Patent GB-462045-A (GB)
Title: Improved synthetic resins and compositions containing the same
IPC: C08G8/28
Filed: 1935-05-24
Abstract: Resins prepared by the condensation of polynuclear phenols with aldehydes are modified by treatment with hydrogen in the presence of a hydrogenation catalyst.  The resin may be treated in the molten state or in solution in an organic solvent, preferably at a temperature of 140--225 DEG  C. and under a pressure of 150--4000 lbs. per sq. in.  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 a nickel catalyst prepared by digesting a nickel-aluminium alloy with caustic soda.  As polynuclear phenols the following are mentioned: 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, p - (4 - methylcyclohexyl)phenol, di(4-hydroxyphenyl)sulphide and sulphone, p : p<1>-dihydroxydiphenyl, di(4-hydroxyphenyl)cyclohexane, p : p<1>-dihydroxybenzophenone, p : p<1>-dihydroxydiphenylether, b  - di(4 - hydroxyphenyl)naphthene, 1 : 1-di(4-hydroxyphenyl)-4-methylcyclohexane, di(4-hydroxynaphthyl)-methane and ar-tetrahydro-b -naphthol.  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, linseed, sunflower seed, citicica, perilla, walnut and safflower seed oils; (5) natural and synthetic waxes, e.g. beeswax, candelilla wax, montan wax, lauryl stearate and hydrogenated castor oil; (6) bitumens, e.g. asphalt.  The following examples are given of the preparation of hydrogenated resins: (1) 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 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) p-dihydroxydiphenyl 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) chinawood oil, a naphtha mixture and cobalt linoleate; (2) ethyl cellulose, toluene, butyl and ethyl acetates, and ethyl alcohol; (3) ethyl cellulose and dibutyl phthalate.  Compositions containing the resins can 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:Resins prepared by the condensation of polynuclear phenols with aldehydes are subjected to catalytic hydrogenation.  The resin may be treated in the molten state or in solution in an organic solvent, preferably at a temperature of 140--225 DEG  C. and under a pressure of 150--4000 lbs. per sq. in.  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 a nickel catalyst prepared by digesting a nickel-aluminium alloy with caustic soda.  Lists are given of both the phenolic and aldehydic components of the resinous starting material.  The following examples are given: (1) 1 mol. of di (4-hydroxyphenil) dimethylmethane is allowed to stand with 2,5 mols. of formaldehyde in aqueous solution containing 2 mols. of caustic soda 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) p-dihydroxydiphenyl is condensed with formaldehyde and the product hydrogenated in butyl acetate solution under similar conditions to those of (1).