Patent GB-872126-A (GB)
Title: A process for the production of polysulphides containing hydroxyl groups
IPC: C07B45/06
Filed: 1959-09-10
Abstract: Polysulphides containing hydroxyl groups are prepared by interacting a 1,2-alkylene oxide, or a substitution product thereof, with sulphur and hydrogen sulphide in the presence of a basic catalyst, the sulphur being used in an amount of at least substantially 1 gm. atom per 2 moles of alkylene oxide or substitution product thereof.  The specified minimum quantity of sulphur yields a disulphide product; about 2 gm. atoms of sulphur yield a tri-sulphide and proportionately greater amounts of sulphur yield the higher polysulphides.  Specified alkylene oxides are ethylene, propylene, butylene, styrene and cyclohexene oxides; glycide, glycide ethyl ether, glycide acetate, glycidic acid ethyl ester, 9:10-epoxy stearic acid, epichlorhydrin; butadiene, isoprene and dialkyl dioxides, diglycide ether, phenoxy propene oxide, p-phenylene di-oxypropene oxide and piperazine dipropene oxide.  Suitable catalysts include alkali metal hydroxides, sulphides and carbonates, ammonium acetate, and organic bases such as triethylamine, tripropylamine and piperidine, and their salts with weak organic acids such as formic, acetic and benzoic acids; a basic catalyst may be formed in situ.  The catalyst is generally used in amounts of from 1 to 20% by weight of the alkylene oxide.  The hydrogen sulphide is preferably used in molar excess.  Reaction may be effected at up to 140 DEG C. or higher and, if desired, under pressure.  In typical Examples: (1) hydrogen sulphide is fed into a cooled mixture of propylene oxide, sulphur, triethylamine catalyst and dioxane diluent, then propylene oxide and hydrogen sulphide and finally hydrogen sulphide alone are fed in and the product is distilled to recover bis(hydroxypropyl)disulphide; (2) styrene oxide, sulphur and hydrogen sulphide are similarly reacted whereupon additional sulphur and styrene oxide are added and reacted by feeding in hydrogen sulphide and styrene oxide so yielding bis(phenylhydroxyethyl)disulphide; (6) a mixture of water, sulphur and thiodiglycol is heated to form triethylol sulphonium hydroxide catalyst and then hydrogen sulphide and ethylene oxide are passed in while slowly adding sulphur to give bis(hydroxyethyl)trisulphide which is reduced to monothioglycol with zinc and acid.  Other hydroxy poly sulphides prepared are bis(o-hydroxy cyclohexyl)trisulphide, bis(phenoxyhydroxy propyl)trisulphide, bis(hydroxy propyl) trisulphide and bis(hydroxy ethyl)disulphide which on reduction yields hydroxy ethyl mercaptan.  The poly sulphides may be used as plasticizers and additives for fuels and mineral oils.ALSO:Mineral oils comprise as additives organic hydroxy polysulphides obtained by reacting a 1,2-alkylene oxide or substitution product thereof with sulphur and hydrogen sulphide under specified conditions (see Group IV(b)).  Named hydroxy polysulphides are bis(b -hydroxy ethyl) di- and tri-sulphides, bis (hydroxy propyl) di- and tri-sulphides, bis(phenyl hydroxy ethyl) disulphide, bis(o-hydroxy cyclohexyl) trisulphide and bis (phenoxy hydroxy propyl) trisulphide.  Numerous alkylene oxides and substitution products thereof yielding other hydroxy polysulphides are mentioned.