Patent GB-808955-A (GB)
Title: Epoxidized esters of adipic acid
IPC: C08K5/15
Filed: 1955-08-26
Abstract: An ester product comprising at least one epoxidized diester of adipic acid in which the alcohol moieties, which may be the same, or different, are derived from oleyl, linoleyl, or linolenyl alcohol, said epoxidized ester containing an average of at least 70 epoxy groups per 100 alcohol moieties, is used as a plasticizer and stabilizer for halogen-containing resins such as polyvinyl chloride, polyvinyl bromide, copolymers of a vinyl halide and a vinyl ester of a lower aliphatic acid, e.g. copolymers of vinyl chloride and vinyl acetate or propionate, copolymers of vinyl chloride and vinylidene chloride and copolymers of a vinyl halide with ethyl acrylate, or methyl methacrylate.  The amount of epoxy adipate used may be as little as 2 per cent but amounts of 40 to 70 per cent based on the weight of plastic material are preferred for the production of flexible sheeting.  Other conventional additives such as pigments, dyes, extenders, fillers, release agents, mould lubricants and other plasticizers may be included. The preparation of the epoxy adipates is described in Group (V (b).  The esters may be derived from the pure alcohols and be single products such as di-(9,10-epoxyoctadecyl) adipate or may be derived from oil alcohols obtained by reduction of soybean, linseed, safflower, cottonseed, and perilla oils in which case mixed esters are obtained.  In an example, polyvinyl chloride, basic lead sulphate, stearic acid and, as plasticizer, di/9,10-epoxyoctadecyl adipate, epoxidized soybean alcohol adipate, or epoxidized linseed alcohol adipate, are blended then milled on a roller mill at 163 DEG  C. to produce sheets of the composition which are then subjected to various tests. Specifications 741,492, 758,728 and 791,285, [Group IV (b)], are referred to.ALSO:The invention comprises an ester product consisting of or comprising at least one epoxidized diester of adipic acid in which the alcohol moieties, which may be the same or different are derived from oleyl, linoleyl, or linolenyl alcohol, said epoxidized ester containing an average of at least 70 epoxy groups for every hundred alcohol moieties in the ester.  A preferred product is Di-(9,10-epoxyoctadecyl) adipate.  The novel products are obtained by epoxidizing oleyl, linoleyl, or linolenyl adipates or mixtures thereof.  The epoxidation may be effected by means of peracetic acid or performic acid formed in situ in an aqueous solution in contact with the unsaturated adipate and which contains formic acid, acetic acid, or acetic anhydride and preferably an auxiliary acid agent.  A preferred procedure using hydrogen peroxide, formic acid and an ionizable acidic agent is described in Specification 791,285.  The unsaturated adipic esters may be prepared from oleyl, linoleyl and linolenyl alcohols in pure form but also suitable are the so-called "oil alcohols" which are mixtures of alcohols obtained by reduction of esters of the fatty acids of vegetable oils by means of sodium and an alcohol such as ethanol or butanol.  Such oil alcohols are obtained from soybean, linseed, safflower, cottonseed, and perilla oils.  The use of such oils results in mixed esters of adipic acid such as oleyl linoleyl adipate, linolenyl linoleyl adipate and oleyl linolenyl adipate, which may then be epoxidized.  The products are excellent plasticizers and stabilizers for halogen containing resins and plastics (see Group IV (a)).  In examples, (1) dioleyl adipate is obtained heating a mixture of adipic acid and oleyl alcohol under reflux in toluene in the presence of zinc chloride for 20 hours, after which the volatile constituents are distilled off and the ester is converted to di-(9,10-epoxyoctadecyl) adipate by mixing with aqueous formic acid at 25-35 DEG  C., adding hydrogen peroxide and agitating the mixture for 24 hours; (2) the adipic acid ester of soybean alcohols is prepared and epoxidized in a similar manner; (3) the adipic ester of linseed alcohols is prepared and epoxidized as in (2).  Specifications 741,492 and 758,728 are referred to.