NO133934B - - Google Patents
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- NO133934B NO133934B NO740631A NO740631A NO133934B NO 133934 B NO133934 B NO 133934B NO 740631 A NO740631 A NO 740631A NO 740631 A NO740631 A NO 740631A NO 133934 B NO133934 B NO 133934B
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- Norway
- Prior art keywords
- compound
- magnesium
- aluminum
- general formula
- metal
- Prior art date
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- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkoxy compound Chemical class 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 150000002681 magnesium compounds Chemical class 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 125000004367 cycloalkylaryl group Chemical group 0.000 claims 1
- 229910052740 iodine Chemical group 0.000 claims 1
- 239000011630 iodine Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000005329 float glass Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 48
- 239000003054 catalyst Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HUEOOADXKMLSBR-UHFFFAOYSA-N N-bis(N-phenylanilino)alumanyl-N-phenylaniline Chemical compound [Al+3].[N-](c1ccccc1)c1ccccc1.[N-](c1ccccc1)c1ccccc1.[N-](c1ccccc1)c1ccccc1 HUEOOADXKMLSBR-UHFFFAOYSA-N 0.000 description 4
- 229910010062 TiCl3 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- SUGSOWIHVFOQDM-UHFFFAOYSA-M [Cl-].C1(=CC=CC=C1)[N-]C1=CC=CC=C1.C1(=CC=CC=C1)[N-]C1=CC=CC=C1.[Al+3] Chemical compound [Cl-].C1(=CC=CC=C1)[N-]C1=CC=CC=C1.C1(=CC=CC=C1)[N-]C1=CC=CC=C1.[Al+3] SUGSOWIHVFOQDM-UHFFFAOYSA-M 0.000 description 2
- HIQUHUMFCYYNNK-UHFFFAOYSA-M bis(diethylamino)alumanylium;chloride Chemical compound [Cl-].CCN(CC)[Al+]N(CC)CC HIQUHUMFCYYNNK-UHFFFAOYSA-M 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- IPIRKMFIBLNVRC-UHFFFAOYSA-M magnesium;diphenylazanide;bromide Chemical compound Br[Mg+].C=1C=CC=CC=1[N-]C1=CC=CC=C1 IPIRKMFIBLNVRC-UHFFFAOYSA-M 0.000 description 2
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- KJDWJQVRPWIXEP-UHFFFAOYSA-N [K].C1(=CC=CC=C1)NC1=CC=CC=C1 Chemical compound [K].C1(=CC=CC=C1)NC1=CC=CC=C1 KJDWJQVRPWIXEP-UHFFFAOYSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VDMBOJYURSJLLO-UHFFFAOYSA-M aluminum diphenylazanide bromide Chemical compound [Br-].C1(=CC=CC=C1)[N-]C1=CC=CC=C1.C1(=CC=CC=C1)[N-]C1=CC=CC=C1.[Al+3] VDMBOJYURSJLLO-UHFFFAOYSA-M 0.000 description 1
- QTRQHYHCQPFURH-UHFFFAOYSA-N aluminum;diethylazanide Chemical compound [Al+3].CC[N-]CC.CC[N-]CC.CC[N-]CC QTRQHYHCQPFURH-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- HEVSIKNIWJEAAA-UHFFFAOYSA-M magnesium;diethylazanide;bromide Chemical compound [Br-].CCN([Mg+])CC HEVSIKNIWJEAAA-UHFFFAOYSA-M 0.000 description 1
- TXZBQHZEKIROSD-UHFFFAOYSA-N magnesium;diphenylazanide Chemical compound [Mg+2].C=1C=CC=CC=1[N-]C1=CC=CC=C1.C=1C=CC=CC=1[N-]C1=CC=CC=C1 TXZBQHZEKIROSD-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/04—Changing or regulating the dimensions of the molten glass ribbon
- C03B18/06—Changing or regulating the dimensions of the molten glass ribbon using mechanical means, e.g. restrictor bars, edge rollers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
- Laminated Bodies (AREA)
- Glass Compositions (AREA)
Abstract
Fremgangsmåte ved fremstilling av tynt flyteglass.Process for the production of thin float glass.
Description
Fremgangsmåte til polymerisering av ethylen, o-olefiner eller diolefiner med minst en vinyl-dobbeltbinding i molekylet. Process for the polymerization of ethylene, o-olefins or diolefins with at least one vinyl double bond in the molecule.
