Patent GB-445434-A (GB)
Title: A process for the manufacture and production of polymerisation products from thiovinyl ethers
IPC: C08F28/00
Filed: 1934-10-25
Abstract: Products suitable for the production of films, threads, coatings, lacquers, priming compositions, mastics, insulation, and for the production of plastic masses by pressing, rolling, injection moulding, blowing or cutting, are obtained by polymerizing by heat, light, or polymerization catalysts, vinyl ethers of monovalent or polyvalent mercaptans, the said ethers containing only one vinyl group attached to the sulphur atom of a monovalent mercaptan or containing one or more thio-vinyl groups in the case of a polyvalent mercaptan.  Softeners, fillers, and pigments may be added; the products include interpolymers and mixed polymers obtained by adding other polymerizable compounds or their polymers, and the products may be treated with halogen e.g. by chlorination using organic solvents. Polymerization may be effected in the presence of accelerators, retarders, or solvents, or in aqueous emulsion (Example 9).  The thio-vinyl ethers may be derived from mercaptans of the aliphatic, aliphatic-aromatic, aromatic, hydromatic, or heterocyclic series, e.g. from alkyl or hydroxyalkyl mercaptans, aromatic mercaptans, di- and poly-sulphydryls of benzene, naphthalene, anthracene, anthraquinone, mono- and poly-sulphydryls of other isocyclic or of heterocyclic compounds, and from aralkylsulphydryls.  Thio - vinyl ethers specified are those derived from ethyl, propyl, isobutyl, octodecyl, and octodecenyl mercaptans, thioalkylene glycols, thioglycerines, thiophenol, thiocresol, mercapto-benzo-thiazole, and from phenylethyl mercaptan; vinyl-p-tolyl sulphide, 1.8-chlorthionaphthol vinyl ether, vinyl dodecyl sulphide and S-vinyl thioglycollic butyl ester. Substances specified for forming the mixed polymers and interpolymers are vinyl ethers and esters, vinyl chloride, styrene, acrylic and methyl-acrylic acids and their derivatives, isopropenyl-methyl-ketone, vinyl-methyl-ketone, butadiene, isoprene, vinyl-acetylene, linseed oil, chinawood oil, vinyl-octodecenyl ether, vinyl octodecyl ether, and styrene. Accelerators specified are boron fluoride, tin, zinc and aluminium chlorides, phosgene, sulphur dioxide, carbon dioxide, thionyl chloride, hydrogen fluoride and chloride, and the halogens, e.g. iodine; active carbon and bleaching earths; hydrogen, sodium, barium and benzoyl peroxides; ozone, and oxygen.  Retarders specified are the oxides, hydroxides and carbonates of alkali metals, calcium hydroxide, the alkali and alkaline earth metals, methylamine, dimethylamine, butylamine, piperidine, aniline, p-phenylene-diamine, dimethylaniline, ethanol, cyclohexanol, glycol, hydroquinone, pyrocatechol, and pyrogallol.  Solvents specified are benzene, toluene, xylene, ligroin, cyclohexane, ethers, ketones and alcohols. Dilute acids or anhydrous mineral acids should not be present with alcohols or other hydroxy compounds.  The temperature should not exceed about 200 DEG  C. Softeners specified are dibutylphthalate, tricresylphosphate, polybenzylnaphthalene, chlorinated naphthalene, and chlorinated diphenyl.  In the examples: (1) vinyl ethyl sulphide is treated with liquid sulphur dioxide; (2) to (7) vinyl-p-tolyl sulphide is polymerized alone at 70--90 DEG  C. or by irradiation at 50--60 DEG  C. or by heating with boron fluoride, bleaching earth, zinc chloride, iodine, or by treating with liquid sulphur dioxide; (8) a mixture of vinyl-octodecenyl ether and vinyl-p-tolyl sulphide is heated with zinc chloride or boron fluoride; (9) vinyl-p-tolyl sulphide is heated with water in the presence of a condensation product from an aminoalkyl sulphonic acid and a fatty acid, sodium isobutylnaphthalene sulphonate, and hydrogen peroxide, to form a white emulsion of the polymer; (10) 1.8-chlorthionaphthol vinyl ether is treated with liquid sulphur dioxide; (11) a mixture of vinyl-octodecyl-, vinyl - dodecyl-, or vinyl - octodecenylsulphide with vinyl octodecyl ether is treated with liquid sulphur dioxide; (12) vinyl-octodecyl- or vinyl-dodecyl-sulphide alone or with other vinyl compounds, or S-vinyl-thioglycollic acid butyl ester, is treated with liquid sulphur dioxide; (13) vinyl octodecyl sulphide is polymerized by iodine; (14) a mixture of vinyl-p-tolyl sulphide and styrene is polymerized by heat.  The thio - vinyl ethers may be obtained as described in Specification 427,903.  Monothiovinyl ethers of polyvalent mercaptans are obtained in similar manner using insufficient acetylene for reaction with all the mercapto groups. S-vinyl-thioglycollic butyl ester is obtained by reacting thioglycollic butyl ester in butanol with acetylene under pressure at 145--175 DEG  C. in the presence of zinc acetate.