Patent GB-1015797-A (GB)
Title: Thio enol ethers
IPC: C08K5/372
Filed: 1964-07-03
Abstract: Unsaturated thioethers having the formula RSR1, where R is cycloalkenyl, alkenyl having at least 3 carbon atoms or aralkenyl, the ethylenic double bond in each case being attached to a carbon atom adjacent to the sulphur atom, and where R1 is alkyl, alkenyl, aryl or aralkyl are used as stabilizers for halogen-containing resins.  Preferably the resin is a vinyl chloride resin consisting of monomers of vinyl chloride alone or a mixture of monomers comprising at least 70% vinyl chloride by weight.  Vinyl chloride may be copolymerized with ethylenically unsaturated compounds such as esters of ethylenic monocarboxylic and dicarboxylic acids, ester of ethylenic alcohols, vinyl ethers, vinyl ketones, vinylidene chloride, styrene, trichloroethylene, 1 - fluoro - 1chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chloro allylidene diacetate.  Chlorinated polyethylene, polyvinyl bromide and polyvinyl fluoride may also be used as the resin.  The unsaturated thioethers are particularly useful in conjunction with tin compounds such as dibutyl tin oxide, dibutyl tin dilaurate, dioctyl tin oxide and dioctyl tin dilaurate. Both the unsaturated thioethers and the tin compounds are used in amounts of 0.01 to 10% by weight of the resin,  A plasticizer may also be employed e.g. di-2-ethylhexylphthalate, dibutyl sebacate, dioctyl sebacate and tricresyl phosphate.  An example describes the use of 1-thiododecyl cyclohexene as stabilizer, in conjunction with dibutylin oxide, for a vinyl chloride homopolymer.  It is stated that 1-thiophenyl cyclohexene, 1-thiododecyl cyclopentene, 9 - thioheptadecene - 7, d - dodecyl1 - phenyl - 1 - thioethylene or 2 - thiooctylpropene may replace the 1-thiodecyl cyclohexene to obtain similar results.ALSO:The invention comprises unsaturated thioethers having the formula RSR1, where R is cycloalkenyl, alkenyl having at least 3 carbon atoms or aralkenyl, the ethylenic double bond in each case being attached to a carbon atom adjacent to the sulphur atom, and where R1 is alkyl, alkenyl, aryl or aralkyl.  They may be prepared by reacting an appropriate aldehyde or ketone with an appropriate mercaptan or thiophenol in a hydrocarbon solvent and preferably in the presence of an acid catalyst such as benzenesulphonic acid, p-toluene sulphonic acid, hydrochloric acid, hydrobromic acid or sulphuric acid.  A preferred group of compounds are prepared by reacting cyclohexanone with an appropriate mercaptan or thiophenol, alternatively cyclopentanone, aliphatic aldehydes having at least three carbon atoms, dialkyl ketones or alkyl aryl ketones may be used.  The aldehyde or ketone employed must have a hydrogen atom attached to a carbon atom alpha to the carbonyl group.  To purify the product, the reaction mixture may be washed with a weakly alkaline solution such as aqueous sodium bicarbonate or potassium bicarbonate and the product is recovered by distillation, usually at reduced pressure.  Numerous examples of the unsaturated thioethers are given and the unsaturated thioethers may suitably be used as stabilizers, particularly with tin compounds, for halogen containing vinyl and vinylidene resins (see Division C3).