Carbonato nitriles

• Main Author: RIEDEMAN WILLIAM L
• Format: Patent
• Language: English
• Published: 29.10.1957
• Subjects: CHEMISTRY; COMPOSITIONS BASED THEREON; METALLURGY; ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; USE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES ASCOMPOUNDING INGREDIENTS

A carbonato nitrile of a fatty acid containing at least one carbonato group <FORM:0769623/IV(a)/1> and containing a total of from 16 to 22 carbon atoms excluding the carbonyl atom(s) (see Group IV (b)) is used as a plasticizer for cellulosic esters and vinyl halide resins, e.g. polymers of vinyl chloride and bromide; copolymers of vinyl chloride with vinyl acetate or propionate, vinylidene chloride, ethyl acrylate or methyl methacrylate. Compositions may contain 10-50 per cent, preferably 35-50 per cent of the carbonato nitrile based on the total weight. In an example, a composition comprises polyvinyl chloride, 9, 10 carbonatostearonitrile, tribasic lead sulphate and stearic acid.ALSO:The invention comprises a carbonato nitrile of a fatty acid containing at least one carbonato group <FORM:0769623/IV(b)/1> and containing a total of from 16 to 22 carbon atoms excluding the carbonyl carbon atom(s). The preferred products are carbonatostearonitriles. The novel products may be prepared by reacting phosgene with a fatty acid nitrile containing 16 to 22 carbon atoms and at least one pair of hydroxyl groups on adjacent carbon atoms, e.g. 9,10-dihydroxystearonitrile, in the presence of a hydrogen chloride acceptor such as pyridine, quinoline, isoquinoline, dimethyl aniline, diethyl aniline, trimethylamine, triethylamine, tri-n-butylamine or weakly basic anionexchange resins. The reaction may be effected at - 10 DEG C. to the boiling-point of the reaction mixture, preferably - 10 DEG to 60 DEG C. Phosgene may be bubbled into the nitrile or the latter may be reacted with a solution of phosgene in an organic solvent such as benzene. The carbonato nitriles may also be prepared by reacting the polyhydroxylated nitrile with a dialkyl carbonate, such as dimethyl or diethyl carbonate, by ester-interchange in the presence of a catalyst, such as metallic sodium or alkali metal alkoxides, at a temperature high enough to distil the alcohol out of the reaction mixture. Aromatic hydrocarbons may be used as solvents or an excess of the alkyl carbonate may be so used. Suitable polyhydroxy nitriles may be obtained by reacting a fatty acid nitrile containing 16 to 22 carbon atoms and one or more double bonds, e.g. oleonitrile, eruconitrile, elaeostearonitrile, lineonitrile, linolenonitrile, clupanodononitrile or palmitoleonitrile, with hydrogen peroxide and a large excess of formic or acetic acid to produce an hydroxy-acyloxy derivative which is converted to the polyhydroxy nitrile by hydrolysis or alcoholysis. The parent fatty acids are obtainable from animal and vegetable oils, e.g. soybean, rapeseed, linseed, sardine and whale oils by hydrolysis. Mixtures of nitriles from a mixture of such fatty acids may be used. In examples, 9,10-carbonatostearonitrile is produced by reacting 9,10-dihydroxystearonitrile with (1) diethyl carbonate in the presence of sodium at 96 DEG C. until the liberation of ethyl alcohol ceased; (2) phosgene in benzene solution in the presence of a weakly basic anion-exchange resin. The products are useful as plasticizers for vinyl halide resins (see Group IV (a)).