Patent GB-770585-A (GB)
Title: Substituted aliphatic acids and esters thereof
IPC: C07C69/63
Filed: 1955-04-12
Abstract: As plasticisers for polyvinyl halide resins, aliphatic acids which contain at least one acyloxy-halo group of the formula <FORM:0770585/IV(a)/1> in which X is chlorine or bromine and R is a hydrogen atom or a C1 to C5 alkyl group, said acid containing 16 to 22 carbon atoms excepting those in the acyloxy side chain, and esters of such acids, are said to be suitable.  There may also be used the corresponding acids in which a carbonato group replaces the acyloxy-halo group.  The esterifying group may be derived from an alkanol, benzyl alcohol, a glycol, polyalkylene glycol, glycerol or pentaerythritol.  The preparation of the compounds is described (see Group IV (b)).  Specification 769,622 is referred to.ALSO:The invention comprises an aliphatic acid which contains at least one acyloxy-halo group of the formula <FORM:0770585/IV(b)/1> in which X is chlorine or bromine and R is a hydrogen atom or a C1 to C5 alkyl group, said acid containing 16 to 22 carbon atoms excepting those in acyloxy side chain, and to esters of such acids.  Alkyl, hexyl and glyceridic esters are referred to.  The preferred compounds of the invention have the formula <FORM:0770585/IV(b)/2> in which R is a hydrogen atom or a C1 to C7 alkyl group, preferably a methyl or ethyl group, R1 represents a monovalent hydrocarbon radical containing 1 to 14 carbon atoms and X represents an atom of chlorine or bromine. These compounds are useful as plasticizers for vinyl halide resins. They are prepared by reacting the appropriate unsaturated acid or ester thereof with a tertiary alkyl hypochlorite or hypobromite, preferably tertiary butyl hypochlorite, and an aliphatic acid.  The use of formic and acetic acids (which yield formyloxy-halo and acetoxy-halo derivatives) is preferred, 20-60 DEG  C. being a preferred reaction temperature.  Acids suitable as starting compounds include oleic, erucic, eleaostearic, linoleic, linolenic, clupanodonic, palmitoleic, palmitolenic acids such as are obtained by the saponification of, for example, soybean, rapeseed, linseed, sardine and whale oils.  The esters employed may be of ethyl, isopropyl, n, sec. or tert-butyl, tert-amyl, n-octyl, 2-ethylhexyl, octadecyl, lauryl, cyclohexyl or benzyl alcohols, glycols, polyalkylene glycols, glycerol and pentaerythritol.  Mixed esters such as ethyleneoleate-linoleate, glyceryl di-oleate monolinoleate and butylene linoleate-oleate, and oils such as soybean, corn, cottonseed, safflower, sunflower, sesame, poppyseed, walnut, peanut, linseed, sardine, perilla and fish oils in general can also be used. The acyloxyhalo acids obtained, give on reaction with aqueous caustic the dihydroxy acids, which can be esterified and then converted to carbonato esters by reaction with phosgene.  In examples: (1) oleic acid is reacted at 12 DEG  to 16 DEG  C. with formic acid and tert.-butyl hypochlorite in the presence of p-toluenesulphonic acid to give a mixture of 9,10- and 10,9-formoxychlorostearic acid; (2) a mixture of n-hexyl 9,10- and 10,9-formoxychlorostearate was prepared similarly from n-hexyl oleate.  From the appropriate starting materials are prepared similarly (3) poly-(formoxychloro) soybean oil; (4) a mixture of n-hexyl 9,10- and 10,9-acetoxychlorostearates; (5) poly(acetoxychloro) soybean oil. The products are suitable as plasticizers for vinyl halide resins (see Group IV (a). Specification 769,622 is referred to.