Patent GB-851059-A (GB)
Title: Process for polymerization and the products produced thereby
IPC: C08F291/00
Filed: 1957-03-29
Abstract: Graft and block polymers are made by polymerizing a compound containing a polymerizable CH2=C < group in an aqueous medium at a pH not greater than 6,0 and at a temperature between -5 DEG C. and 100 DEG C. in the presence of a ceric salt which is soluble in at least one of the components of the reaction system, and a polymeric organic reducing agent capable of being oxidized by the ceric salt and capable of initiating the polymerization, the reducing agent being an aldehyde or an acetal or a compound containing the <FORM:0851059/IV(a)/1> group wherein X is OH, RCO, SH and NHR, wherein R is hydrogen, alkyl, aralkyl or aryl, the open bonds of the <FORM:0851059/IV(a)/2> group being essentially organic residues and/or hydrogen. Monomers specified are styrene and various alkyl and halogen substituted styrenes, acrylic, methacrylic and chloroacrylic acids, anhydrides, amides and nitriles, C1-10 acrylates, acrylic esters of various nitroalkanols, acrylic esters of various polyhydric alcohols, butadiene, isoprene, chloroprene, allyl and methallyl esters of various saturated and unsaturated acids, vinyl acetate, propionate and butyrate, vinyl and vinylidene chlorides, vinyl ethyl, propyl and isobutyl ethers, divinylsulphone, divinylsulphide and vinyl pyridine.  Polymeric reducing agents specified are polyvinyl alcohol and its partially formylated, acetylated, sulphated, nitrated and cyanoethylated derivatives, cellulose, regenerated cellulose, the partial acetic, propionic and nitric esters and partial methyl, ethyl, hydroxyethyl ethers of cellulose, starch and its partially cyanoethylated and acetylated derivatives, polymers of beta-hydroxyethyl acrylate and methacrylate, polyvinyl pyrrolidone, polymers of C1-C3 alkyl vinyl ketones, polyamines made by treating acrylamide polymers with sodium hypochlorite, polymers of acrolein, 3-butenal, 3-pentenal and 5-chloro-3-pentenal, various mercaptoalkyl acrylates and methacrylates, polyvinyl formal, acetal and butyral, graft copolymers containing reducing groups, e.g. a graft copolymer of polyacrylamide and polyvinyl alcohol and, for the purpose of forming block polymers, polymers having terminal reducing groups, e.g. polyethylene glycol, polyethylene imines and polymers obtained by polymerizing unsaturated monomers in the presence of trimethylene glycol and 1,4-butanediol.  Ceric salts specified are ceric ammonium nitrate, ceric sulphate, ceric dihexyl sulphoccinate and other salts obtained by reacting an inorganic ceric salt with organic sulphur containing acids.  When polymerization is carried out in emulsion there is used an emulsifying agent, various alkali metal organic sulphonates and sulphates being specified for this purpose. Polymerisation may be carried in such a way as to graft two monomeric materials, e.g. methyl acrylate and acrylamide, on to the same preformed polymer, e.g. polyvinyl alcohol.ALSO:Oil-soluble ceric salts of organic sulphurcontaining acids are prepared by reacting an inorganic ceric salt, e.g. ceric ammonium nitrate, with an organic sulphur containing monobasic or polybasic acid or an alkali metal salt thereof, e.g. the sulpho derivatives of aliphatic dibasic acids and alkyl esters thereof, monoalkyl esters of sulphuric acid and alkyl benzene and naphthalene sulphonates.  Salts specified are ceric dihexyl and dioctyl sulphosuccinates, diheptyl sulphoglutarate, didecyl sulphosuberate, dilaurylsulphosebacate, diamyl sulphomaleate, dimethyl sulphofumarate, dibutyl sulphodimethyl succinate and dilauryl sulphomethylglutarate.  The preparation of ceric dihexyl sulphosuccinate is described by a process which involves mixing aqueous solutions of ceric ammonium nitrate and sodium dihexyl sulphosuccinate and filtering off the precipitated ceric salt.ALSO:Textile fabrics made from cellulosic fibres, e.g. those of cotton, viscose rayon and cuprammonium rayon, are treated by graft polymerizing thereon an ethylenically unsaturated compound in an aqueous medium with the aid of a ceric salt (see Group IV(a) ).  In examples: (6) acrylonitrile is grafted on to a cotton fabric; (7) acrylonitrile is grafted on to a viscose rayon fabric; (8) acrylamide is grafted on to a cotton fabric; (9) methyl acrylate is grafted on to a cotton fabric; (10) methylene bisacrylamide is grafted on to a viscose rayon fabric; and (11) acrylamide is grafted on to a cotton fabric which is then treated with formaldehyde to give a fabric of improved wrinkle recovery.