| 摘要 |
A process for polymerizing butadiene-1,3 comprises contacting butadiene-1,3 under polymerization conditions with a catalyst selected from (1) a catalyst comprising (a) a compound of formula RnM where R is alkyl, cycloalkyl, aryl, aralkyl or alkaryl, M is aluminium, gallium, indium or thallium and n is the valence of the metal M, (b) a titanium halide of formula TiX4 where X is chlorine or bromine, and (c) an inorganic iodide of formula M1Ix where M1 is beryllium, zinc, cadmium, aluminium, gallium, indium, thallium, silicon, germanium, tin, lead, phosphorus, arsenic or bismuth and x is 2 to 5; and (2) a catalyst comprising (a1) a compound RnM as defined above, (b1) titanium tetraiodide and (c1) an inorganic halide of formula M11Xy where M11 is aluminium, gallium, indium, thallium, germanium, tin, phosphorus, antimony, arsenic or bismuth, X is chlorine or bromine and y is 2 to 5. The process may be effected batchwise or continuously, in the solid phase or in the presence of diluents, e.g. benzene, toluene, xylene, ethylbenzene, propane, butane, pentane, isopentane, hexane, isohexane, isooctane, decane, cyclohexane, methylcyclohexane, styrene, butene-1, butene-2, vinyl halides, trichloroethylene, chlorobenzene and chloronaphthalene. Specified organometallic compounds are trimethyl, triethyl, triisobutyl, tri-n-dodecyl, tricyclopentyl, triphenyl, tri-p-tolyl and tribenzyl aluminium. Many suitable titanium and inorganic halides are specified and examples describe the polymerization of butadiene in the presence of toluene and catalysts comprising triisobutyl aluminium and titanium tetrachloride with (I) antimony triiodide and (II and III) aluminium triiodide; triisobutyl aluminium and titanium tetraiodide with (IV) antimony trichloride, (V) phosphorus trichloride, (VI) stannic chloride and (VII) aluminium trichloride. The products may be purified by steam stripping, the catalysts inactivated by adding ethyl alcohol or isopropyl alcohol, and the polymer stabilized by the addition of an antioxidant, e.g. phenylbeta-naphthylamine or 2,21-methylene-bis(4-methyl-6-tert. butylphenol). The products have a predominantly cis-1,4 configuration and may be compounded with fillers, other polymers, e.g. natural rubber and polyethylene, and conventional vulcanizing ingredients. They may be used in the manufacture of tyres and gaskets.
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