Patent GB-932620-A (GB)
Title: Improvements in or relating to the preparation of macromolecular compounds
Inventor: HART RENE MAURICE
IPC: C08F8/12
Filed: 1960-05-31
Abstract: Polymers bearing sulphonic acid groups are made by homo- or copolymerizing an olefinically unsaturated monomer bearing at least one sulphonyl fluoride group, and hydrolysing the resulting polymer in an alkaline medium.  Monomers specified containing sulphonyl fluoride groups are fluorosulphonyl substituted acrylamides and methacrylamides, vinyl ureas, vinyl carbamates, acrylates and methacrylates and styrenes, e.g. N-(fluorosulphonyl phenyl) acrylamides and methacrylamides (ortho, meta and para) and nuclear methoxy, chloro, and dimethylamino derivatives thereof, N-vinyl-N1-(m-fluorosulphonyl phenyl) urea, 1-(m-fluorosulphonyl phenyl)-ethyl vinyl carbamate, 1-(m-fluorosulphonyl phenyl) ethyl acrylate and methacrylate, fluorosulphonyl styrenes (meta and para), which may be homopolymerized, or copolymerized with monomers such as acrylic acid, methyl, ethyl and butyl acrylates, methyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, acrylamide, maleic anhydride, itaconic acid, styrene, vinyl toluene, divinyl benzene, N-vinyl pyrrolidone and N-vinyl carbazole, including terpolymerization with mixtures of such monomers.  Polymerization may be effected in bulk, solution, emulsion or suspension with the aid of ultra-violet light or initiators such as azobisisobutyronitrile, benzoyl peroxide, potassium persulphate and a persulphate-bisulphite mixture.  In emulsion polymerization sodium lauryl sulphate may be used as an emulsifier, and polyvinyl alcohol may be used as a suspending agent in suspension polymerization.  The hydrolysis may be carried out with the polymer in solution or suspension in water or mixtures of water and an organic solvent, e.g. acetone.  Suitable hydrolytic agents are sodium and potassium hydroxides.  If desired the hydrolysis may be carried out in such a way as to hydrolyse a comonomer, e.g. maleic anhydride or methyl acrylate, present in the copolymer. After hydrolysis the polymers may be converted to the free acid form by treatment with an ion-exchange resin.  The resulting polymers may be used as cation-exchange resins, e.g. a divinyl benzene-styrene-m-sulphonic acid copolymer, thickening agents, textile finishing agents, additives to photographic gelatine, binders in silver halide emulsions, as additives to baryta paste and, in the case of acrylonitrile copolymers, in the preparation of dyeable films and fibres.  Specification 861,984 is referred to.ALSO:The preparation of ethylenically unsaturated fluorosulphonyl substituted compounds is described, as follows:-(A) N-(fluorosulphonylphenyl) acrylamides and methacrylamides (ortho, meta and para) and nuclear methoxy, dimethylamino and chloro derivatives thereof are prepared by the reaction of an aminoarylsulphonyl fluoride with acrylyl or methacrylyl chloride or anhydride; (B) N-vinyl-N1-(m-fluorosulphonyl phenyl) urea and the corresponding p-isomer are obtained by the reaction of vinyl isocyanate with an aminobenzene sulphonyl fluoride; (C) 1-(m-fluorosulphonylphenyl)-ethyl vinyl carbamate is obtained by the reaction of vinyl isocyanate with 1-(m-fluorosulphonyl phenylethanol; (D) 1-(m-fluorosulphonylphenyl)-ethyl acrylates and methacrylates are made by reacting 1-(m-fluorosulphonylphenyl)- ethanol with acrylyl or methacrylyl chloride; and (E) m- and p-fluorosulphonyl styrenes may be made from the appropriate fluorosulphonyl acetophenone by hydrogenating it to form an alpha- (fluorosulphonylphenyl) ethanol, which is dehydrated to yield the desired compound.  Specification 861,984 is referred to.