Patent GB-421542-A (GB)
Title: Improvements in or relating to the manufacture of synthetic resinous compositions
IPC: C09F1/00
Filed: 1933-03-21
Abstract: Derivatives of natural resins or unsaturated fatty acids or their esters are obtained by treating them with an aromatic hydrocarbon or an alkyl, alkoxy or aryloxy derivative thereof in the presence of an anhydrous metallic chloride.  Suitable natural resins include rosin, Kauri, Congo, Manila, Sandarac, Damar, Pontianac, Sierra Leone and Zanzibar, heat treated natural resins such as run congo and abietic acid.  Esters gums include natural resins esterified with monohydric alcohols, polyhydric alcohols and chlorhydrins such as ethyl alcohol, glycol, glycerin and ethylene chlorhydrin.  Derivatives of natural resins still containing unsaturated linkages such as rosin glyceride, ethyl abietate, congo glycollide and lime-hardened rosin may be used. Suitable fatty acids or esters thereof include linseed oil, cotton seed oil, chinawood oil, soya bean oil, rape seed oil, menhaden oil, perilla oil, sardine oil, rubber seed oil, safflower oil, sperm oil, walnut oil or alkyl, alkoxyalkyl, aryl, alkoxyaryl, aryloxyalkyl and aryloxyaryl esters of unsaturated fatty acids such as ethyl and methyl oleate, ethyoxy ethyl erucate, benzyl eleostearate, dibenzylin elaidate, tolyloxyethyl linolenate, phenoxybenzyl ricinoleate and the butyl ester of linseed oil fatty acids.  Suitable hydrocarbons or derivatives thereof include benzene, toluene, xylene, mesitylene, cymene, ethylbenzene, diphenyl, naphthalene, anisol, phenetol and diphenyl ether. Suitable anhydrous metallic chlorides include aluminium, ferric, titanium and zinc chlorides.  In examples (1) crude abietic acid is dissolved in benzene and heated with aluminium chloride the intermediate product formed being treated with hydrochloric acid to liberate the derivative of abietic acid formed; (2) ester gum is similarly treated with toluene and (3) abietic acid with naphtha to yield derivatives of the natural resin; (4) alkali refined linseed oil is dissolved in benzene and heated with aluminium chloride to yield a phenyl-linseed oil; (5) cottonseed oil is dissolved in toluene and heated with aluminium chloride to yield a tolyl-cottonseed oil and (6) ethyl oleate is dissolved in xylene and heated with aluminium chloride to yield xylyl ethyl stearate.  The derivatives may be used, with or without the addition of known modifying agents, in the manufacture of polyhydric alcohol-polybasic acid resins.  Suitable polyhydric alcohols include glycerol, ethylene glycol, diethylene glycol, polyvinyl alcohol, polyglycerol, triethanolamine, pentaerythritol and alkyl and aryl ethers of polyhydric alcohols containing at least two hydroxyl groups such as monobenzylin and the diethyl ether of pentaerythritol.  Suitable polybasic acids include phthalic anhydride and succinic, adipic, sebacic, maleic, itaconic, tartaric, citric, dilactylic, thiodilactylic, salicylacetic, chlorophthalic, diphenic, pyromellitic and naphthalic acids. Suitable modifying agents include esters such as linseed oil, cottonseed oil, castor oil, ester gum, congo glycollide, ethyl abietate, stearin, triacetin, butyl acetate, dibutyl tartrate and ethyl benzoate, monohydric alcohols such as amyl, benzyl and cyclohexyl alcohols, ether alcohols such as dibenzylin and ethoxyethyl alcohol; ester alcohols such as diacetin and butyl lactate, and monobasic acids such as stearic, oleic, butyric, lactic, salicylic and benzoic acids, the fatty acids of chinawood, cotton seed, soya bean and coconut oils and natural acidic resins such as rosin, kauri and congo.  The resins may be made in an atmosphere of inert gas such as nitrogen or carbon dioxide, in open or closed vessels of glass, enamel or metals such as iron or aluminium, with or without the addition of esterification catalysts such as sulphuric acid, phosphoric acid or various sulphonic acids or in the presence of an inert solvent such as aromatic hydrocarbons, chlorobenzene, dichloroethyl ether, diethyl ether of glycol and menthane.  In examples resins are prepared from (7) phenylstearic acid, glycerol and phthalic anhydride; (8) phenylabietic acid, glycerol, phthalic anhydride and linseed oil fatty acids; (9) tolylester gum, glycerol and phthalic anhydride; (10) tolyl linseed oil acids, glycerol and phthalic anhydride; (11) tolyl cottonseed oil, glycerol and phthalic anhydride and (12) phenyl linseed oil, glycerol and phthalic anhydride.  The modified polyhydric alcohol-polybasic acid resins, alone or in conjunction with cellulose derivatives such as nitrocellulose, benzyl cellulose, ethyl cellulose, cellulose butyrate and cellulose acetopropionate, natural gums or their esters such as rosin, kauri damar, ester gum and ethyl abietate, drying oils such as linseed and chinawood oil, synthetic resins such as phenol or amine aldehyde condensation products or vinyl polymerization products, bitumens, driers, pigments, fillers, lakes, plasticizers or solvents, may be used as lacquers, binders, cements, coating and impregnating agents for cloth, wood pulp and porous stone, sandwiching or adhesive in the manufacture of safety glass, sizing materials, binding agents for sheets of mica or cellulose acetate, in preparing insulating materials and laminated products, linoleum plastics and moulding plastics.  The treated natural resins may also be used in the manufacture of coating compositions.  In examples, lacquers are prepared containing (13) the treated rosin of example 3, ethyl cellulose, butyl acetate, ethyl acetate, ethoxyethyl acetate, ethyl alcohol, butyl alcohol and aliphatic hydrocarbons; (14) tolyl ester gum, chinawood oil, linseed oil, mineral spirits, cobalt linoleate; and (15) resin of example 8, nitro cellulose, butyl acetate, ethyl acetate, cellosolve acetate, ethyl alcohol, butyl alcohol, toluene, hi-flash naphtha, aliphatic hydrocarbons.  The esters of treated unsaturated fatty acids may be used as softeners for cellulose derivatives, waterproofing agents for impregnation of textile fabrics, paper, stone, stucco, wall board, porous materials, and water-repellent paints for metals and, together with treated or untreated natural resins, as varnishes.  The Specification as open to inspection under Sect. 91 refers in general to arylating natural resins and fatty acids or their esters and the use thereof.  This subject-matter does not appear in the Specification as accepted.ALSO:Derivatives of natural resins or unsaturated fatty acids or their esters obtained by treating them with an aromatic hydrocarbon or an alkyl, alkoxy or aryloxy derivative thereof in the presence of an anhydrous aluminium chloride are used in the preparation of coating compositions or impregnating agents.  In an example ester gum treated with toluene is blended with chinawood oil, linseed oil, mineral spirits and cobalt linoleate to yield a varnish.  The esters of the treated fatty acids may be used as waterproofing agents for impregnation of textile fabrics, paper, stone, stucco, wallboard, porous materials and water-repellent paints for metals.