Patent GB-962792-A (GB)
Title: Process for the manufacture of polymers of oxacycloalkanes
IPC: C08G65/18
Filed: 1960-05-30
Abstract: A process for the manufacture of polymers of oxacycloalkanes comprises polymerization or copolymerization of the oxacycloalkane or oxacycloalkanes in the presence or absence of an inert solvent, at a temperature of from -80 to + 150 DEG C., and in the presence of a two component catalyst, in which catalyst the first component is (a) an organoaluminium compound of the general formula R.A1R1,R2 in which R represents an alkyl group containing 1 to 6 carbon atoms or an ethoxy group, R1 represents a hydrogen or halogen atom or an alkyl group containing 1 to 6 carbon atoms and R2 represents a hydrogen or halogen atom or an alkyl group containing 1 to 6 carbon atoms, or (b) a zinc dialkyl in which the alkyl groups contain from 1 to 6 carbon atoms, or (c) one of the following mixtures of organoaluminium compounds and organozinc, organoboron or organotitanium compounds: A1(R)3+Zn(R1)2, in which each of R and R1 represents C2H5 or CH3, or A1(R)3+B(R1)3, in which each of R and R1 represents C2H5, C4H9 or CH3, or A1(R)3+Ti(OR1)4, in which each of R and R1 represents CH3 or C2H5, and in which catalyst system the second component comprises at least one organic halogen compound containing the grouping <FORM:0962792/C3/1> Halogen or the grouping <FORM:0962792/C3/2> attached to a carbon atom.  Organo-aluminium compounds specified are aluminium trimethyl, aluminium triethyl, aluminium tri-isobutyl, di-isobutylaluminium hydride, diethylaluminium chloride, diethylethoxyaluminium, methylaluminium dichloride, and ethylaluminium dichloride. Organic halogen compounds specified are 4-chloromethyl-1, 3-dioxolone-2; 4-chloromethyl-1, 3-dioxolone; epichlorohydrin, 2-chloroethyl methyl ether, bis-2-chloroethyl ether, 2,2,2-tris (2-chloro-1, 1,2-tri-fluoroethoxymethyl)-ethanol and ethyl hexafluoropropyl ether.  The oxacycloalkanes polymerizable by the process of the invention may be oxacyclopropane; oxacyclopentane; diethylene glycol formal; oxacyclobutanes of the general formula (A): <FORM:0962792/C3/3> <FORM:0962792/C3/4> where A, X and X1 each represents a halogen or hydrogen atom or an alkyl or an alkoxy group; or oxacyclobutanes of the general formula B where each of R1 to R6 represents a hydrogen atom or a methyl or ethyl group.  Inert solvents specified include butane, pentane, hexane, cyclohexane, hydrogenated Diesel oils having a boiling range of 180 DEG  to 250 DEG C., benzene, toluene, methylchloride, methylene chloride, chloroform, carbon tetrachloride, fluorodichloromethane and o-dichlorobenzene or mixtures thereof.  Many examples are given and the process is compared with similar processes omitting the organic halogen compound or using other catalysts e.g. the addition product of BF3 with tetrahydrofuran. Specifications 723,777, 758,450 and 769,116 are referred to.  Reference has been directed by the Comptroller to Specifications 819,407 and 832,283.ALSO:Catalysts for the polymerization or copolymerization of oxacycloalkanes comprise (A) either (a) an organoaluminium compound of the general formula R.AlR1.R2 in which R represents an alkyl group containing 1-6 carbon atoms or an ethoxy group, R1 represents a hydrogen or halogen atom or an alkyl group containing 1-6 carbon atoms and R2 represents a hydrogen or halogen atom or an alkyl group containing 1-6 carbon atoms, or (b), a zinc dialkyl in which the alkyl groups contain from 1-6 carbon atoms, or (c), one of the following mixtures of organoaluminium compounds and organozinc, organoboron or organotitanium compounds:  Al(R)3 + Zn(R1)2, in which each of R and R1 represents C2H5 or CH3 or Al(R)3 + B(R1)3, in which each of R and R1 represents C2H5,C4H9 or CH3, or Al(R)3 + Ti(OR1)4, in which each of R and R1 represents C2H5 or CH3, and (B) at least one organic halogen compound containing the grouping <FORM:0962792/B1-B2/1> Halogen, or the grouping <FORM:0962792/B1-B2/2> Halogen. Organoaluminium compounds specified are aluminium triethyl, aluminium trimethyl, aluminium tri-isobutyl, di-isobutylaluminium hydride, diethylaluminium chloride, diethylethoxyaluminium, methylaluminium dichloride and ethylaluminium dichloride.  Organic halogen compounds specified are 4-chloromethyl-1,3-dioxolone-2; 4-chloromethyl-1,3-dioxolane; epichlorohydrin; 2,2,2-tris (2-chloro-1,1,2-trifluoroethoxymethyl)ethanol; 2-chloroethyl methyl ether; bis-7-chloroethyl ether and ethyl hexafluoropropyl ether. Specifications 723,777, 758,450 and 769,116 are referred to. Reference has been directed by the Comptroller to Specifications 819,407 and 832,283.