Foreliggende oppfinnelse angår en The present invention relates to a
fremgangsmåte til polymerisering av ethylen, a-olefiner eller di-olefiner med minst process for the polymerization of ethylene, α-olefins or di-olefins with at least
én vinyl-dobbeltbinding i molekylet, eller one vinyl double bond in the molecule, or
blandinger av slike stoffer. Ifølge oppfinnelsen utføres polymeriseringen ved hjelp mixtures of such substances. According to the invention, the polymerization is carried out using
av nye polymeriseringskatalysatorer som of new polymerization catalysts which
er funnet å være meget fordelaktige til polymerisering av de ovenfor nevnte monomere. have been found to be very advantageous for the polymerization of the above-mentioned monomers.
Polymerisering av hydrocarbonmono-mere som inneholder minst én vinyl-dobbeltbinding i molekylet under anvendelse Polymerization of hydrocarbon monomers containing at least one vinyl double bond in the molecule in use
av katalysatorer fremstillet av organiske of catalysts made from organic
metallforbindelser som inneholder metall-til-carbonbindinger, og forbindelser av metal compounds containing metal-to-carbon bonds, and compounds of
overgangsmetaller, er tidligere beskrevet. transition metals, have previously been described.
I slike katalysatorer er der tilstede sterkt In such catalysts there is a strong presence
reaktive organometalliske bindinger. reactive organometallic bonds.
I fremgangsmåten ifølge oppfinnelsen In the method according to the invention
anvender man polymeriseringskatalysatorer som fremstilles ved å bringe en organisk polymerization catalysts are used which are produced by bringing an organic
aluminium- eller magnesiumforbindelse i aluminum or magnesium compound i
kontakt med en halogen- eller adkoksy-forbindelse av et overgangsmetall av gruppene IV, V, VI eller VIII av elementenes contact with a halogen or adoxy compound of a transition metal of groups IV, V, VI or VIII of the elements
periodiske system, og det karakteristiske periodic table, and the characteristic
hovedtrekk ved oppfinnelsen er at i nevnte main feature of the invention is that in said
aluminium- eller magnesiumforbindelse er aluminum or magnesium compound is
metallet bundet til nitrogenatomer, mens the metal bound to nitrogen atoms, while
der ikke er tilstede metall-til-carbonbin-dinger i polymeriseringskatalysatorene. where no metal-to-carbon bonds are present in the polymerization catalysts.
Det er videre funnet at en viss gruppe It is further found that a certain group
forbindelser av denne type er særlig fordel- compounds of this type are particularly advantageous
aktige som katalysatorer for nevnte for-mål, nemlig forbindelsen som tilsvarer den generelle formel active as catalysts for said purpose, namely the compound corresponding to the general formula
i hvilken Me betegner Magnesium eller aluminium, R, og R2 er like eller forskjellige og betegner alkyl-, cycloalkyl-, aryl eller alkylarylgrupper eller sammen med nitro-genatomet danner en heterocyclisk forbindelse, X betegner klor, brom eller jod, n er et helt tall, eller kan være lik 0, m er et helt tall, således at n + m er lik valensen av metallet Me. in which Me denotes magnesium or aluminium, R and R2 are the same or different and denote alkyl, cycloalkyl, aryl or alkylaryl groups or together with the nitrogen atom form a heterocyclic compound, X denotes chlorine, bromine or iodine, n is an integer number, or can be equal to 0, m is an integer, so that n + m is equal to the valence of the metal Me.
Der kan også med fordel anvendes forbindelser med den generelle formel: Compounds with the general formula can also be advantageously used:
i hvilken X betegner klor, brom eller jod, og R betegner en alkyl-, cycloalkyl-, aryl-eller alkylarygruppe. in which X represents chlorine, bromine or iodine, and R represents an alkyl, cycloalkyl, aryl or alkylary group.
Blant de forbindelser som tilsvarer den første av de ovenfor oppførte generelle formler som, sammen med forbindelsene av overgangsmetallene, er særlig fordelaktige til fremstilling av de nye polymeriseringskatalysatorer er alkyl-, cycloalkyl- og aryl-substituerte amider, de tilsvarende derivater av heterocycliske forbindelser som inneholder nitrogen i ringen og de tilsvarende halogenider som f. eks. aluminium-tris(dialkylamider) og -tris(dialkylamider), de tilsvarende pyrrol- og carba-zol-derivater, klorider og bromider av magnesium, dialkylamider og aluminium-bis-dialkylamider. Among the compounds corresponding to the first of the general formulas listed above which, together with the compounds of the transition metals, are particularly advantageous for the preparation of the new polymerization catalysts are alkyl-, cycloalkyl- and aryl-substituted amides, the corresponding derivatives of heterocyclic compounds containing nitrogen in the ring and the corresponding halides such as aluminum tris(dialkylamides) and -tris(dialkylamides), the corresponding pyrrole and carbazole derivatives, chlorides and bromides of magnesium, dialkylamides and aluminum bis-dialkylamides.
