Patent GB-462046-A (GB)
Title: Improved synthetic resins and their manufacture
IPC: C08G8/28
Filed: 1935-05-24
Abstract: Phenol - aldehyde resins are catalytically hydrogenated at a temperature of at least 140 DEG  C. and preferably under a pressure of at least 150 lbs. per sq. in.  The resin may be treated in the molten state or in solution in an organic solvent.  Suitable catalysts are those of the iron and platinum groups, particularly the hydrogen reduction products of nickel carbonate, oxides, hydroxides, chromate, vanadate and tungstate or the nickel catalysts described in U.S.A.  Specification 1,628,190. Preferably, the reaction is effected within the temperature range of 140--225 DEG  C., using pressures of 150--4000 lbs. per sq. in. The resinous starting materials may be prepared from either mononuclear or polynuclear phenols.  As mononuclear phenols, the following are mentioned: o- and p-cresols, p-chlorphenol, p-nitrophenol, p-tert-butyl and amyl-phenols, 3 - methyl-6-isopropylphenol, 1 : 2 : 4 - xylenol, creosole, guaiacol, pseudo-cumenol, resorcinol, hydroquinone, m - dihydroxytoluene, 3 : 4-dihydroxytoluene, 1 : 2 : 3- and 1 : 2 : 4-trihydroxybenzenes and 1 : 3-dihydroxy-4-acetylbenzene. Polynuclear phenols referred to are p : p<1>-dihydroxydiphenyl, di(4-hydroxyphenyl)-cyclohexane, p : p<1>-dihydroxybenzophenone, p : p<1> - dihydroxydiphenylether, di(4-hydroxyphenyl)sulphide and sulphone, b -di(4-hydroxyphenyl)naphthane, 1 : 1-di(4-hydroxyphenyl)-4-methylcyclohexane, di(4-hydroxynaphthyl)-methane, ar-tetrahydro-b -naphthol, di (4-hydroxy-3-methylphenyl)dimethylmethane, di-(4 - hydroxy - 3 - chlorphenyl)dimethylmethane, di(4 - hydroxynaphthyl)methylethylmethane, di (4 - hydroxy - 3 - methylphenyl)ethylmethane, 1 : 1-di(4-hydroxy-3-methylphenyl)cyclohexane, di(2-hydroxy-5-methylphenyl)dimethylmethane, di(4 - hydroxy - 3 - methylphenyl)phenylmethane, a -and b -naphthols, hydroxyxanthones, p-cyclohexylphenol and p-(4-methylcyclohexyl)phenol.  The preferred aldehyde is formaldehyde, but hexamethylenetetramine, methylene chloride, methylal, paraformaldehyde, furfural and benzaldehyde may also be employed.  The products may be made up into compositions with (1) other synthetic resins, e.g. polyhydric alcohol-polycarboxylic acid resins modified or not with drying oils or their acids, coumarone-indene resins, amine-aldehyde resins, polyvinyl resins, polyacrylic and polymethacrylic resins; (2) cellulose esters and ethers, e.g. ethyl cellulose, benzyl cellulose, crotyl cellulose, nitrocellulose, cellulose propionate and cellulose isobutyrate; (3) natural resins, their esters and hydrogenation products of both, e.g. hydrogenated or unhydrogenated rosin, kauri, copals, ester gum and ethyl abietate; (4) oils, e.g. castor, olive, coconut, cotton seed, chinawood, sunflower seed, linseed, citicica, perilla and walnut oils; (5) natural and synthetic waxes, e.g. beeswax, candelilla wax, montan wax, lauryl stearate and hydrogenated castor oil; (6) bitumens, e.g. asphalt; (7) alcohols, e.g. ethyl, isopropyl, isobutyl, heptyl, benzyl, phenylethyl, abietyl, furfuryl and tetrahydrofurfuryl alcohols, decahydro-b -naphthol, di(4-hydroxycyclohexyl)dimethylmethane, dicyclohexanolpropane, dimethyl-a -thienyl alcohol, triethanolamine, and the alcohols obtained by the hydrogenation of carbon oxides or of vegetable oils. The following examples are given of the preparation of hydrogenated resins: (1) phenol is heated with aqueous formaldehyde in the presence of ammonium hydroxide or chloride and the product treated in alcohol solution with hydrogen at elevated temperature and pressure for some hours in a shaking autoclave using a nickel-on-kieselguhr catalyst; (2) 1 mol. of di(4 - hydroxyphenyl)dimethylmethane is allowed to stand with 2,5 mols. of formaldehyde in aqueous solution containing 2 mols. of caustic soda and the resulting resin then hydrogenated as in (1); (3) p-hydroxydiphenyl is condensed with formaldehyde and the product hydrogenated in butyl acetate solution under similar conditions to those of (1).  According to further examples, the hydrogenated resins are made up into varnishes with (1) abietyl alcohol, chinawood oil, blown linseed oil, toluene, ethoxyethanol and a cobalt drier; (2) blown linseed oil, a solvent and cobalt linoleate; (3) chinawood oil, a naphtha mixture and cobalt linoleate; (4) pyroxylin, toluene, butyl and ethyl acetates, and butyl and ethyl alcohol; (5) ethyl cellulose, toluene, butyl and ethyl acetates, and ethyl alcohol. Compositions containing the resins may also be used as moulding plastics; impregnating and coating agents for paper, cloth, porous stone and rubberized fabrics; sandwiching material or adhesive in the manufacture of shatter-proof glass; adhesives, cements and sealing waxes; and binders for mica, asbestos and cotton-flock.ALSO:Phenol-aldehyde resins are catalytically hydrogenated at a temperature of at least 140 DEG  C. and preferably under a pressure of at least 150 lbs. per sq. in.  The resin may be treated in the molten state or in solution in an organic solvent.  Suitable catalysts are those of the iron and platinum groups, particularly the hydrogen reduction products of nickel carbonate, oxides, hydroxides, chromate, vanadate and tungstate or the nickel catalysts described in U.S.A.  Specification 1,628,190. Preferably the reaction is effected within the temperature range of 140--225 DEG  C., using pressures of 150--4000 lbs. per sq. in. The resinous starting material is prepared from either mono- or poly-nuclear phenols on the one hand and formaldehyde or other aldehyde on the other; lists are given of both components.  The following examples are given: (1) phenol is heated with aqueous formaldehyde in the presence of ammonium hydroxide or chloride and the product treated in alcohol solution with hydrogen at elevated temperature and pressure for some hours in a shaking autoclave using a nickel-on-kieselguhr catalyst; (2) 1 mol. of di (4-hydroxyphenyl) dimethylmethane is allowed to stand with 2,5 mols. of formaldehyde in aqueous solution containing 2 mols. of caustic soda and the production then hydrogenated as in (1); (3) p-hydroxydiphenyl is condensed with formaldehyde and the product hydrogenated in butyl acetate solution under similar conditions to those of (1).