Patent GB-826659-A (GB)
Title: Polymerizable organic sulfides and polymers thereof
IPC: B01J39/20
Filed: 1956-01-24
Abstract: The invention comprises organic sulphides having the general formula CH2=C(R)-S-R1-OR11 wherein R is hydrogen or a methyl group, R1 is a methylene (-CH2-), ethylidene or isopropylidene group and R11 is a C1-8 alkyl group.  The sulphides may be prepared by reacting b -mercapto ethanol or b -mercapto propanol with a halogenated ether X-R1-O-R11 X being chlorine or bromine, and dehydrating the resulting alcohol HOCH2CH(R)-S-R1-O-R11 at a temperature above about 150 DEG C.  The first step is suitably effected at below 50 DEG  C. in the presence of a hydrogen-halide acceptor e.g. an alkali metal hydroxide or carbonate, lime or an organic base such as tertiary amine or a quaternary ammonium hydroxide; inert solvents may be present.  The dehydration may be effected by heating in the presence of a dehydration catalyst such as alumina or an alkali metal hydroxide; if desired, the method of flash dehydration may be used.  The sulphides may be used in the formation of polymers and copolymers (see Group IV (a)). Named sulphides are those of the formulae CH2=CH-S-CH2OC2H5, CH2=C(CH3)-S-CH2-O-CH3, CH2=CH-S-CH2-O-CH3, CH2 : CH-S-CH2-O-C4H9 (e.g. n-butyl), CH2 : CH-S-CH(CH3)-O-C2H5 and CH2 : CH-S-CH2-O-C8H17 (e.g. 2-ethyl hexyl). In the first stage of the synthesis of the lastnamed sulphide some di-(2-ethylhexyl) formal is formed.  Several other alkyl radicals are specified as examples of "R."  Specification 826,658, [Group IV (a)], is referred to.ALSO:The invention comprises a polymer containing recurring units of the formula <FORM:0826659/IV (a)/1> wherein R represents hydrogen or a methyl group, R1 is a methylene, ethylidene or isopropylidene group and R11 is a C1-8 alkyl group, which may be prepared by the homopolymerization of an organic sulphide having the general formula CH2=C(R)-S-R1-O-R11, the R's being as defined above or by its copolymerization with another such sulphide or with another polymerizable compound containing one or more CH2=C< groups.  Numerous examples of such comonomers are given including esters of acrylic, a -chloracrylic and methacrylic acids, vinyl hydrocarbons, vinyl chloride, vinylidene chloride, various vinyl, allyl and methallyl esters, acrylonitrile and vinyl pyridine. Comonomers containing a plurality of CH2=C< groups, e.g. di- and trivinyl benzene, divinyl naphthalene, diallyl phthalate and ethylene glycol dimethacrylate give rise to insoluble cross-linked copolymers. may be rendered insoluble and non-thermoplastic by heating.  The polymers can be treated with an aqueous solution of an oxidizing agent and thus be converted to products containing units of the formula <FORM:0826659/IV (a)/2> Insoluble cross-linked polymeric products containing the recurring unit <FORM:0826659/IV (a)/3> and also units of a cross-linking agent containing in its monomeric form two or more CH2-C< groups can be oxidized, for example, with aqueous H2O2, to yield cation-exchange resins.  Polymerization may be effected with the aid of heat, ultra-violet light or a free-radical catalyst, of which many are specified. In examples: (1) the sulphide CH2=CHSCH2OCH2 is homopolymerized to a thermoplastic polymer which on heating becomes insoluble in ethylene dichloride; (2) the same sulphide is copolymerized with ethyl or methyl methacrylate, n-butyl acrylate or styrene; (3) vinyl 2-ethyl hexoxymethyl sulphide is copolymerized with ethyl acrylate; (4) vinyl ethoxy methyl sulphide is copolymerized with ethyl or methyl methacrylate or styrene; (5) vinyl methoxy methyl sulphide is copolymerized with divinyl benzene in aqueous emulsion yielding an insoluble cross-linked copolymer which is oxidized with aqueous H2O2 containing some sulphuric acid, yielding a sulphonated cationexchange resin.  Specification 826,658 is referred to.