Patent GB-1361325-A (GB)
Title: Method for controlled polymerization and copolymerization of monomers with olefinic double bond able to polymerize by a cationic mechanism
IPC: C08F210/10
Filed: 1972-07-21
Abstract: 1361325 Photopolymerization CESKOSLOVENSKA AKADEMIE VED 21 July 1972 [29 July 1971] 34293/72 Heading C3P Olefinically unsaturated monomers capable of cationic polymerization are polymerized by a method in which polymerization is catalyzed by a halide of vanadium, titanium or zirconium and accelerated by addition of activators and by action of light. Specified activator are MxAy where M is alkali metal, alkaline earth metal, copper, zinc, boron, aluminium, silicon, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, uranium, iron, cobalt or nickel, A is -O-, -OH or -OR where R is alkyl or aryl, x is 1 or 2 and y is 1 to 5; reaction products of boron trifluoride with aluminium or magnesium hydroxides and/or alkoxides; compounds Al(OH) 2 X, Al(OH)X 2 , Al(OR) 2 X, Al(OR)X 2 , Mg(OR)X and Mg(OH)X where X is halogen, -O- or -OH and in hydroxy compounds also -OR; uni- and bivalent metal aluminates, silicates and carbonates; activated carbon; and finely dispersed zinc, copper, aluminium and iron. The polymerization may be controlled by metering the catalyst and/or activator to the reaction system and by controlling the illumination. Specified monomers are styrene, α-methylstyrene, vinylethers, butadiene, isoprene, chloroprene, dimethallyl, 2,3- dimethylbutadiene, piperylene, cyclohexadiene, cyclopentadiene, alkoxybutadienes and particularly isobutylene with and without butadiene. Examples describe the polymerization of isobutylene in the presence of vanadium tetrachloride and (1) lithium t. butoxide, (2) barium oxide, (3) potassium or sodium hydroxide, (9) ferric oxide, (10) calcium hydroxide, (11) molybdenum trioxide, (12) cupric oxide, (16) aluminium sec. butoxide with and without boron trifluoride, (25) dipropoxy aluminium fluoride, (30) copper, iron, zinc or aluminium, (31) magnesium aluminate, magnesium silicate or silica, (32) n-butyl orthoborate, (33) activated carbon and (35) potassium, magnesium, ferrous or zinc carbonate; titanium tetrachloride and (4) sodium hydroxide, (5) alumina, (6) vanadium oxide, (21) aluminium hydroxide and boron trifluoride, (22) partially hydrolysed aluminium sec. butoxide and boron trifluoride, (23) dihydroxy aluminium fluoride and (24) magnesium hydroxide and boron trifluoride; titanium tetrabromide and (7) magnesium oxide; titanium tetraiodide and (8) calcium oxide; and (29) vanadium tetrabromide and aluminium hydroxide or vanadium tetraiodide and magnesium hydroxide; and the copolymerization of isobutylene and butadiene using vanadium tetrachloride and (13) molybdenum trioxide and (14) potassium hydroxide; of isobutylene and isoprene with (15) vanadium tetrachloride and potassium hydroxide; of isobutylene, butadiene and styrene using vanadium tetrachloride and (17) sodium ethoxide and (26) titanium tetrabromide, aluminium t.-butoxide and boron trifluoride; of isobutylene and 2,3-dimethylbutadiene using vanadium tetrachloride and (18) potassium phenoxide; of isobutylene and chloroprene using vanadium tetrachloride and lithium t.butoxide; of isobutylene and vinyl isobutyl ether using (20) vanadium tetrachloride and barium hydroxide; of isobutylene, butadiene and isoprene using (27) vanadium tetrachloride, titanium tetraiodide, aluminium sec. butoxide and aluminium chloride; of C 4  petroleum fractions using (28) vanadium tetrachloride, aluminium sec. butoxide and aluminium trichloride; and of vinyl isobutyl ether and dimethylbutadiene using (34) titanium tetraiodide and aluminium oxide.