Aluminum chlorofluoride polymerization catalysts

The invention comprises aluminium chlorofluorides having a fluoride content of 9,7 to 72,8% by weight based on the total halogens present, the balance of the halogen being chloride, containing crystallites having radii of 500 Angstrom units or less. Aluminium chlorofluorides mentioned have the empirical formulae AlCl2F, AlClF2, Al2Cl5F, Al2Cl3F3 and Al2ClF5. The aluminium chlorofluorides are prepared by reacting stoichiometric proportions of anhydrous aluminium chloride dissolved in an inert solvent with hydrogen fluoride, boron trifluoride, benzotrifluoride or ethylidene fluoride, or by fusing mixtures of aluminium chloride and aluminium trifluoride. In examples aluminium chlorofluorides are prepared by reacting aluminium chloride with boron trifluoride and with ethylidene fluoride, in ethyl chloride.ALSO:Olefinic or diolefinic hydrocarbons or halohydrocarbons are polymerized by contacting them with a catalyst comprising an aluminium chlorofluoride having a fluoride content of 9,7 to 72,8% by weight based on the total halogens present, the balance of the halogen being chloride, containing crystallites having radii of 500 Angstrom units or less. Aluminium chlorofluorides mentioned have the empirical formulae AlCl2F, AlClF2, Al2Cl5F, Al2Cl3F3 and Al2ClF5. The monomers may be contacted with the aluminium chlorofluoride at -100 DEG C. to 250 DEG C. at atmospheric or superatmospheric pressure, with or without an inert diluent present. One part by weight aluminium chlorofluoride may be mixed with 0,1 to 20 parts by weight of a co-catalyst, e.g. antimony pentachloride, antimony trichloride, tin tetrachloride, titanium tetrachloride, titanium trichloride, silicon tetrachloride, ferric chloride, aluminium bromide, chromium trichloride, zirconium tetrachloride and zinc chloride. In examples aluminium chlorofluorides are used as catalysts, in some examples in conjunction with titanium tetrachloride, to form polymers of ethylene, cyclopentene, styrene, dicycloheptadiene, isobutylene and isoprene, and copolymers of isobutylene with isoprene, isobutylene with styrene, dicycloheptadiene with isoprene, and propylene with isoprene. Other monomers mentioned are butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, vinyl fluoride, chlorprene, methylstyrenes, ethylstyrenes, isopropylstyrenes, butylstyrenes, chloro-styrenes, chloromethylstyrenes and chloroisopropylstyrene.