Patent GB-829213-A (GB)
Title: Improvements in or relating to low temperature emulsion polymerization of unsaturated compounds
IPC: C08F4/32
Filed: 1957-01-09
Abstract: Hydrogenated rosin acid carbinols may be prepared from rosin, rosin acids or rosin acid containing materials (a) by heating with carbon monoxide and hydrogen under pressure in the presence of a cobalt carbonyl catalyst; or (b) reacting with formaldehyde in the presence of glacial acetic acid, hydrolysing the carbinol acetate formed and thereafter hydrogenating.  The rosin or rosin acid containing material may be wood and gum rosins, e.g. N-wood rosin, pine wood rosin and WW-gum rosin, tall oil, rosins separated from tall oil, e.g. sulphate wood rosin, partially hydrogenated or dehydrogenated rosin acids, polymerized rosin acids or rosin acid derivatives, e.g. abietic acid, dihydroabietic acid, neoabietic acid, dextropimaric acid and the methyl, ethyl and glyceryl esters or the nitriles of these acids.  The hydrogenated rosin acid carbinols may be converted to alkali metal, e.g. potassium, salts by neutralizing with alkali. The salts may be used as emulsifiers in emulsion polymerization systems (see Group IV (a)).  Cobalt carbonyls.-Cobalt hydrocarbonyl may be prepared by heating cobalt carbonate in cyclohexane with a 1 : 1 mixture of carbon monoxide and hydrogen under pressure.  On cooling the resulting solution crystals of cobalt octacarbonyl are precipitated.  U.S.A. Specification 2,891,024 is referred to.ALSO:Organic compounds containing the CH2=C< group are polymerized in aqueous emulsion at temperatures below 10 DEG  C. in the presence of an organic peroxide, an electromotive couple having a standard oxidation-decuction potential between -1.0 and -0.3 volt and an emulsifier comprising an alkali metal salt of a hydrogenated rosin acid carbinol.  Specified monomers are conjugated dienes, e.g. butadiene-1,3, isoprene, 2,3-dimethyl butadiene-1,3, chloroprene, piperylene, mixtures thereof with styrene, p-chlorostyrene, p-methoxystyrene, vinyl naphthalene, acrylic acid, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, methyl vinyl ketone, methyl isopropenyl ketone and methyl vinyl ether; and vinyl acetate, styrene, methyl methacrylate, vinyl chloride, vinylidene chloride and vinyl pyridine.  Specified peroxides are benzoyl peroxide, tert.-butyl hydroperoxide, triethylmethyl hydroperoxide, a ,a  - dimethylbenzyl hydroperoxide, 1,3 - dimethylcyclopentyl 1 - hydroperoxide, a ,a  - dimethyl - p - methylbenzyl hydroperoxide, a ,a  - dimethyl - p - isopropylbenzyl hydroperoxide, a ,a  - ethylmethylbenzyl hydroperoxide, and p-menthane hydroperoxide.  The couple may comprise nickel hydroxide/nickel oxide or preferably ferrous and ferric ions. Ferrous sulphate or chloride may be employed together with potassium pyrophosphate, gluconates, citrates, reducing sugars, ethylenedinitrilo-tetracetic acid, o-phenanthraline or polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine.  The rosin acid carbinols may be prepared by reacting carbon monoxide and hydrogen, in the presence of a cobalt carbonyl catalyst, with rosin acids or rosin acid containing materials, e.g. abietic acid, dihydroabietic acid, neoabietic acid, dextropimaric acid, partially hydrogenated or dehydrogenated rosin acids, polymerized rosin acids, derivatives thereof such as the methyl, ethyl and glyceryl esters and nitriles, wood and gum rosins such as N-wood rosin, pine wood rosins, WW gum rosin and tall oil; or by reacting rosin with formaldehyde in glacial acetic acid and hydrolysing.  Additional emulsifiers, e.g. sodium alkaryl sulphonates, modifiers, e.g. mercaptans such as tertiary dodecyl mercaptan, viscosity stabilizers, e.g. trisodium phosphate and potassium chloride, and antifreezes, e.g. methanol, ethanol, ethylene glycol, glycerol, acetone and methyl acetate, may be added to the polymerization system.  U.S.A.  Specification 2,891,024 is referred to.