Patent GB-708022-A (GB)
Title: Process for the production of stabilized aryl esters of alkane sulphonic acids and polyvinyl halides plasticized therewith
IPC: C08K5/42
Filed: 1951-10-12
Abstract: Vinyl halide polymers are plasticized by means of aryl esters of alkane sulphonic acids having the general formula R1 (SO3R2)#c wherein R1 is a saturated branched chain aliphatic radical containing preferably 6-24 carbon atoms, R2 is a phenyl group substituted or not by one or more groups inert towards a sulphonyl chloride group and #c is an p  integer, preferably 1-3, the esters being stabilized by heating to 110 DEG -300 DEG C. and removing the gaseous products formed (see Group IV (b)).  Inert substituents which may be present include chlorine, bromine, iodine or fluorine atoms and methyl, ethyl, propyl, isopropyl, butyl, tert.-butyl, methoxy, ethoxy, propoxy, iso-propoxy and tert.-butyl phenyl groups.  The stabilized esters render stable and flexible at low temperatures polymers of vinyl halides, e.g. the chloride, bromide and/or fluoride or co-polymers thereof with, for example, vinylidene chloride; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; methyl acrylate, ethyl acylate, propyl acrylate, butyl acrylate, allyl acrylate and the corresponding methacrylates; styrene, o- and p-chlorostyrenes, 2 : 5-dichlorostyrene, 2 : 4-dichlorostyrene, p-ethylstyrene, divinyl benzene, vinyl naphthenate, and a -methyl styrene; butadiene and chloroprene; acrylamide, acrylic acid anilide, acrylonitrile; the methyl, ethyl propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl and phenyl esters of maleic, crotonic, itaconic and fumaric acids.  The plasticizer may be present in amounts of from 5-300 parts by weight per 100 parts of polymer.  It may be used in conjunction with other plasticizers such as di(2-ethylhexyl) phthalate, dibutyl phthalate, tricresyl phosphate tri(2-ethylhexyl) phosphate, dibutyl sebacate, alkyl diaryl phosphates and alkyl benzyl phosphates.  Examples are given wherein the esters are derived from phenol and the mixed mono and polysulphonyl chlorides obtained by sulphochlorination of C10-12, C16 and C20-24 branched chain alkanes respectively.ALSO:Aryl esters of alkane sulphonic acids having the general formula R1(SO3R2)x wherein R1 is a saturated branched chain aliphatic radical containing preferably 6-24 carbon atoms, R2 is a phenyl group substituted or not by one or more groups inert towards a sulphonyl chloride group and x is an integer of preferably 1-3 are stabilized by heating the crude aryl alkane sulphonate at 110-300 DEG  C. and removing the gaseous products formed.  The esters may be prepared by the catalytic sulphochlorination of the appropriate alkane or petroleum fraction containing the same and then reacting the resulting sulphony chloride or polysulphonyl chloride with a phenol in the presence of ammonia or an alkali metal or earth metal hydroxide or carbonate and also if desired an inert diluent. The phenol may contain such substituents as chlorine, bromine, iodine, fluorine, methyl, ethyl, propyl, isopropyl, butyl, tert.-butyl, tert.-butyl-phenyl, methoxy, ethoxy, propoxy, and iso-propoxy.  The stabilized esters may be used as plasticizers for vinyl halide polymers (see Group IV (a)) and modifiers for cellulose nitrate coatings and as hydraulic liquids. In examples (1) a C16 branched chain alkane is sulpho-chlorinated in presence of mercury vapour light and then reacted with phenol and aqueous sodium hydroxide; the product is heated under a gradually reduced pressure to 195-200 DEG  C. and held there for at least an hour at 1.5-2 mm. pressure; (2) and (3) petroleum hydrocarbons consisting essentially of C10-12 and C20-24 branched chain alkanes are employed likewise.  In each case stabilized esters of mixed mono and poly-sulphonic acids are obtained.  A peroxide catalyst may replace the ultra-violet light in the sulphochlorination.