Patent GB-665595-A (GB)
Title: Improvements in and relating to alkyd resins
IPC: C08G63/46
Filed: 1949-12-20
Abstract: Alkyd resins are prepared by heating (1) a succinic acid having an open-chain hydrocarbon radical containing 18-20 carbon atoms substituted on one of its chain carbon atoms or an ester or anhydride thereof with (2) an open-chain polyhydric alcohol containing at least three hydroxy groups and 3-7 carbon atoms or an ester thereof. Specified acids are 1-octadecenyl-; 3-octadecenyl-; octadecyl-; nonadecyl-; 3-nonadecenyl-; 2,5-octadecadienyl-; and 1-eicosenyl-succinic acids and specified esters are the methyl, ethyl, butyl and amyl esters.  Specified alcohols are glycerol, pentaerythritol, hexanetriols, heptanetriols, trimethylolpropane and the esters thereof with formic, acetic, propionic and butyric acids. The reaction may be accomplished by heating the acid and alcohol to 100-300 DEG  C., if desired in presence of a catalyst, e.g. p-toluene-sulphonic acid, zinc chloride, stannic chloride, calcium acetate, barium acetate, zinc acetate or hydrochloric acid or a diluent, e.g. benzene, toluene, xylene, cyclohexanone, chloroform or carbon tetrachloride and preferably under a blanket of an inert gas, e.g. nitrogen, carbon dioxide, helium or methane.  When esters of the substituted succinic acids or polyhydric alcohols are used the reactions are carried out in presence of an ester interchange catalyst, e.g. sodium or potassium alcoholates; p - toluenesulphonic acid; copper; nickel; tin; zinc; pyridine or potassium carbonate. Specified modifying agents are the fatty acids of linseed, soybean, tung oil, oiticia oil, dehydrated castor oil, walnut oil, cotton seed oil and castor oil; the monoglycerides of linseed oil, soybean oil and tung oil fatty acids; lactic, benzoic, chlorobenzoic, salicylic, stearic, palmitic, butyric and cinnamic acids; cellulose derivatives, protein plastics, rosin, phenol-aldehyde resins, ureaaldehyde resins and polyamides; resins formed from styrene, alpha-methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, methyl acrylate and methyl methacrylate; polymers and copolymers of butadienes, pentadienes, hexadienes and nonadienes; the divinyl, diallyl and dimethallyl esters of oxalic, malonic, citric and tartaric acids; the divinyl, diallyl and dimethallyl polyethers of glycol and diethylene glycol and the corresponding di- and tri-ethers of glycerol; vinyl, allyl and methallyl acrylates; and divinyl, diallyl and dimethallyl phthalates.  The alkyd resins may be combined with colophony, shellac, copal, dammar, camphor, naphthalene, anthacene, aryl phosphates, alkyl and aryl phthalates, pitch, asphalt, asbestos, sand, clay, talc, mica, wood flour and cotton.  Specified curing catalysts for the resins are finely-divided iron, zinc oxide, peroxides, stannic chloride and boron trifluoride.  Siccative agents, e.g. lead, cobalt or manganese naphthenates may be added to the alkyds, modified with drying components.  In examples: (1) 1-octadecenylsuccinic anhydride is heated with glycerol in a stream of carbon dioxide; (2) octadecyl succinic anhydride is heated with glycerol in a stream of carbon dioxide; (4) 1-octadecenylsuccinic acid is heated with linseed fatty acid and glycerol; (3) 1-octadecenylsuccinic anhydride is heated with pentaerythritol in a stream of carbon dioxide; (6) glycerol is heated respectively with 3 - octadecenyl - succinic acid; nonadecyl - succinic acid; 3-nonadecenyl-succinic acid and 1-eicosenyl-succinic acid. Specification 464,276 is referred to.  The Specification as open to inspection under Sect. 91 is not limited to polyhydric alcohols having three to seven carbon atoms but refers also to hexahydroxyl cyclohexane, polyallyl alcohol and its acetate, polymethallyl alcohol and polyolein alcohol.  This subject-matter does not appear in the Specification as accepted.ALSO:Succinic anhydrides having an open-chain hydrocarbon radical containing 18-20 carbon atoms substituted on one of its chain carbon atoms are prepared by condensing an olefinic hydrocarbon containing 18-20 carbon atoms with maleic anhydride at an elevated temperature and under pressure.  The unsaturated hydrocarbon substituted anhydrides thus prepared may be converted into the saturated form by treating them with hydrogen gas under pressure of from 200-1000 lb./sq. inch at 100-200 DEG  C. in presence of a hydrogenation catalyst.  Anhydrides referred to are 1-octadecenyl-; 3-octadecenyl-; octadecyl-; nonadecyl-; 3-nonadecenyl-; 2,5-octadecadenyl-; and 1-eicosenyl-succinic anhydrides.  In examples: (1) octadecene-1 and maleic anhydride are heated for 6 hours at 250 DEG  C. to produce octadecenyl succinic anhydride; (2) the anhydride of example (1) is mixed with iso-octane and the mixture hydrogenated in presence of a nickel catalyst at 150 DEG  C. and 1000 p.s.i. pressure for 11 hours to produce octadecyl succinic anhydride.  The anhydrides are condensed with polyhydric alcohols to produce alkyd resins (see Group IV (a)).  Specification 464,276 is referred to.