Blant fordelaktige forbindelser som tilsvarer den annen av de ovenfor oppførte generelle formler er bis(magnesiumhalo-genid)-alkylamidene og -arylamidene som f. eks. C(1Hr>N(MgJ)2. Among advantageous compounds corresponding to the second of the general formulas listed above are the bis(magnesium halide)-alkylamides and -arylamides such as, e.g. C(1Hr>N(MgJ)2.
Noen av disse forbindelser, særlig visse magnesiumforbindelser, er tidligere kjent. Derimot er aluminiumforbindelser som inneholder aluminium-til-nitrogen-bindinger, ikke tidligere kjent. Some of these compounds, especially certain magnesium compounds, are previously known. In contrast, aluminum compounds containing aluminium-to-nitrogen bonds are not previously known.
Dise forbindelser kan fremstilles ved å omsette aluminiumklorid med det tilsvarende Grignards reagens eller ved å omsette aluminiumklorid med det tilsvarende kaliumamid. I særdeleshet kan magnesium-difenylamidbromid fremstilles således som beskrevet av B. Oddo (Gazzetta Chimica Italiana, 41, I, 255 (1911)), ved å omsette difenylamin med ethylmagnesiumbromid. Fra den herved erholdte forbindelse kan aluminium-tris (dif enylamid), fremstilles, i alminnelighet ved en utvekslingsreaksjon med vannfritt aluminiumklorid på føl-gende måte: En oppløsning av 12 g aluminiumklorid i 100 ml ether tilsettes langsomt og under omrøring samt i nitrogenatmosfære til en oppløsning av magnesium-difenylamid (som kan fåes fra en opløsning av 0,3 mol ethylmagnesiumbromid i 200 ml vannfri ether og 50 g difenylamin i 150 ml vannfri benzen). These compounds can be prepared by reacting aluminum chloride with the corresponding Grignard reagent or by reacting aluminum chloride with the corresponding potassium amide. In particular, magnesium diphenylamide bromide can be prepared as described by B. Oddo (Gazzetta Chimica Italiana, 41, I, 255 (1911)), by reacting diphenylamine with ethylmagnesium bromide. From the compound thus obtained, aluminum tris (diphenylamide) can be produced, generally by an exchange reaction with anhydrous aluminum chloride in the following way: A solution of 12 g of aluminum chloride in 100 ml of ether is added slowly and with stirring and in a nitrogen atmosphere to a solution of magnesium diphenylamide (which can be obtained from a solution of 0.3 mol of ethylmagnesium bromide in 200 ml of anhydrous ether and 50 g of diphenylamine in 150 ml of anhydrous benzene).
Mot slutten av tilsetningen skiller det seg ut et hvitt bunnfall som består av mag-nesiumhalogenidet. Blandingen kokes derpå i ytterligere 2 timer under omrøring, hvorpå hele mengden av tilstedeværende væske (ether og benzen) fjernes ved av-destillasjon, først under atmosfæretrykk og derpå under avtagende trykk ned til 1 mm Hg, mens man oppvarmer kolben på olje-bad til 150° C. Towards the end of the addition, a white precipitate consisting of the magnesium halide separates. The mixture is then boiled for a further 2 hours with stirring, after which the entire amount of liquid present (ether and benzene) is removed by de-distillation, first under atmospheric pressure and then under decreasing pressure down to 1 mm Hg, while heating the flask in an oil bath to 150°C.
Det herved erholdte, faste residuum ekstraheres flere ganger med vannfri benzen, idet man hver gang dekanterer den klare mørkebrune væske i nitrogenatmosfære ned i en 500 ml kolbe. The solid residue thus obtained is extracted several times with anhydrous benzene, each time decanting the clear dark brown liquid in a nitrogen atmosphere into a 500 ml flask.
På denne måte får man en oppløsning som inneholder ca. 25 g aluminium-tris-(difenylamid) i 300 ml benzen. In this way, a solution containing approx. 25 g aluminum tris-(diphenylamide) in 300 ml benzene.
Dannelsen av forbindelser som inne- The formation of compounds that contain
holder aluminium-til-nitrogen-bindinger, f. eks. ved omsetning av aluminium-klorid med kalium-difenylamin eller ved difenylamin-Grignard-reagens, påvises enten ved hydrolyse av det erholdte produkt eller ved reaksjon mellom dette og ethylklorformiat. holds aluminum-to-nitrogen bonds, e.g. by reaction of aluminum chloride with potassium diphenylamine or with diphenylamine Grignard reagent, is detected either by hydrolysis of the product obtained or by reaction between this and ethyl chloroformate.
