Patent GB-992113-A (GB)
Title: Metal halides
IPC: C08G65/26
Filed: 1961-05-16
Abstract: The invention comprises a compound useful as a catalyst in the polymerization of olefins and organic cyclic oxides (see Division C3) comprises (A) at least one of antimony, arsenic, bismuth and phosphorus; (B) at least one of chromium, molybdenum, titanium, vanadium and zirconium; (X) at least one of bromine, chlorine and iodine; and (Z) fluorine; where the total of the gram atoms of B plus Z is greater than the total of the gram atoms of A plus X; and a process for the preparation thereof by reacting a compound having the formula BXm and a compound having the formula AY where B is chromium, molybdenum, titanium, vanadium or zirconium, X is bromine, chlorine, iodine or a mixture thereof, m is equal to the valence of B, A is antimony, arsenic, bismuth or phosphorus and Y consists of three fluorine atoms or two fluorine atoms and one atom of chlorine, bromine or iodine. The reaction may be carried out in the presence of a free halogen and/or a minor molar proportion of a higher bromide, chloride or iodide of the A element.  In examples, a catalyst is prepared by reacting titanium tetrachloride with antimony trifluoride.ALSO:Olefins and organic cyclic oxides are polymerized in the presence, as catalyst, of a compound comprising (A) at least one of antimony, arsenic, bismuth and phosphorus; (B) at least one of chromium, molybdenu, titanium, vanadium and zirconium; (X) at least one of chlorine, bromine and iodine; and (Z) fluorine; where the total of the gram atoms of B plus Z is greater than the total of the gram atoms of A plus X, and, essentially in the case of the olefins and preferably in the case of the cyclic oxides, a metal-containing reducing cocatalyst.  Cocatalysts which may be used are those conventionally used in making Ziegler type catalysts, e.g. metal hydrides, organo-metallic compounds, and mixtures of AlCl3 with aluminium trialkyls, lead tetraethyl, sodium hydride, zinc diethyl, phenyl sodium, isoamyl sodium or Grignard reagents. Preferred olefin monomers are those having the formula H2C=CHR, where R is hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbon radical having from 1 to 8 carbon atoms. Organic cyclic oxide monomers which may be used include one or more cyclic oxides having one or more oxygen-carbon rings having 2 to 6 carbon atoms and one oxygen in the ring and being saturated or unsaturated.  Mono- and poly-epoxides mentioned include alkylene oxides, glycidyl ethers and esters, oxetane, substituted oxetanes, furan, dihydrofuran, substituted furans, pyran, benzopyran polymethylene oxides, vinyl cyclohexane dioxide, limonene dioxide, the reaction product of the diglycidyl ether of pentane diol and bisphenol A, bis-1,11-(3,4-epoxy-6-methyl phenyl) methyl formate and the diglycidyl ether of a polyalkylene or arylene ether glycol.  In the examples ethylene, propylene and butadiene and propylene oxide are polymerized using a catalyst comprising the reaction product of titanium tetrachloride and antimony trifluoride.ALSO:A catalyst for use in polymerizing organic cyclic oxides and olefins (see Division C3) comprises a compound comprising (A) at least one of antimony, arsenic, bismuth and phosphorus; (B) at p  least one of chromium, molybdenum, titanium, vanadium and zirconium; (X) at least one of bromine, chlorine and iodine; and (Z) fluorine; where the total of the gram atoms of B plus Z is greater than the total of the gram atoms of A plus X, and a metal-containing reducing cocatalyst.  The cocatalysts may be those conventionally used in making Ziegler type catalysts, e.g. metal hydrides, organo-metallic compounds, and mixtures of AlCl3 with aluminium trialkyls, lead tetraethyl, sodium hydride, zinc diethyl, phenyl sodium, isoamyl sodium or Grignard reagents.