Patent GB-621953-A (GB)
Title: Improvements in or relating to drying oils
Filed: 1945-11-27
Abstract: Drying oils which dry more rapidly than natural oils are obtained by reacting together (a) a fatty oil of the drying type, (b) a polyhydric alcohol other than glycerol, and (c) a monobasic acid having in the molecule an open chain of up to 12 carbon atoms and 2, 3 or 4 conjugated double bonds, one of these being in the 2-position with respect to the carboxyl group.  The monobasic acid (c) may contain in its molecule the structural unit <FORM:0621953/III/1> where n is 2, 3 or 4 and each of the indicated free valency bonds is satisfied by hydrogen, an alkyl group, an alkenyl group or an aryl group.  Thus monobasic acid (c) may be sorbic acid, octatrien-(2,4,6)-oic-(8) acid, decatetren-(2,4,6,8)-oic-(10) acid, b -styryl-acrylic acid, a -methyl sorbic acid, a -ethyl sorbic acid, g ,e -dimethyl sorbic acid, b -d -dimethyl sorbic acid, a  - methyl - d - phenyl - a -g  - butadiene - a -carboxylic acid, a -ethyl-d -phenyl-a ,g -butadiene-a -carboxylic acid, (2,6)-dimethyl-octadien(4,6)-oic-(8) acid or (2,6)-dimethyl-decatrien(2,6,8)-oic-(10) acid.  Alternatively, the monobasic acid (c) may contain in its molecule the cross-conjugated structural unit <FORM:0621953/III/2> where the indicated free valencies are satisfied by hydrogen, alkyl groups, alkenyl groups or aryl groups.  Thus monobasic acid (c) may be a ,b -di-isopropylidene-propionic acid, a -vinyl cinnamic acid, a -isopropenyl cinnamic acid, a -isopropenyl-furfural-acetic acid or d -phenyl-a -isopropenyl-a ,g -butadiene-a -carboxylic acid.  The drying oil may be a fast-drying conjugated oil such as tung or oiticica oil or a slow-drying unconjugated oil such as linseed, soyabean, perilla, dehydrated castor or similar vegetable or fish oil.  The polyhydric alcohol (b) may be chosen from glycols, polyglycols, polyglycerols, pentaerythritol and sorbitol. Reactants (a), (b) and (c) may be reacted simultaneously, if desired, in the presence of a volatile solvent such as xylene, and a large excess of acid may be employed, the excess being distilled off or otherwise removed after esterification is complete.  The synthetic drying oils obtained may be incorporated with oil-soluble synthetic resins to give coating compositions. Suitable resins are oil-soluble phenolic resins, e.g. p-phenyl phenol-formaldehyde and p-hydroxy benzoic acid-formaldehyde resins, and oil-soluble alkyd resins.  In examples, soyabean oil and sorbic acid are reacted together with pentaerythritol or diethylene glycol in the presence of xylene and a toluene solution of lithium naphthenate, and the drying oils thus obtained are used to make varnishes, together with conventional phenol-formaldehyde resins.  The Specification as open to inspection under Sect. 91 refers to the preparation of drying oils by reacting together (a) a drying oil fatty acid having from 12 to 22 carbon atoms in the chain (the chain being taken as including the carboxyl group), or the drying oil itself, or a mono- or di-glyceride of the acid or a partial or complete ester of a polyhydric alcohol other than glycerol with the acid, (b) any polyhydric alcohol, including glycerol, and the reactant (c) already mentioned.  The drying oil fatty acid or derivative thereof (a) may be lauric, myristic, palmitic, stearic, linoleic, linolenic, oleic, eleostearic, liconic, ricinoleic or clupanodonic acid, or the mono- or di-glycerides or other alcohol esters of these acids.  In the case where reactant (a) is a drying oil, the oil may be subjected to a preliminary ester-interchange with the polyhydric alcohol (b) and the product then reacted with monobasic acid (c).  In examples: (1) linseed oil fatty acids and sorbic acid are reacted together with pentaerythritol or trimethylol propane; (2) linseed oil fatty acids and glycerol are reacted with sorbic acid, styryl acrylic acid or octatrienoic acid; (3) soyabean oil fatty acids and glycerol are reacted with sorbic acid or styryl acrylic acid; (4) dehydrated castor oil fatty acids and glycerol are reacted with sorbic acid; (5) linseed oil, glycerol and sorbic acid are reacted together in the presence of calcium naphthenate or alternatively the linseed oil and glycerol are reacted together in presence of calcium naphthenate, lead naphthenate or litharge and the product reacted with sorbic acid; (6) alkali-isomerized soyabean oil or alkali-isomerized linseed oil fatty acids and glycerol are reacted with sorbic acid; (7) tung oil and glycerol are reacted with sorbic acid in the presence of calcium naphthenate and (8) linseed oil and glycerol are reacted with a -vinyl-cinnamic acid in the presence of calcium naphthenate.  