Patent GB-786657-A (GB)
Title: New substituted fatty acid esters
IPC: C11C3/00
Filed: 1955-04-12
Abstract: The invention comprises a carbonato fatty acid ester which contains in the alcohol moiety thereof from 1 to 18 carbon atoms and in the acid moiety or moieties thereof a group or group of the formula <FORM:0786657/IV (b)/1> in the proportion of at least one such group for each acid moiety of the ester, each acid moiety containing from 16-22 carbon atoms excluding carbonato carbon atoms.  It also comprises an ester product comprising a mixture of two or more fatty acid esters each containing in an acid moiety thereof the carbonato group shown above, there being present in the ester product an average ratio of at least one such group for each acid moiety, the alcohol and acid moieties of the esters having the above specified carbon contents.  The carbonato esters may be prepared from esters which contain 1-18 carbon atoms in each alcohol moiety and whose acid moieties each contains 16-22 carbon atoms and at least one pair of hydroxyl groups on adjacent carbon atoms.  One method comprises reacting these esters with phosgene, preferably in the presence of a mildly basic hydrogen chloride acceptor such as a tertiary amine or weakly basic anion exchange resin preferably at -10 DEG  to +60 DEG C.; an inert solvent may be present.  Another method comprises reacting the esters with a dialkyl carbonate in the presence of an alkali metal or alkali metal alkoxide, in ester-interchange; an inert solvent may be present and the temperature is such that the liberated alkanol is distilled off. The hydroxylated esters used as starting materials may be prepared from the esters of corresponding unsaturated acids by reaction with hydrogen peroxide and excess of formic or acetic acid to yield a hydroxyacyloxy derivative which is converted to the required polyhydroxylated ester by hydrolysis of the acyloxy group or by alcoholysis with a lower aliphatic alcohol according to the method of U.S.A.  Specification 2,669,572.  The unsaturated esters used may be derived from such acids as oleic, erucic, elaeostearic, linoleic, elupanodonic, palmitoleic and palmitolenic acids and mono- and polyhydric alcohols, including typically, ethyl, tert. amyl, 2-ethylhexyl, lauryl, cyclohexyl and benzyl alcohols, propylene glycol, butanediol, dodecanediol-1,12, diethylene glycol and pentaerythritol; mixed esters such as ethylene oleate-linoleate, glyceryl di-oleate monolinoleate and butylene-linoleateoleate and vegetable and animal oils including typically soybean, safflower, linseed, sardine and cottonseed oils are utilizable.  It is not necessary for every double bond present in the acid moiety to be carbonated.  The carbonato esters are useful as plasticizers for vinyl resins and cellulosic esters (see Group IV (a)).  In (1) a mixture of the lauryl and myristyl esters of 9,10-dihydroxy stearic acid is reacted in benzene with phosgene using an anion exchange resin catalyst to give the corresponding carbonate esters; the n-octyl, 2-ethylhexyl and a mixture of decyl and lauryl esters of carbonator-9 : 10-stearic acid may be obtained in like manner; (2) n-hexyl 9 : 10-dihydroxystearate is heated in ester-exchange with diethyl carbonate using sodium as catalyst yielding hexyl 9 : 10-carbonato stearate; (3) 2-ethyl butyl 9 : 10-dihydroxy stearate in pyridine is reacted with a toluene solution of phosgene yielding 2-ethyl butyl 9 : 10-carbonato stearate; the 2-ethylhexyl, n-butyl and b -chloroethyl esters are prepared in like manner; (4) benzyl 9 : 10-dihydroxy stearate is reacted with phosgene in a manner similar to (3) yielding the benzyl 9 : 10-carbonato stearate; (5) 2-ethyl butyl ester tetra hydroxy stearic acid (derived from linoleic acid) is reacted with 2.8 mols. phosphene in a manner analogous to (3) yielding a carbonato ester averaging more than 1 but not quite 2 carbonato groups.ALSO:Vinyl halide resins and cellulosic esters are plasticised by means of carbonato fatty acid esters which contain in the alcohol moiety thereof from 1 to 18 carbon atoms and in the acid moiety or moieties thereof a group or groups of the formula <FORM:0786657/IV (a)/1> in the proportion of at least one such group for each acid moiety of the ester, each acid moiety containing 16 to 22 carbon atoms excluding the carbonato carbon atoms.  The plasticising esters include ester products comprising a mixture of 2 or more fatty esters each containing in an acid moiety thereof the carbonato group shown above, there being present in the ester product an average ratio of at least one such group for each acid moiety, the alcohol and acid moieties of the esters having the above specified carbon contents.  The vinyl resins are vinyl halide polymers, e.g. those of vinyl chloride or bromide, copolymers of a vinyl halide and vinyl ester of a lower aliphatic acid, e.g. vinyl acetate or propionate; copolymers of vinyl halides and vinylidene halides; and copolymers of vinyl halides and other copolymerizable compounds containing a vinylidene group such as methyl methacrylate and ethyl acrylate.  The esters may be present in amounts of 10-50 per cent of the plasticised resin.  An example describes the plasticising of polyvinyl chloride, containing stearic acid as lubricant and tribasic lead sulphate as stabilizer, by means of the chloroethyl, n-butyl, 2-ethylbutyl, n-hexyl, 2-ethylhexyl and mixed lauryl-myristyl esters of 9 : 10-carbonato stearic acid.  Numerous other carbonato esters are referred to including carbonato derivatives of vegetable and animal oils, e.g. soybean and safflower oils.  The preparation of the carbonato compounds is described (see Group IV (b)).