I første tilfelle får man difenylamin med godt utbytte, rn ens man i det annet tilfelle får et uretan med strukturformelen: In the first case, you get diphenylamine in good yield, while in the second case you get a urethane with the structural formula:
Andre forbindelser som tilfører den ovenfor angitte klasse kan fremstilles ved hjelp av lignende metoder. Other compounds which add to the above class can be prepared by similar methods.
Foruten aluminium- og magnesiumforbindelser av de foran angitte typer er Besides aluminum and magnesium compounds of the above types are
andre forbindelser i hvilket et atom aluminium eller magnesium er bundet til nitrogen og som ikke inneholder organiske grup-per i molekylet egnede som katalysatorbe-standdeler. Sådanne forbindelser er disse other compounds in which an atom of aluminum or magnesium is bound to nitrogen and which do not contain organic groups in the molecule suitable as catalyst components. Such connections are these
metallers nitrider, og aluminiumnitrid er særlig godt egnet. metal nitrides, and aluminum nitride are particularly suitable.
Alle slike forbindelser koblet med forbindelser av overgangsmetaller, fortrinsvis halogenholdige forbindelser, av metaller som tilhører gruppene IV, V, VI eller VIII av elementenes periodiske system, som f. eks. Ti, Ur, V, Cr, Mo, Ma, Fe, Co, Ni gir nye katalysatorer i hvilke direkte bindinger mellom carbonatomer og metallatomer ikke er tilstede, og som er fordelaktig til polymerisering av ethylen, høyere a-olefiner og diolefiner som inneholder minst én vinyl-dobbeltbinding. All such compounds coupled with compounds of transition metals, preferably halogen-containing compounds, of metals belonging to groups IV, V, VI or VIII of the periodic table of the elements, such as e.g. Ti, Ur, V, Cr, Mo, Ma, Fe, Co, Ni provide new catalysts in which direct bonds between carbon atoms and metal atoms are not present, and which are advantageous for the polymerization of ethylene, higher α-olefins and diolefins containing at least one vinyl double binding.
Av de forbindelser av overgangsmetaller som kan anvendes til fremstilling av disse nye katalysatorer er halogenider i hvilke metallet har en valens som er lavere enn den maksimale valens, f. eks. titan-di-og -triklorid, vanadiumdi- og -triklorid, molybden-tri- og -pentaklorid og kobolt-diklorid, særlig fordelaktige. Among the compounds of transition metals that can be used for the production of these new catalysts are halides in which the metal has a valence that is lower than the maximum valence, e.g. titanium di- and -trichloride, vanadium di- and -trichloride, molybdenum tri- and -pentachloride and cobalt dichloride, particularly advantageous.
Polymerisering under anvendelse av katalysatorer ifølge oppfinnelsen utføres fortrinnsvis i nærvær av oppløsningsmidler bestående av aromatiske forbindelser som oppløser minst en del av den forbindelse som inneholder metall-til-nitrogen-bindin-gen. Polymeriseringen utføres fortrinnsvis ved temperaturer mellom romtemperatur og 200° C, fortrinnsvis mellom 50 og 150° C. Polymerization using catalysts according to the invention is preferably carried out in the presence of solvents consisting of aromatic compounds which dissolve at least part of the compound containing the metal-to-nitrogen bond. The polymerization is preferably carried out at temperatures between room temperature and 200° C, preferably between 50 and 150° C.
De herved erholdte polymerisater har en meget regelmessig struktur som hittil bare kunne oppnåes ved anvendelse av katalysatorer fremstillet under anvendelse av organiske metallforbindelser. Ved anvendelse av f. eks. ethylen som utgangsmate-riale får man fullstendig lineære polymerisater i hvilke forgreninger av kjeden ikke kan observeres ved undersøkelse i spektrets infrarøde område. Graden av polyme-risatenes lineære struktur og deres krystal-linitet er større enn hva der er tilfellet for polymerisater erholdt med de mest vanlige Ziegler-katalysatorer fremstillet av titan-tetraklorid og alkylaluminium-forbindelser. The polymers obtained in this way have a very regular structure which until now could only be achieved by using catalysts produced using organic metal compounds. When using e.g. ethylene as starting material, completely linear polymers are obtained in which branching of the chain cannot be observed by examination in the infrared region of the spectrum. The degree of linear structure of the polymers and their crystallinity is greater than what is the case for polymers obtained with the most common Ziegler catalysts made from titanium tetrachloride and alkyl aluminum compounds.
Ved polymerisering av propylen, buten-1 og andre a-olefiner får man ved anvendelse av katalysatorer ifølge oppfinnelsen i høy grad krystallinske produkter med et høyt innhold av isotaktiske makromole-kyler. In the polymerization of propylene, butene-1 and other α-olefins, by using catalysts according to the invention, highly crystalline products with a high content of isotactic macromolecules are obtained.
