Patent GB-715743-A (GB)
Title: Esters of hydrocarbon-substituted succinic acids and compositions containing the same
IPC: C08K5/11
Filed: 1950-12-22
Abstract: Film forming materials such as cellulose derivatives, vinyl-type polymers, and resinous products obtained by condensing aldehydes with NH2-containing compounds may be plasticized with di-esters of a succinic acid having an open chain hydrocarbon radical containing from 18 to 26 carbon atoms joined to one of the methylene groups of the succinic acid molecule and a saturated monohydric alcohol which is not a partial ester of a polyhydric alcohol (see Group IV (b)). The open chain hydrocarbon radical may be straight chained or branched, saturated or unsaturated, and several such radicals are specified, the preferred radicals being 1-octa-decenyl, octadecyl, 3-nonadecenyl, monodecyl, docosyl, heneicosenyl, eicosyl, 3, 5-diethyloctadecenyl, 4-isoamylheptadecyl and 6-butyloctadecyl.  The esterifying alcohol is preferably an aliphatic saturated monohydric alcohol containing from 1 to 8 carbon atoms but other monohydric alcohols are also specified.  The aldehydes used for the condensation with the NH2-containing compound may be formaldehyde, or compounds engendering formaldehyde (e.g. paraformaldehyde and hexamethylene tetramine), acetaldehyde, propionaldehyde, butyraldehyde, acrolein, methacrolein, crotonaldehyde, benzaldehyde and furfural, mixtures thereof, or mixtures of formaldehyde or materials yielding formaldehyde with such aldehydes.  The NH2-containing compounds are exemplified by urea, thiourea, diurea, hydroxy urea, ethanol urea, unsymmetrical diphenyl urea, diethylene triurea, methyl urea, acetyl urea, phenyl thiourea, asymmetrical diethyl urea, methylol ureas, guanidine, dicyandiamide, guanyl urea, guanyl thiourea and melamine. Cellulose derivatives, are exemplified by cellulose-nitrate, -acetate, -acetate butyrate, -propionate, -isobutyrate, -crotonate, -stearate and -valerate; ethyl cellulose, methyl cellulose, butyl cellulose, benzyl cellulose, glycol cellulose, cellulose acetostearate, cellulose aceto-propionate, cellulose aceto-tartarate and mixtures thereof.  Specified vinyl-type monomers are the homopolymers and copolymers of the vinyl-type monomers such as styrene, alpha-methylstyrene, dichloro-, styrene, vinyl naphthalene, vinyl phenol-, acrylic acid, and the alpha-alkyl substituted acrylic acids, the esters of these unsaturated acids, such as methyl acrylate, methyl methacrylate, butyl methacrylate, and propyl acrylate; the vinylidene halides, such as vinylidene-chloride, -bromide, and -fluoride; the vinyl esters of the inorganic acids, such as the halogen acids and hydrocyanic acid, e.g. vinyl chloride, vinyl bromide, acrylonitrile and methacrylonitrile; the vinyl esters of the monocarboxylic acids such as vinyl-acetate, -chloroacetate, -benzoate, -valerate, and -caproate; the vinyl esters of the polycarboxylic acids such as divinyl succinate, divinyl adipate, vinyl allyl phthalate, vinyl methyl glutarate; the vinyl esters of the unsaturated acids such as vinyl acrylate, vinyl crotonate, and vinyl methacrylate.  The preferred vinyl type polymers are the vinyl halide polymers which term is stated to refer to polymers containing at least 60 per cent. by weight of a vinyl halide such as the chloride or bromide, e.g. polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate, vinylidene chloride, or methyl methacrylate.  A single di-ester may be used as the plasticizer or a mixture of two or more of the di-esters may be used and there may also be present known plasticizing agents such as dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate.  For the preparation of coating compositions the film-forming material and plasticizer are preferably mixed together in an organic solvent such as acetone, ethylene glycol ethyl ether, ethyl acetate, butyl acetate, toluene, a xylene, mixture of isomeric xylenes, or a mixture of two or more such solvents.  Other agents which may be p  included in the compositions are:-pigments and colouring materials such as titanium pigments, copal, kauri, damar, and ester gums.  The coating compositions in suitable solvents may be applied to a surface such as steel or metal either primed or unprimed by spraying, brushing or other method and the solvent may be evaporated off at room temperature or by baking the coating by application of infra-red rays or in an oven.  