Details of tests are given in which varnishes made up of linseed oil fatty acid-glycerol-sorbic acid or soyabean oil fatty acid-glycerol-sorbic acid synthetic drying oils, p-phenyl phenol-formaldehyde or p-hydroxy-benzoic acid-formaldehyde synthetic resins and driers are compared with similar varnishes containing tung oil or dehydrated castor oil as the drying oil. This subject-matter does not appear in the Specification as accepted.ALSO:Drying oils which dry more rapidly than natural oils are obtained by reacting together (a) a fatty oil of the drying type, (b) a polyhydric alcohol other than glycerol, and (c) a monobasic acid having in the molecule an open chain of up to 12 carbon atoms and 2, 3 or 4 conjugated double bonds, one of these being in the 2-position with respect to the carboxyl group.  The synthetic drying oil obtained may be incorporated with oil-soluble synthetic resins to give coating compositions.  Suitable resins are oil-soluble phenolic resins, e.g. p-phenyl phenol-formaldehyde and p-hydroxy benzoic acid-formaldehyde resins, and oil-soluble alkyd resins.  In examples, soyabean oil and sorbic acid are reacted together with pentaerythritol or diethylene glycol in the presence of xylene and a toluene solution of lithium naphthenate, and the drying oils thus obtained are used to make varnishes together with conventional phenol-formaldehyde resins.  The Specification as open to inspection under Sect. 91 refers to the preparation of drying oils by reacting together (a) a drying oil fatty acid having from 12 to 22 carbon atoms in the chain (the chain being taken as including the carboxyl group), or the drying oil itself, or a mono- or di-glyceride of the acid or a partial or p  complete ester of a polyhydric alcohol other than glycerol with the acid, (b) any polyhydric alcohol, including glycerol, and the reactant (c) already mentioned.  The drying oil fatty acid or derivative thereof (a) may be lauric, myristic, palmitic, stearic, linoleic, linolenic, oleic, eleostearic, liconic, ricinoleic or clupanodonic acid, or the mono- or di-glycerides or other alcohol esters of these acids.  In the case where reactant (a) is a drying oil, the oil may be subjected to a preliminary ester-interchange with polyhydric alcohol (b) and the product then reacted with monobasic acid (c).  Details of tests are given in which varnishes made up of linseed oil fatty acid-glycerol-sorbic acid or soyabean oil fatty acid-glycerol-sorbic acid synthetic drying oils, p-phenyl phenol-formaldehyde or p-hydroxy-benzoic acid-formaldehyde synthetic resins and driers are compared with similar varnishes containing tung oil or dehydrated castor oil as the drying oil.  This subject-matter does not appear in the Specification as accepted.ALSO:Drying oils which dry more rapidly than natural oils are obtained by reacting together (a) a fatty oil of the drying type, (b) a polyhydric alcohol other than glycerol and (c) a monobasic acid having in the molecule an open chain of up to 12 carbon atoms and 2, 3 or 4 conjugated double bonds, one of these being in the 2-position with respect to the carboxyl group.  The monobasic acid (c) may contain in its molecule the structural unit <FORM:0621953/IV (b)/1> where n is 2, 3 or 4 and each of the indicated free valency bonds is satisfied by hydrogen, an alkyl group, an alkenyl group or an aryl group.  Thus, monobasic acid (c) may be sorbic acid, octatrien - (2,4,6) - oic - (8) acid, decatetren - (2,4,6,8) - oic - (10) acid, b -styryl-acrylic acid, a -methyl sorbic acid, a -ethyl sorbic acid, g ,e -dimethyl sorbic acid, b ,d -dimethyl sorbic acid, a  - methyl - d  - phenyl - a ,g  - butadiene - a  - carboxylic acid, (2,6)-dimethyl-octadien (4,6)-oic-(8) acid or (2,6)-dimethyl-decatrien (2,6,8)-oic-(10) acid.  Alternatively, the monobasic acid (c) may contain in its molecule the cross-conjugated structural unit <FORM:0621953/IV (b)/2> where the indicated free valencies are satisfied by hydrogen, alkyl groups, alkenyl groups or aryl groups.  Thus, monobasic acid (c) may be a ,b  - di - isopropylidine-propionic acid, a  - vinyl cinnamic acid, a -isopropenyl cinnamic acid, a -isopropenyl-furfural-acetic acid or d -phenyl-a -isopropenyl-a ,g -butadiene-a -carboxylic acid.  The drying oil may be a fast-drying conjugated oil such as tung or oiticica oil or a slow-drying unconjugated oil such as linseed, soyabean, perilla, dehydrated castor or similar vegetable or fish oil.  The polyhydric alcohol (b) may be chosen from glycols, polyglycols, polyglycerols, pentaerythritol and sorbitol. Reactants (a), (b) and (c) may be reacted simultaneously, if desired in the presence of a volatile solvent such as xylene, and a large excess of acid may be employed, the excess being distilled off or otherwise removed after esterification is complete.  In examples, soyabean oil and sorbic acid are reacted together with pentaerythritol or diethylene glycol in the presence of xylene and a toluene solution of lithium naphthenate.  The Specification as open to inspection under Sect. 91 refers to the preparation of drying oils by reacting together (a) a drying oil fatty acid having from 12 to 22 carbon atoms in the chain (the chain being taken as including the carboxyl group), or the drying oil itself, or a mono-or di-glyceride of t