Ved polymerisering av diolefiner, særlig butadien, kan polymeriseringen ved pas-sende valg av polymeriseringsbetingelser og av forbindelsen av overgangsmetall til dannelse av katalysatoren, rettes mot dannelsen av polymerisater med forskjellig struktur. In the polymerization of diolefins, especially butadiene, the polymerization can be directed towards the formation of polymers with different structures by appropriate selection of polymerization conditions and of the compound of transition metal to form the catalyst.
I det følgende beskrives som eksempler noen utførelsesformer for oppfinnelsen. In the following, some embodiments of the invention are described as examples.
Eksempel 1. Example 1.
5 g aluminium-tris-(difenylamid) og 2 g TiCL, i 250 ml vannfri benzen føres i nitrogenatmosfære inn i en 1100 ml rysteautoklav. Man setter rystningen igang og ethylen tilføres til et trykk på 45 atmosfærer ved romtemperatur. Autoklavens temperatur heves derpå raskt til 100° C. 5 g of aluminium-tris-(diphenylamide) and 2 g of TiCL, in 250 ml of anhydrous benzene are introduced in a nitrogen atmosphere into a 1100 ml shaking autoclave. The shaking is started and ethylene is added to a pressure of 45 atmospheres at room temperature. The temperature of the autoclave is then quickly raised to 100°C.
Autoklaven rystes ved denne temperatur i ca. 8 timer, hvorpå man avbryter oppvarmingen. Når temperaturen i autoklavens indre er falt til 40° C, blåser man ut den gassformige fase som består av ikke reagert ethylen. Ved analyse finner man at denne er fri for andre hydrocarboner når unntaes benzendamper. The autoclave is shaken at this temperature for approx. 8 hours, after which the heating is interrupted. When the temperature inside the autoclave has fallen to 40° C, the gaseous phase consisting of unreacted ethylene is blown out. On analysis, it is found that this is free of other hydrocarbons when benzene vapors are excluded.
Fra autoklaven tar man ut en meget kompakt masse bestående av polyethylen og som etter tørring veier 130 g. A very compact mass consisting of polyethylene is taken out of the autoclave and weighs 130 g after drying.
Rensningen av råprodukt utføres ved å bryte opp den kompakte masse, behandle den gi entagende ganger med methanol som er surgjort med konsentrert saltsyre, vaske den påny med methanol og sluttelig tørre polymerisatet ved 80° C under forminsket trykk. The purification of raw product is carried out by breaking up the compact mass, treating it several times with methanol acidified with concentrated hydrochloric acid, washing it again with methanol and finally drying the polymerizate at 80° C under reduced pressure.
Det erholdte polyethylen har en gjen-nomsnittlig molekylvekt på 780 000 (be-stemt viskosimetrisk) og et innhold av krystallinske bestanddeler på 80 pst. be-stemt ved røntgenundersøkelse. Polymerisatet er fritt for forgrenede kjeder og har et høyt smeltepunkt (134° C). The polyethylene obtained has an average molecular weight of 780,000 (determined viscometrically) and a content of crystalline constituents of 80 per cent, determined by X-ray examination. The polymer is free of branched chains and has a high melting point (134° C).
Eksempel 2. Example 2.
Man går frem således som angitt i eksempel 1, men anvender som katalysator 6 g magnesium-(difenylamid)-bromid og Proceed as indicated in example 1, but use 6 g of magnesium (diphenylamide) bromide as catalyst and
3 g TiCl3. Man får 43 g fast polyethylen 3 g of TiCl3. You get 43 g of solid polyethylene
med egenskaper lignende egenskapene hos det i eksempel 1 erholdte polyethylen. with properties similar to the properties of the polyethylene obtained in example 1.
Eksempel 3. Example 3.
Man anvender 5 g aluminium-bis- (difenylamid)-klorid erholdt fra Al[N(C(iH;-)2] og A1C1., i vannfri ether med påfølgende fjernelse av etheren ved oppvarming til 140 ° C under forminsket trykk, 1 mm Hg. Sammen med denne forbindelse innføres 1 g TiCl3 og 200 ml vannfri benzen i en 650 ml rysteautoklav i nitrogenatmosfære. One uses 5 g of aluminum bis-(diphenylamide) chloride obtained from Al[N(C(iH;-)2] and A1C1., in anhydrous ether with subsequent removal of the ether by heating to 140 ° C under reduced pressure, 1 mm Hg. Together with this compound, 1 g of TiCl3 and 200 ml of anhydrous benzene are introduced into a 650 ml shaking autoclave in a nitrogen atmosphere.
