Patent GB-570662-A (GB)
Title: Manufacture of rubber-like materials
IPC: C08F220/44
Filed: 1943-05-28
Abstract: A sübstantially uniform polymeric material of chloroprene and acrylic nitrile, wherein a high percentage of the nitrile employed is in a combined form, is prepared by beginning the polymerization with a predetermined ratio of the two monomers emulsified in aqueous emulsion, and from time to time as the polymerization proceeds, adding more monomeric chloroprene to the emulsion in a quantity sufficient to restore substantially the original ratio of the two monomers, such addition always being made at least as soon as all of the monomeric chloroprene in the mass is polymerized. As few as four additions added portionwise is satisfactory.  The proportion of monomeric acrylic nitrile to the total monomeric material used should desirably be between 15 to 40 per cent and especially preferred are processes wherein monomeric nitrile represents 20 to 30 per cent of the total polymerizable material, and the product contains at least 10 per cent and preferably more than 15 per cent of combined acrylic nitrile.  Additional components which may be added to improve the working properties of the polymer include the isomeric octyl mercaptans and xylyl mercaptans (prepared by reduction of the mixture of sulphonyl chlorides obtained from commercial xylene) and, to improve the product, sulphur and sulphur dioxide.  Emulsifying agents may be employed in forming the emulsion, such as sulphated oleyl acetate, the sulphate esters of long chain alcohols including octadecyl, cetyl and oleyl alcohols, and sulphonated naphthalene compounds with an aliphatic side chain; in alkaline emulsion, soluble soaps of fatty acids such as sodium or ammonium oleate may be used. Polymerization accelerators desirable for use in alkaline emulsions are ammonium, potassium or sodium persulphate, benzoyl peroxide and ascaridol.  The temperature employed is generally below 40 DEG  C. Coagulation may be brought about by freezing or by the addition of a salt such as sodium chloride or aluminium sulphate, or an alcohol. In compounding and curing the polymers, there may be used zinc oxide especially with magnesium or lead oxides and reinforcing carbon blacks.  In examples (examples 1, 2 and 3 are for comparison only): (1) and (2) a solution of chloroprene and acrylic nitrile containing small addition sulphur and xylyl or octyl mercaptan is emulsified with water containing small additions of hydrogen chloride, and sodium salts of sulphated oleyl acetate and of dinaphthyl methane sulphonic acids; the polymerized dispersion obtained on heating is treated with a benzene solution of tetraethyl thiuram disulphide and coagulated with sodium chloride solution and the plastic product is compounded with phenyl a -naphthylamine, semi - reinforcing carbon black, litharge and zinc oxide and then cured; (3) a mixture of chloroprene, acrylic nitrile and small additions of sulphur, octyl mercaptan and sulphur dioxide is emulsified and treated as in example (1) above.  Illustrating the invention example (4) describes the preparation of a polymer containing the same components as in example (1), the chloroprene being added in 7 parts of gradually decreasing size calculated so as to maintain the required constant ratio between the unreacted reactants.  The product worked up as before, has improved acrylic nitrile content and greater resistance to solvents. U.S.A. Specifications 2,066,331 and 2,140,048 are referred to.