GB670159A - Improvements in the manufacture of glycol sulphite and its polymers - Google Patents

Abstract

Polymeric glycol sulphite is prepared by subjecting, by simple contact in the liquid state, the oxonium compound (CH2)2.O.SO2 which results from the combination of ethylene oxide with sulphur dioxide at a low temperature, e.g. 0 DEG C., to the action of a catalyst selected from the group consisting of amines, amides, sulphamides and phosphines. In a modification, a liquid mixture of ethylene oxide and a catalyst of the group specified is reacted with an amount of sulphur dioxide equimolecular to the ethylene oxide, the oxonium compound being formed in situ and converted into glycol sulphite polymer as it is formed. The catalyst is preferably used in an amount of 3-5 per cent by weight of the oxonium compound or ethylene oxide treated. The polymerization is preferably effected at between 0 DEG and 10 DEG C. at ordinary pressure; raised pressures and agitation accelerate rate of reaction. The preferred catalyst is a tertiary or heterocyclic amine; primary and secondary amines and polyamines are referred to. The polymer is practically insoluble in water, ethyl alcohol and benzine but is soluble in monomeric glycol sulphite. The polymer is converted into monomeric glycol sulphite on heating to temperatures above 140 DEG C. In examples: (1) the oxonium compound is allowed to stand for about 30 hours at between 0 DEG and 5 DEG C. in presence of pyridine yielding a viscous polymer of glycol sulphite which is substantially quantitatively converted into the monomer on heating at between 140 DEG and 150 DEG C. for 30-60 minutes, the monomer being isolated by reduced pressure distillation; (2) sulphur dioxide is passed into a mixture of ethylene oxide and diethylaniline catalyst at between 0 DEG and 10 DEG C. and the product maintained at the same temperature for 30-40 hours to form glycol sulphite polymer; this is treated as in (1) to form monomeric glycol sulphite. U.S.A. Specification 2,413,405 is referred to. The Specification as open to inspection under Sect. 91 defines the catalysts as compound arising from the substitution of one or more hydrogen atoms by organic radicals in the compounds which the elements of the 5th Group form with hydrogen and is not restricted to the use of liquid state in the production of the oxonium compound and glycol sulphite polymer. This subject-matter does not appear in the Specification as accepted.ALSO:Monomeric glycol sulphite is prepared by heating to a temperature above 140 DEG C. the glycol sulphite polymer obtained either by subjecting by simple contact in the liquid state, the oxonium compound (CH2)2.O.SO2, which results from the combination of ethylene oxide with sulphur dioxide at a low temperature, e.g. 0 DEG C., to the action of a catalyst selected from the group consisting of amines, amides, sulphamides and phosphines, or in a modification by reacting a liquid mixture of ethylene oxide and a catalyst of the class specified above with an amount of sulphur dioxide equimolecular to the ethylene oxide, the said oxonium compound being formed in situ and converted into glycol sulphite polymer as it is formed (see Group IV (a)). The preferred catalysts are primary and heterocyclic amines; they are used in amounts of 3-5 per cent. In examples: (1) a glycol sulphite polymer obtained by allowing the sbove-mentioned oxonium compound to stand for about 30 hours at between 0 DEG and 5 DEG C. in presence of pyridine is heated under ordinary pressure at between 140 DEG and 150 DEG C. for 30-60 minutes and the monomeric glycol sulphite recovered by distillation under reduced pressure; (2) sulphur dioxide is passed into a mixture of ethylene oxide and, as catalyst, diethyl aniline at between 0 DEG and 10 DEG C., the product being converted into glycol sulphite polymer on standing at the same temperature and treated as in (1) to yield the monomer. U.S.A. Specification 2,413,405 is referred to. The Specification as open to inspection under Sect. 91, defines the catalysts as compounds arising from the substitution of one or more hydrogen atoms by organic radicals in the compounds which the elements of the 5th Group form with hydrogen and is not restricted to the use of the liquid state to the production of the oxonium compound and glycol sulphite polymer. This subject-matter does not appear in the Specification as accepted.