURE FOR USE AS CATALYST OR ORGANIC REAGENT, AND PROCEDURE FOR PREPARING SUCH HYDROCARBON SOLUTION | |
| NO152009B (en) | PROCEDURE FOR THE PREPARATION OF AN ACTIVE POLYMERIZATION CATALYST | |
| US11130826B2 (en) | Preformed catalytic system comprising a rare earth metal metallocene | |
| US4128567A (en) | Aluminium polymeric compounds of polyimine nature | |
| EP0021700B1 (en) | Process for preparing ethylene polymer wax | |
| US5633353A (en) | Halogenated organometallic complexes and their use in the polymerization of unsaturated monomers | |
| NO752291L (en) | ||
| USRE25179E (en) | Production of ai kyi alumnium hydrides | |
| US4370449A (en) | Transition metal composition and production thereof | |
| US4208304A (en) | Catalyst system for producing ethylene polymers | |
| NO156564B (en) | COMPLEX SALTS AND PROCEDURES FOR PREPARING THEREOF. | |
| US4476288A (en) | Catalysts comprising magnesium and a transition metal | |
| US4169927A (en) | Process for the polymerization of ethylene | |
| NO750159L (en) | ||
| Balducci et al. | Advances in Catalysts Based on Aluminum Hydride Derivatives for the Synthesis of High-Cis Polyisoprene | |
| US3277131A (en) | Preparation of pure alkoxytitanium iodides | |
| JPH0118084B2 (en) | ||
| US4213878A (en) | Transition metal composition and process | |
| US3607854A (en) | Method of producing cis-1,4-polyisoprene | |
| NO180013B (en) | Catalyst component for (co) polymerization of ethylene, catalyst comprising such, and process of (co) polymerization of ethylene | |
| GB1582141A (en) | Production of transition metal composition useful as an olefine polymerisation catalyst or component thereof | |
| DK146475B (en) | PROCEDURE FOR POLYMERIZATION OF ALFA OLEFINES OR DIOLEFINES |