Patent GB-813991-A (GB)
Title: Preparation of epoxidized acids, esters and nitriles
Filed: 1955-09-28
Abstract: Resins liable to degradation by heat or light such as chlorinated rubbers and vinyl and vinylidene halide resins, are stabilized and plasticised by means of esters of epoxidized C16-22 saturated aliphatic acids or epoxidized C16-22 saturated aliphatic nitriles. Also vinyl resins may be stabilized by means of heavy metal, e.g. lead or cadmium, salts of epoxidized C16-22 saturated aliphatic acids.  n-Hexyl 9 : 10-epoxy stearate and epoxidized soybean oil are specified for use with polyvinyl chloride.  The epoxy compounds are prepared in specified manner (see Group IV (b)).  Specification 770,585 is referred to.ALSO:C16-22 epoxy acids, esters and nitriles are prepared by reacting under substantially anhydrous conditions at least two equivalents of a strong base with a compound which is a C16-C22 saturated aliphatic acid, an ester of such an acid or a C16-22 saturated aliphatic nitrile and which compound has in the C16-22 chain at least one acyloxy-halo group of the formula <FORM:0813991/IV (b)/1> in which X represents chlorine or bromine and R is hydrogen or a C1-5 alkyl group, the reaction being conducted at such a temperature that an epoxidized compound is formed by conversion of the acyloxy halo group(s) present in the starting materials into the corresponding epoxy groups.  The range of carbon atoms 16-22 specified above excludes any carbon in the vicinal substituent in the starting materials.  The reaction is preferably effected in an inert solvent and at temperatures from - 10 DEG  C. to 150 DEG  C. Suitable strong bases include sodium and potassium hydroxides, quaternary ammonium hydroxides, e.g. trimethyl benzyl ammonium hydroxide, and anion-exchange resins containing quaternary ammonium hydroxide groups.  The C16-22 aliphatic compounds to be epoxidized may be obtained by reacting the corresponding olefinically unsaturated acids, esters or nitriles with a tertiary alkyl hypochlorite or bromite in the presence of a C1-6 alkanoic acid, preferably formic or acetic acid.  They may be derived from oleic, erucic, eleostearic, linoleic, linolenic, clupadonic, palmitoleic and palmitolenic acids, which may be obtained by saponification of animal or vegetable oils or fats containing them, the corresponding nitriles and the esters of these acids with mono-or polyhydric alcohols including ethyl, isopropyl, sec.-butyl, tert.-amyl, 2-ethyl-hexyl, lauryl, cyclohexyl, benzyl and phenethyl alcohols, ethylene glycol, hexamethylene glycol, dodecanediol-1:12, diethylene and triethylene glycols, glycerol and penta erythritol and animal and vegetable oils such as soyabean, cottonseed, rapeseed, safflower, linseed and sardine oils.  The resulting starting materials may have a plurality of acyloxy halo groupings when the initial acids contain a plurality of double bonds.  The epoxy ester and epoxy nitrile products and heavy metal salts of the epoxidized acids, e.g. the cadmium and lead salts may be used as plasticizers or stabilizers in resins (see Group IV (a).  In examples: (1) n-hexyl oleate is converted into a mixture of the n-hexyl esters of 9, 10 and 10,9-chloroformoxy stearic acids substantially as described in Specification 770,585 and the mixture is reacted with excess of caustic potash in anhydrous ethanol and the resulting n-hexyl 9:10-epoxy stearate is recovered; (2) n-hexyl 13:14-(14, 13)-formoxy chloro behenate, prepared from n-hexyl erucate, is similarly treated with ethanolic KOH at 0 DEG -5 DEG  C. yielding n-hexyl 13:14-epoxy behenate; (3) 9:10 (10:9)-formoxychloro stearonitrile is reacted as in (2) yielding 9:10-epoxystearonitrile; (4) an epoxidized soybean oil is similarly obtained from formoxy chloro soybean oil; (5) 2-ethyl butyl 9:10 (10:9)-chloro formoxy stearate (100 gms.) is reacted with an anion-exchange resin (250 gms.) prepared from trimethylamine and a chloromethylated copolymer of styrene and divinyl benzene (see U.S.A. Specification 2,591,573) the reaction being carried out in methanol with a partial conversion to 2-ethybutyl epoxy stearate.