Patent GB-690930-A (GB)
Title: Improvements in or relating to a process for producing polymeric materials
IPC: C08F36/04
Filed: 1949-11-22
Abstract: In the polymerization of unsaturated organic compounds containing a CH2=C< group and having at least one of the disconnected valencies attached to an electronegative group, in aqueous alkaline emulsion containing an emulsifying agent which will remain in the aqueous phase after the addition of an acidic coagulant, a polymer containing a rosin acid is obtained by adding a rosin acid compound to the polymer latex in an amount between 1 and 10 parts per 100 parts by weight of monomer.  1,3-Butadiene, isoprene, piperylene, 2,3-dimethyl-, 3-furyl-, 3-methoxy-, 2-chloro- or bromo- and 2-chloro-3-methyl-1,3-butadienes; styrene, p-chloro-, p-methoxy- and a -methyl-styrenes, and vinyl naphthalene; acrylic and methacrylic acids, methyl and ethyl acrylates, methyl-a -chloroacrylates, methyl ethyl and butyl methacrylates, methyl ethacrylate, acrylonitrile, methacrylonitrile, and methacrylamide; methyl isopropenyl and methyl vinyl ketones; methyl vinyl ether, vinyl ethinyl alkyl carbinols; vinyl acetate and chloride; vinylidene chloride; vinyl furane, carbazole and acetylene may be polymerized or copolymerized in the presence of emulsifying agents such as alkali metal alkyl sulphates and sulphonates, sulphated and sulphonated succinic esters and salts of alkyl aromatic sulphonates, e.g. sodium and potassium alkyl benzene, toluene and naphthalene sulphonates with 15 to 30 carbon atoms per molecule and sodium "Lorol" (Registered Trade Mark) sulphates, aralkyl polyether alcohols, and condensation products of alkyl phenols with ethylene oxide or mixtures thereof, in a process which may be continuous, or batchwise, and using temperatures between -50 DEG  and 70 DEG  C. Polymerization is preferably short-stopped and the monomer removed by distillation before the addition of the rosin acid compound, e.g. sodium or potassium soaps obtained from wood rosin or disproportionated rosin acids such as abietic, dehydro-, dihydro-, and tetrahydro-abietic acids which may be added in carbon-tetrachloride or benzene solution, the polymer then being coagulated by brine-acid or acid methods.  In examples, butadiene-styrene copolymers are prepared: (1) in an aqueous-methanol medium using sodium alkyltoluene sulphonate as emulsifier, 2-(4-methoxybenzene diazomercapto) naphthalene and potassium ferricyanide as redox catalyst, in the presence of potassium hydroxide, trisodium phosphate and a blend of aliphatic tertiary C12, C14 and C16 mercaptans. Polymerization is effected at -10 DEG  C., the ferricyanide and mercaptan being added portionwise, is short stopped at 60 per p  cent conversion by addition of a hydroquinone-di-tertiarybutyl hydroquinone mixture, stabilized by phenyl-beta-naphthylamine and coagulated by the brine-acid method; (IV) using a mixture of sodium alkyl sulphonate and potassium laurate adjusted to a pH of 11.0 with potassium hydroxide; (V) using potassium laurate/myristate with sodium alkyl toluene sulphonate as emulsifier, cumene hydroperoxide as catalyst, sodium pyrophosphate and ferrous sulphate as activator, and a mercaptan blend in an emulsion of pH 9.5; (VI) as in (V) using sodium di-secondary butyl naphthalene sulphonate or alkyl polyether alcohol as emulsifier; (VII) as in (V) using sodium alkyl toluene sulphonate as emulsifier, with the addition of glycerine.  The copolymer, compounded with carbon black, zinc oxide, asphalt softener, sulphur, N-cyclohexyl-2-benzo-thiazolesulphenamide and stearic acid may be cured by heat to give improved flex-life, tack, tensile strength and elongation.