Patent GB-835674-A (GB)
Title: Improvements in catalysts for aqueous emulsion polymerizations
IPC: C08F2/16
Filed: 1958-09-30
Abstract: A polymerization catalyst comprises a metal borohydride to which may be added a watersoluble cobaltous, nickelous, manganous, ferrous or cuprous salt which forms a precipitate with the borohydride.  The borohydride may be of an alkali or alkaline earth metal, thorium, mercury, gold or lead.  The examples refer to the use of sodium or potassium borohydride in one example with the addition of cobaltous chloride.ALSO:In the aqueous emulsion polymerization or copolymerization of monounsaturated compounds containing a CH2 = C< group attached to at least one electronegative grouping or of butadiene or its derivatives, the catalyst used is a metal borohydride which is stable in water and to which may be added a water-soluble cobaltous, nickelous, manganous, ferrous or cuprous salt which forms a precipitate with the borohydride.  Specified monomers are styrene, vinylnaphthalene, alpha-methylstyrene, parachlorostyrene, dichlorostyrenes, acrylic acid, methacrylic acid, methyl acrylate or methacrylate, ethyl acrylate, acrylonitrile, methacrylonitrile, methacrylamide, vinyl chloride, vinylidene chloride, methyl vinyl ether, methyl vinyl ketone, 2-, 3- or 4-vinyl pyridine, 2-methyl - 5 - vinyl pyridine, 5 - ethyl - 2 - vinyl pyridine, 2 - methyl - 6 - vinyl pyridine, 2 - ethyl - 4 - vinyl pyridine, 2,4 - dimethyl - 6 - vinyl pyridine, butadiene, isoprene, chloroprene, 2,3-dimethylbutadiene and piperylene and copolymers preferably comprise up to 70% of a comonomer with a conjugated diene. Suitable borohydrides are those of the alkali metals, alkaline earth metals, magnesium, thorium, mercury, gold and lead, used in amounts of 0.1-10 parts per 100 parts of monomer.  Polymerization is effected at - 20 DEG  to 100 DEG  C. in water, e.g. 0.5-3 parts per part of monomer, preferably alkaline, e.g. pH 7.5-13.5 using conventional anionic, ampholytic or non-ionic surface-active emulsifying agents. The anionic emulsifying agents are compounds of the formula RCOOM, RSO3M and ROSO3M where R contains at least one C8 group and M is alkali metal, ammonium or amine and include soaps of fatty acids and abietic acid, dehydrogenated, hydrogenated and disproportionated rosin soaps, alkyl sulphonates or sulphates, sulphonated or sulphated ethers, sulphonated alkyl esters of fatty acids, sulphonated glycol esters of fatty acids, sulphonated alkyl amides of fatty acids, alkylated aryl sulphonates, hydroaromatic sulphonates, alkyl sulphosuccinates and arylsulphonate-formaldehyde condensation products.  The ampholytic agents are the higher alkyl betaines and the non-ionic agents include monoethers of polyglycols with fatty alcohols or alkyl phenols, monoesters of polyglycols, polyoxyethylenepolyoxypropylene glycols and partial esters of polyhydric alcohols or polyglycol ethers thereof with fatty and/or resin acids.  Polymerization regulators such as the C6-C18 aliphatic mercaptans or aromatic mercaptans can be added in amounts of 0.1-1 part per 100 parts of monomer. Oxygen may be present or an oxygen scavenger such as pyrogallol may be added.  At the desired conversion a shortstopping agent can be added, e.g. hydroxylamine, dinitrochlorobenzene, di - tert. - butyl hydroquinone or alpha-nitrosobeta naphthol in amounts of 0.05-1 part per 100 parts of monomer.  The examples illustrate the polymerization of butadiene, butadiene-styrene, styrene and styrene-methyl methacrylate, using as catalyst potassium or sodium borohydride in one example with the addition of cobaltous chloride.