Patent GB-1251550-A (GB)
IPC: C08J5/22
Filed: 1969-07-09
Abstract: 1,251,550. Cation exchange membranes. TOKUYAMA SODA K.K. 9 July, 1969, No. 34699/69. Heading C3P. Cation exchange membranes of dimension at least one centimetre in two directions and comprising an insoluble, infusible organic high molecular weight polymer having at its surface cation exchange groups and amido groups from the cation exchange group by reaction with an amine having one amino group containing at least one hydrogen atom bonded to nitrogen atom, in proportions such that the percentage [A/(A+B)] x 100 is 15 to 1 x 10<SP>-5</SP> where A is the number of amido groups and B is the number of free cation exchange groups per gram of dry membrane, may be prepared by reacting a polymer having acid halide or carboxylic anhydride groups with an amine containing at least one primary or secondary amino group and hydrolysing the residual acid halide or anhydride group with an aqueous alkaline solution. Reaction with the amine may be effected in the presence of a dehydrohalogenating agent and/or a water soluble ammonium or metal salt. Residual primary or secondary amino groups in the amine moiety may be converted to tertiary groups or quaternized with alkyl halides, alkylene dihalides, aldehydes or epichlorohydrin. The membranes may be prepared by any conventional method and many examples are given including polymerizing pastes of styrene, divinyl benzene, polyvinyl chloride, dioctylphthalate and benzoyl peroxide on polyvinyl chloride cloth, chlorosulphonating the product and reacting with (1) diethylamine, diethanolamine, diphenylamine, phthalimide, piperazine, p-aminosalicylic acid, dodecylamine, polyethylene polyamines, m-phenylene diamine, Bismark brown, auramine, isonicotinic acid hydrazide and chrysoidine, and (2, 3 and 5) polyethyleneimine, and hydrolysing; (4) polymerizing a paste of styrene, divinyl benzene, polyethylene, dioctylphthalate, and benzoyl peroxide on polyethylene net, reacting with phosphorus trichloride and polyethyleneimine and hydrolysing; (6) polymerizing a paste of methacrylic acid, divinyl benzene, polyvinyl chloride, dioctyl phthalate and benzoyl peroxide on polyvinyl chloride cloth, converting to acid chloride groups with phosphorus trichloride, reacting with polyethyleneimine and hydrolysing; (7) treating a sheet rolled from chlorosulphonated styrene/ divinyl benzene copolymer and polystyrene with polyethyleneimine and trimethylamine and hydrolysing; (8) swelling a polyvinyl chloride sheet with styrene, divinyl benzene and benzoyl peroxide and polymerizing between regenerated cellulose sheets, chlorosulphonating, reacting with polyethyleneimine and triethanolamine, and hydrolysing; (9) acetalizing film cast from sulphonated polystyrene and polyvinyl alcohol, converting to acid chloride with phosphorus pentachloride, reacting with polyethyleneimine and triethanolamine and hydrolysing; (10) polymerizing a paste of styrene, divinylbenzene, vinyl sulphonyl chloride and dioctyl phthalate between glass plates, treating with polyethyleneimine and triethanolamine and hydrolysing; (12) polymerizing a paste of styrene, divinyl benzene, polyvinyl chloride, chlorosulphonated polyethylene and dioctyl phthalate on polyvinyl chloride cloth, sulphonating, reacting with polyethyleneimine and hydrolysing; (13) treating glass cloth with styrene/butadiene copolymer latex, chlorosulphonating, amidating and hydrolysing; (14) polymerizing styrene absorbed in polytetrafluoroethylene film, chlorosulphonating, amidating and hydrolysing; amidating further membranes with (16) polyvinylamine with or without triethanolamine, (17) polyallylamine and (18) polyaminostyrene and triethanolamine; (21) reacting methacrylic acid/divinyl benzene copolymer with thionyl chloride, polyethyleneimine and triethanolamine and hydrolysing; and (22) reacting styrene/ divinyl benzene/maleic anhydride copolymer with triethanolamine and polyethyleneimine and hydrolysing; and many similar.