Man setter rystningen av autoklaven igang og tilfører ethylen ved romtemperatur til et trykk på 30 atmosfærer, hvorpå blandingen raskt oppvarmes til 120° C. Etter 10 timer er trykket falt til ca. 15 atmosfærer. Oppvarmingen avbrytes da og man tar ut fra autoklaven 41 g av et fast, kompakt polymerisat med lys fiolett farve. Polymerisatet renses som angitt i eksempel 1. The shaking of the autoclave is started and ethylene is added at room temperature to a pressure of 30 atmospheres, after which the mixture is quickly heated to 120° C. After 10 hours the pressure has dropped to approx. 15 atmospheres. The heating is then interrupted and 41 g of a solid, compact polymer with a light violet color is taken out of the autoclave. The polymer is purified as indicated in example 1.
Eksempel 4. Example 4.
3,5 g magnesium-(diethylamid)-bro-mid, 1,5 g TiCl3 og 250 ml vannfri benzen føres i nitrogenatmosfære inn i en 1-liters roterende autoklav som inneholder 6 kuler av rustfritt stål med diameter 25 mm. 3.5 g of magnesium (diethylamide) bromide, 1.5 g of TiCl 3 and 250 ml of anhydrous benzene are introduced under a nitrogen atmosphere into a 1 liter rotary autoclave containing 6 stainless steel spheres with a diameter of 25 mm.
Ethylen tilføres autoklaven ved romtemperatur til et trykk på 40 atmosfærer. Autoklaven settes i rotasjon og oppvarmes til 120° C. Etter 10 timer hvorunder trykket er falt til ca. 15 atmosfærer, avbrytes oppvarmingen. Man får 30 g krystallinsk, fast polyethylen ved å gå frem således som angitt i foregående eksempler. Ethylene is supplied to the autoclave at room temperature to a pressure of 40 atmospheres. The autoclave is put into rotation and heated to 120° C. After 10 hours during which the pressure has dropped to approx. 15 atmospheres, the heating is interrupted. 30 g of crystalline, solid polyethylene is obtained by proceeding as indicated in previous examples.
Eksempel 5. Example 5.
Ved å gå frem således som angitt i eksempel 1, men anvende som katalysator 6 g aluminium-tris-(N-carbazyl) og 0,8 g TiCl3 i 250 ml vannfri benzen, får man 15 g polyethylen etter 15 timer ved 120° C. By proceeding as indicated in example 1, but using as catalyst 6 g aluminum-tris-(N-carbazyl) and 0.8 g TiCl3 in 250 ml anhydrous benzene, 15 g polyethylene is obtained after 15 hours at 120° C .
Eksempel 6. Example 6.
6 g aluminium-bis-difenylamid-bro-mid, 1,5 g TiCL, og 120 ml vannfri benzen føres under nitrogenatmosfære inn i en autoklav med volum 1100 ml. 6 g of aluminum bis-diphenylamide bromide, 1.5 g of TiCL, and 120 ml of anhydrous benzene are introduced under a nitrogen atmosphere into an autoclave with a volume of 1100 ml.
Autoklaven tilføres 150 g propylen (med renhet over 99 pst.) hvorpå temperaturen raskt heves til 150° C under om-røring i autoklaven. Etter 14 timer avbrytes oppvarmingen og autoklaven avkjøles. Når autoklaven er kold, avblåses den gassformige fase, hvorpå den flytende fase taes ut. Fra den flytende fase kan 19 g pulverfor-met polypropylen isoleres ved tilsetning av methanol som er surgjort med konsentrert saltsyre. The autoclave is fed with 150 g of propylene (with purity above 99 per cent), after which the temperature is quickly raised to 150° C while stirring in the autoclave. After 14 hours, the heating is stopped and the autoclave is cooled. When the autoclave is cold, the gaseous phase is blown off, after which the liquid phase is taken out. From the liquid phase, 19 g of powdered polypropylene can be isolated by adding methanol that has been acidified with concentrated hydrochloric acid.
Det erholdte polymerisat viser en kry-stallinitet på ca. 60 pst. ved røntgenunder-søkelse. The polymer obtained shows a crystallinity of approx. 60 per cent by X-ray examination.
Eksempel 7. Example 7.
Ved å gå frem således som angitt i eksempel 1, men anvende en katalysator som er fremstillet av 3,5 g aluminium-tris-difenylamid og 1,5 vanadium-triklorid, får man 110 g lineært polyethylen med molekylvekt 360 000 etter ca. 8 timer. By proceeding as indicated in example 1, but using a catalyst made from 3.5 g of aluminum tris-diphenylamide and 1.5 vanadium trichloride, 110 g of linear polyethylene with a molecular weight of 360,000 is obtained after approx. 8 hours.
Eksempel 8. Example 8.
