GB945154A - A process for the catalytic polymerisation of monomeric epoxy compounds; the resulting polymeric materials; and catalysts suitable for use therein - Google Patents

Abstract

A monomeric epoxy compound is contacted with a polymerization catalyst prepared by commmunicating the solid obtained by heating to fusion a mixture comprising (1) a compound containing the grouping MOR where M is a Group II or III metal and OR is an alkoxy, substituted alkoxy, aryloxy or substituted aryloxy group and (2) either a halogen-containing compound of a metal of Group II to VIII or a mixture of (a) a compound of formula MOR where M is a metal selected from Group II to VIII and OR is as defined above and (b) free halogen or a halogen compound which forms free halogen under the conditions of catalyst preparations with the proviso that the metals in (1) and (2) are different and that the metal compounds are such that the resulting fusion product is a solid at 20 DEG C. Specified monomeric epoxy compounds are epichlorhydrin, ethylene oxide, 1:2 propylene oxide, styrene oxide, cyclohexene oxide, phenylglycidyl ether, tolyl glycidyl ether, chlorophenyl glycidyl ether and naphthyl glycidyl ether. The polymerization may be effected in the presence or absence of a solvent at 0-200 DEG C. and 1-40 atmospheres pressure. Alternatively suspension polymerization techniques using benzene as a disperse phase may be preferred. Examples describe the preparation of polyethylene oxide using as catalysts (1) Al (OC3H7)3 and ZnCl2 and (2) Al(OC3H7)3 and FeCl3. Specifications 876,648, 887,573, 887,988 and 945,151 are referred to.ALSO:A catalyst suitable for use in the polymerization of a monomeric epoxy compound is prepared by comminuting the solid obtained by heating to fusion a mixture comprising (1) a compound of a metal of Group II or III which compound contains in its molecular structure an -OR group attached to a Group II or III metal atom through the oxygen atom of the -OR group, the -OR group representing an alkoxy, a substituted alkoxy, and aryloxy or a substituted aryloxy group, and (2) either a halogen-containing compound of a metal of any of Group II to VIII inclusive or a mixture of (a) a compound of a metal of Group II to VIII which contains in its molecular structure a plurality of -OR groups and (b) free halogen or a halogen compound which forms free halogen under the conditions of catalyst preparation, with the proviso that the metal compounds referred to under (1) and (2) are compounds of different metals and that the metal compounds are such that the resulting fusion product is a solid at 20 DEG C. In a modification the catalyst comprises the fusion product from (1) at least two metal compounds containing the grouping M-OR, M being a metal selected from Group II or III and OR being as defined above and (2) chlorine, bromine or iodine, there also being present a compound of a different metal selected from Group II to VIII. Examples of (1) above are aluminium ethyl diethoxide, aluminium ethyl diisopropoxide, aluminium diethyl ethoxide, aluminium triisopropoxide, aluminium triphenoxide, zinc diethoxide, zinc ethyl ethoxide, zinc diisopropoxide, zinc diphenoxide, magnesium ethoxide, magnesium ethylethoxide, and magnesium ethyl phenoxide. Examples of metal halides are MgCl2, ZnCl2, AlCl3, TiCl4, SnCl4, and FeCl3. Alternatively alkoxy halides or alkyl alkoxy halides, e.g. aluminium, zinc and magnesium ethoxy dichloride or ethyl ethoxychlorides may be used in preparing the catalysts. Compounds of general formula M[R1]c(OR)a[X]b where M is a metal from Group I. II, III, IV or V, R1 is an alkyl, aryl or substituted aroxy group, OR is as defined above and X is a halogen, a, b and c being integers or zeros, may be also used to prepare the catalysts, examples being sodium methoxide, titanium ethyl diethoxychloride, titanium triisopropoxychloride, titanium ethyl triisopropoxide, and titanium phenyl triisopropoxide. Preferred catalysts are prepared by fusing Al(OC3H7)3 and Zn(OC25)2 in the presence of halogen; AlEt3 and Zn(OEt)2 in the presence of halogen; AlEt2Cl and Zn(OEt)2; AlEtCl2 and Zn(OEt)2; ZnOEtCl and AlEt3; AlEt2OEt and ZnOEtCl; AlEt3 and ZnCl2; AlEt2Cl and ZnCl2, AlEtCl2 and ZnCl2; AlEt(OEt)2 and FeCl3; ZnEtOEt and FeCl3; ZnEtCl and FeCl3 and Al(OC4H9)3 and FeCl3. Polymerization examples are given. Specifications 876,648, 887,573, 887,988 and 945,151 are referred to.