The compositions containing the film-forming material and the diester may also be used to impregnate fabrics and fibrous materials to impart rigidity thereto, or to laminate wood or fabrics of cotton or glass fibres, or may be applied to fibres such as wood flour or alpha-cellulose employed in the preparation of moulding powders. In examples: (1) a coating composition containing equal quantities of a melamine-formaldehyde resin and dimethyl octadecenyl succinate in a solvent comprising xylene and n-butanol is cast on tin panels and dried at 110 DEG  C. and the film formed is compared with one formed from the same resin but without the plasticizer; (2) a composition containing an urea-formaldehyde resin and dimethyl octadecenyl succinate in the same solvent as in (1) is cast on tin panels and dried at 100 DEG  C.; (3) coating compositions are prepared by mixing one part of nitrocellulose with one part of dioctyl phthalate, dibutyl phthalate and diethyl octadecenyl succinate respectively in a solvent comprising n-butyl acetate, ethyl acetate, butanol, toluene and low aromatic petroleum lacquer diluent; (4) a composition comprising nitrocellulose and dibutyl phthalate or diethyl octadecenyl succinate in the solvent used in (3) is coated on tin panels and the films compared; (5) coating compositions prepared from nitrocellulose and dioctyl phthalate or diethyl octadecenyl succinate in the solvent as in (3) are coated on strips of cloth; (6) a coating composition is prepared from ethyl cellulose and dimethyl octadeceny succinate in a solvent comprising xylene and n-butanol and coated on tin panels; (7) a coating composition is prepared from polyvinyl chloride and dimethyloctadecenyl succinate in cyclohexanol and coated on tin panels; (8) a coating composition is prepared from nitrocellulose and dibutyl octadecyl succinate in the solvent used in (3) and coated on tin panels.ALSO:The invention comprises as new products diesters of a succinic acid having an open chain hydrocarbon radical containing from 18 to 26 carbon atoms joined to one of the methylene groups of the succinic acid molecule, and a saturated monohydric alcohol which is not a partial ester of a polyhydric alcohol.  The open chain hydrocarbon radical may be straight chained or branched and may be saturated or unsaturated and the esterifying alcohol is preferably an aliphatic alcohol containing from 1 to 8 carbon atoms. Examples of the alkylated succinic acids are 1-octadecenyl-, 3,6-octadecadienyl -, octadecyl -, nonadecenyl -, nonadecyl -, 3,6 - nonadecadienyl -, 9,12 - octadecadienyl -, eicosyl -, 3 - eicosenyl -, heneicosenyl -, 4,7 - heneicosdienyl -, docosyl -, 3,5 - diethyloctadecenyl -, tricosyl -, 3,8 - tricosadienyl -, 3,5,7 - docosatrienyl -, 2,5 - dibutyloctadecyl -, 4,6 - diisoamyldodecyl -, pentacosyl -, 4 - isoamylheptadecyl -, 6 - butyloctadecyl -, tetracosenyl -, and 3,5,7 - tripropyl - 2 - dodecenyl -, - succinic acids.  The anhydrides of the acids containing the unsaturated hydrocarbon radicals may be obtained by condensing an olefinic hydrocarbon with maleic anhydride at elevated temperature, preferably above 200 DEG  C., and under sufficient pressure to maintain the re-actants in the liquid phase, and the alkyl substituted acid anhydrides may be obtained by hydrogenating the corresponding unsaturated substituted acid anhydrides, e.g. by treating with hydrogen at 100-200 DEG  C. and 200 to 1000 pounds per square inch in the presence of a hydrogenation catalyst.  Examples of alcohols which may be used for the esterification are methanol, ethanol, isopropanol, butanol, hexanol, isohexanol, tert.-butanol, heptanol, tert.-octanol, 2-ethylhexanol, 2,5-dimethyl-heptanol, dodecanol, tetradecanol, pentadecanol, octadecanol, 3,5,8-triethyl dodecanol, cyclohexanol, methylcyclohexanol, tert.-butylcyclohexanol, cyclohexylpropanol, hexanediol monoethyl ether, benzyl alcohol, furfuryl alcohol, 3-bromo-octanol, 5-methoxydodecanol, and 3-chloroheptanol.  The diesters may be prepared by direct esterification of the acids or their anhydrides or by reacting a diester of the desired alcohol and maleic anhydride with an olefin by a method similar to that described for preparing the acid anhydrides thus dimethyl octadecenylsuccinate may be obtained by reacting octadecylene with dimethyl maleate.  The esters may also be prepared by reacting the alcohols with an acid chloride in pyridine, or by an ester exchange method.  Preferably they are prepared by reacting the acid anhydrides with the alcohols in the presence of an esterification catalyst and removing water formed during the reaction, preferably by distillation.  Specified esterification catalysts are sulphuric, p-toluene sulphonic, ethyl sulphonic, benzene sulphonic, hydrobromic, chloroacetic and formic acids, boron and silicon fluorides, and acid salts such as monosodium sulphate, zinc chloride, and zinc sulphate.  The esterification may be carried out at atmospheric, superatmospheric, or subatmospheric pressure and is preferably effected at 70 DEG  to 200 DEG  C.  It may also be carried out in the presence of a solvent or diluent such as benzene, toluene, cyclohexane, xylene, and mixtures thereof.  In examples (1) technical octadecene containing octadecene-2 is heated with maleic anhydride in a steel bomb for 6 hours at 250 DEG  C. to yield octadecenylsuccinic anhydride which is then mixed with methanol, concentrated sulphuric acid, and anhydrous aluminium sulphate and the mixture heated at 78 DEG  to 80 DEG  C. with a stream of dry, superheated methanol vapour passing through the liquid, to yield dimethyloctadecenyl succin