1,5 g aluminium-bis-(diethylamid)-monoklorid, 0,25 vannfritt CoCL2 suspendert i 2000 ml vannfri benzen og derpå 65 g butadien (Phillips, ren kvalitet) føres inn i en autoklav med volum 1100 ml. 1.5 g of aluminum bis-(diethylamide) monochloride, 0.25 anhydrous CoCL2 suspended in 2000 ml of anhydrous benzene and then 65 g of butadiene (Phillips, pure grade) are introduced into an autoclave with a volume of 1100 ml.
Omrøringen fortsettes inntil trykket fra en opprinnelig verdi på 2,8 atmosfærer er falt til 0,2 atmosfærer. Oppvarmingen avbrytes da og reaksjonsmassen som er en brun, meget viskos væske, taes ut. Ved tilsetning av methanol til denne masse utskilles der et bunnfall bestående av polybutadien. Dette bunnfall befries fra rester av katalysator ved å oppløse det i benzen i nitrogenatmosfære og felle det påny med methanol. Polymerisatet tørkes sluttelig ved ca. 70° C under et trykk på 20 mm Hg. Stirring is continued until the pressure from an initial value of 2.8 atmospheres has fallen to 0.2 atmospheres. The heating is then interrupted and the reaction mass, which is a brown, very viscous liquid, is taken out. When methanol is added to this mass, a precipitate consisting of polybutadiene is separated. This precipitate is freed from remains of catalyst by dissolving it in benzene in a nitrogen atmosphere and precipitating it again with methanol. The polymer is finally dried at approx. 70° C under a pressure of 20 mm Hg.
Man får 35 g av et polymerisat som ved undersøkelse i spektrets infrarøde område viser seg å inneholde 70 pst. monomere enheter med 1,2-syndiotaktisk kjededannelse. Ved røntgenundersøkelse viser polymerisatet seg å være i høy grad krystallinsk. 35 g of a polymer is obtained which, when examined in the infrared range of the spectrum, is found to contain 70 percent monomeric units with 1,2-syndiotactic chain formation. X-ray examination shows the polymer to be highly crystalline.
Eksempel 9. Example 9.
Man går frem som angitt i foregående eksempler, men anvender en temperatur One proceeds as indicated in previous examples, but uses a temperature
på 43° C. Man får 10 g. polybutadien som ved undersøkelse i spektrets infrarøde område viser seg å inneholde 80 pst. trans-1,4-monomere enheter. at 43° C. 10 g of polybutadiene is obtained which, when examined in the infrared range of the spectrum, is found to contain 80 per cent of trans-1,4-monomeric units.
Eksempel 10. Example 10.
2,5 aluminium-bis- (dif enylamid) -mo-noklorid og 0,3 g vannfritt CoCl2 suspendert i 200 ml benzen føres inn i en 1 liters autoklav. Der tilføres 50 g butadien, hvorpå autoklavens innhold omrøres og holdes på en konstant temperatur av 80° C. Etter noen timer avbrytes oppvarmingen og ved å gå frem som angitt i eksempel 8, får man 12 g polymerisat som inneholder 75 pst. 2.5 aluminum bis-(diphenylamide) monochloride and 0.3 g anhydrous CoCl2 suspended in 200 ml benzene are introduced into a 1 liter autoclave. 50 g of butadiene are added, after which the contents of the autoclave are stirred and kept at a constant temperature of 80° C. After a few hours, the heating is stopped and by proceeding as indicated in example 8, 12 g of polymerizate containing 75 per cent is obtained.
1,2-polybutadien. Polymerisatet er krystallinsk på grunn av 1,2-syndiotaktisk struktur. 1,2-polybutadiene. The polymer is crystalline due to 1,2-syndiotactic structure.
Eksempel 11. Example 11.
Man går frem som angitt i eksempel 10, men anvender som katalysator 2 g aluminium-tris-(diethylamid) og 0,3 g Ti (OC,,!!^ oppløst i 200 ml vannfri benzen. Man får 20 g 1,2-syndiotaktisk polybutadien som ved røntgenundersøkelse viser seg å være krystallinsk. Proceed as indicated in example 10, but use as catalyst 2 g of aluminum tris-(diethylamide) and 0.3 g of Ti (OC,,!!^ dissolved in 200 ml of anhydrous benzene. You get 20 g of 1,2- syndiotactic polybutadiene which on X-ray examination is found to be crystalline.
Eksempel 12. Example 12.
Man går frem som angitt i eksempel 11 under anvendelse av butadien som ut-gangsmateriale, men anvender som katalysator 1 g aluminium-bis-(diethylamid)-monoklorid og 0,3 g CrCl;i suspendert i 150 ml benzen. Man får 15 g polymerisat som inneholder 75 pst. monomere enheter med trans-1,4-kjededannelse. The procedure is as indicated in example 11 using butadiene as starting material, but using as catalyst 1 g of aluminum bis-(diethylamide) monochloride and 0.3 g of CrCl;i suspended in 150 ml of benzene. 15 g of polymer is obtained which contains 75 percent monomeric units with trans-1,4 chain formation.
