Verfahren zur Umsetzung alpha-olefinartiger Verbindungen

摘要

2-methyl-1,4-hexadiene is polymerised with a catalyst comprising 0,34 part vanadium tetrachloride and 0,64 part aluminium tri-isobutyl in 32 parts benzene with cooling. After 16 hours at room temperature the catalyst is destroyed with methanol and hydrochloric acid and the polymer (M.W. 370) of the structure is dissolved in toluene and with addition of a cobalt drier cast on glass and baked at 125 DEG C. for 30 minutes to give a clear film. 2,4-hexadiene can be similarly polymerised using titanium tetrachloride and aluminium tri-isobutyl and cast to a clear, non-tacky film.ALSO:The dimerisation or codimerisation of like or unlike molecules containing a vinyl, CH2=CH - , group is effected at at least 10 atmospheres pressure in the presence of a salt of a noble metal of Group VIII of the periodic table. The compounds generally have the formula CH2=CH - X where X is hydrogen, halogen, hydrocarbon, halohydrocarbon, alkoxycarbonyl, acyloxyalkyl, acyloxy, nitrile, aminoalkyl, hydroxyalkyl or carbonamido and preferably contain no more than 12 carbon atoms. Specified are ethylene, propylene, 1-butene, 1-octene, 1-dodecene, 3-methyl-1-pentene, 3-methyl-4-ethyl-1-hexene, 3-methyl-1-butene, 1-hexene, 5-methyl-1-hexene, 3, 4-dimethyl-1-pentene, 3, 3-dimethyl-1-butene, 1-pentene, 3-methyl-1-hexene, vinyl cyclohexene, 1-decene, styrene, 1, 3-butadiene, 1,4-hexadiene, 2-methyl-1, 3-butadiene, 2-chloro-1, 3-butadiene, 2-fluoro-1, 3-butadiene, vinyl chloride, methyl acrylate, acrylonitrile, acrylamide, allyl alcohol, allyl acetate, allyl butyrate and allylamine. The metal salt may be a halide, sulphate, nitrate or a salt of an aliphatic acid of up to 8 carbon atoms, e.g. ruethenium dichloride, tetrachloride, triiodide, nitrate, trinaphthenate, tristearate, or trichloride, platinum dichloride, tetrachloride, tetraacetate, tetraiodide or platinic sulphate tetrahydrate, palladium dibromide or sulphate, osmium dichloride or trichloride, iridium tetrachloride, tetrabromide or triiodide and their hydrates. The molar ratio of salt to unsaturated compound may be from 0,0001 to 0,1. Temperatures of 20 DEG -275 DEG C. are used, with pressures up to 2,000 atmospheres, and times of 30 minutes-30 hours. An inert liquid reaction medium may be added, e.g. methanol, ethanol, propanol, butanol, cyclohexanol, the dimethyl ether of ethylene glycol, tetrahydrofurane, acetonitrile or propionitrile, in amounts which can equal or exceed the unsaturated compound by 40 fold. A polymerisation inhibitor such as hydroquinone may also be added. The examples describe the following dimerisations and codimerisations : (1) ethylene to give butenes; (6) propylene to hexenes; (10) butadiene to 2, 4, 6-octatriene; (11) butadiene/ethylene to C8 diolafenes; (12) butadiene/ethylene to 1, 4- and 2, 4-hexadienes; (13) butadiene/propylene to 2-methyl-1, 4-hexadiene; (14) propylene/ethylene to pentenes and hexenes; (16) chloroprene/ethylene to chlorohexadienes; (17) styrene/ethylene to 2-phenylbutene; (20 methyl acrylate to dimethyl a -dihydromuconate which on hydrogenation yields dimethyl adipate; (21) methyl acrylate/ethylene to methyl 3-pentenoate; (22) allyl acetate/butadiene to CH3COOC11H17 (one mol allyl acetate +2 mols butadiene); (23) vinyl chloride/ethylene to chlorobutanes.