Patent GB-896999-A (GB)
Title: Polyether-thioether-glycols
IPC: C08G75/12
Filed: 1958-08-01
Abstract: Polyether-thioether glycols having molecular weights of 500 to 60,000 are prepared by reacting a polyether glycol of the formula HO-(CH2CH2O)m-R-O-(CH2CH2O)n-H where R is an alkylene, cycloalkylene or arylene radical which may contain hydroxyl and/or oxalkylated hydroxyl groups, and the sum of m and n is 6 to 200, with a thioether glycol of the formula HO-(CHR1CHR2-S-CHR3CHR4O)p-H where R1, R2, R3 and R4 are hydrogen or alkyl, cycloalkyl or aryl groups, and p is 1 to 200.  The reaction is preferably effected at temperatures of 140 DEG  to 220 DEG C. in the presence of a dehydration catalyst such as p-toluene sulphonic acid or phosphoric acid.  The products preferably have three ethereal oxygen atoms per ethereal sulphur atom. Specified polyether glycols are octaethylene, dodecaethylene and hexadecaethylene glycols, decaoxethylated butane-1,4-diol, decaoxyethylated trimethylolpropane, pentadecaoxethylated hydroquinone and oxyethylated resorcinol or phlorglucinol of p molecular weight about 1,000.  Suitable thioether glycols are thiodiglycol, b ,b 1-dimethylthiodiglycol, b ,b 1-diphenylthiodiglycol and self-condensates thereof. Mono-and poly-hydric alcohols may also be present.  The products are used to prepare polyurethanes by reaction with polyisocyanates.  For this, they may be used together with other compounds containing reactive hydrogen, e.g. polyhydroxy compounds, polyether and thioether glycols, polyesters and polyesteramides.  Specified polyisocyanates are 2,4- and 2,6-toluene-, 4,41-diphenylmethane-, 1,5-naphthalene- and 4,41 - dicyclohexyl - dimethylmethane - diisocyanates. Catalysts such as those disclosed in Specification 769,680 may be used.  The polyurethanes may be cellular or non-porous rubberlike substances or be made into films and coatings.  In Example 6, maleic anhydride is added to octaethylene glycol and thiodiglycol and the condensation product is mixed with toluylene diisocyanate, dimethylbenzyl amine, water, and aqueous solutions of oxethylated oxydiphenyl and of the sodium salt of sulphonated castor oil to give a foamed polyurethane. The polyether-thioether glycols are themselves useful as dust binders for fertilizers.  Specification 791,854 also is referred to. Reference has been directed by the Comptroller to Specifications 818,359 and 819,384.ALSO:Foamed polyurethanes are made from polyether-thioether glycols which have been prepared by reacting a polyether glycol of the formula HO-(CH2CH2O)m-R-O-(CH2CH2) -nH where R is an alkylene, cycloalkylene or arylene radical which may contain hydroxyl and/or oxalkylated hydroxyl groups, and the sum of m and n is 6 to 200 with a thioether glycol of the formula HO(CHR1CHR2-S-CHR3 CHR4 O)pH where R1 R2 R3 and R4 are hydrogen or alkyl, cycloalkyl or aryl groups and p is 1 to 200. In Example 6, octaethylene glycol is condensed with thiodiglycol and a small amount of maleic anhydride, giving a polymer of mol wt. 2800.  This is mixed with toluylene diisocyanate, dimethyl benzyl amine, water and aqueous solutions of oxethylated oxydiphenyl and of the sodium salt of sulphonated castor oil, to give a hard foam.  Reference has been directed by the Comptroller to Specifications 818,359 and 819,384.