Eksempel 13. Example 13.
Man går frem som angitt i ekesmpel 6, men anvender som katalysator 7,85 g bis-(magnesiumjodid)- fenylamid (C(.H5N MgJ2) og 2 g TiCl3 suspendert i 200 ml vannfri benzen. The procedure is as indicated in example 6, but 7.85 g of bis-(magnesium iodide)-phenylamide (C(.H5N MgJ2) and 2 g of TiCl3 suspended in 200 ml of anhydrous benzene are used as catalyst.
Man får 8 g polypropylen med et høyt innhold (ca. 80 pst.) isotaktiske makro-molekyler og som ved undersøkelse i spektrets ultrarøde område viser nærvær av vinyl-endegrupper sammen med et megef mindre innhold av vinyliden-engrupper. You get 8 g of polypropylene with a high content (approx. 80 percent) of isotactic macromolecules and which, when examined in the ultra-red range of the spectrum, shows the presence of vinyl end groups together with a much smaller content of vinylidene groups.
Polymerisatets gr ense viskositet, be-stemt i tetrahydronaftalen ved 135° C er 1,2. The ultimate viscosity of the polymer, determined in tetrahydronaphthalene at 135° C., is 1.2.
Eksempel 14. Example 14.
10 g aluminiumnitrid, fremstillet ved 10 g of aluminum nitride, produced by
direkte omsetning mellom aluminiumpul-ver og nitrogen ved høy temperatur, og direct reaction between aluminum powder and nitrogen at high temperature, and
3 g titantriklorid suspendert i 150 ml hep-tan fares i nitrogenatmosfære inn i en 3 g of titanium trichloride suspended in 150 ml of heptane are placed in a nitrogen atmosphere into a
roterbar autoklav i hvilken der befinner rotatable autoclave in which there is
seg 8 kuler av rustfritt stål. 8 stainless steel balls.
Autoklaven settes i rotasjon og den The autoclave is put into rotation and the
oppvarmes til 100° C. Etter 15 timer tilføres heated to 100° C. After 15 hours added
120 g propylen, hvorpå autoklaven roterer 120 g of propylene, after which the autoclave rotates
i ytterligere 10 timer. Oppvarmingen avbrytes da og hele mengden av gassformig for another 10 hours. The heating is then interrupted and the entire quantity of gaseous
propylen samt massen av polymerisat som propylene as well as the mass of polymer which
inneholder det faste propylenpolymerisat contains the solid propylene polymer
i form av et grått granulat, taes ut av autoklaven. in the form of a gray granule, is taken out of the autoclave.
Etter tilsetning av methanol renses Clean after addition of methanol
polymerisatet ved å fjerne restene av katalysator således som angitt i eksempel 1. the polymer by removing the remains of catalyst as indicated in example 1.
Man får 37 g fast polypropylen som You get 37 g of solid polypropylene which
ved røntgenundersøkelse viser seg å være on X-ray examination turns out to be
delvis krystallinsk. partly crystalline.
Claims (7)
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DE2309445A DE2309445C3 (en) | 1973-02-26 | 1973-02-26 | Process for the production of thin float glass |
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NO740631L NO740631L (en) | 1974-08-27 |
NO133934B true NO133934B (en) | 1976-04-12 |
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BE (1) | BE811051A (en) |
BR (1) | BR7401301D0 (en) |
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DK (1) | DK145570C (en) |
ES (1) | ES423517A1 (en) |
FR (1) | FR2219123A1 (en) |
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DE102017124625A1 (en) | 2016-12-22 | 2018-06-28 | Schott Ag | Thin glass substrate, method and apparatus for its manufacture |
WO2019076492A1 (en) | 2017-10-20 | 2019-04-25 | Schott Ag | Thin glass substrate, in particular thin borosilicate glass substrate, process and apparatus for manufacturing same |
-
1973
- 1973-02-26 DE DE2309445A patent/DE2309445C3/en not_active Expired
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1974
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DE2309445A1 (en) | 1974-10-17 |
BR7401301D0 (en) | 1974-11-19 |
DK145570C (en) | 1983-05-30 |
NO133934C (en) | 1976-07-21 |
DE2309445B2 (en) | 1975-05-15 |
IT1019602B (en) | 1977-11-30 |
JPS502009A (en) | 1975-01-10 |
ES423517A1 (en) | 1976-05-16 |
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NO740631L (en) | 1974-08-27 |
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