Patent GB-451278-A (GB)
Title: Improved manufacture of condensation products
IPC: C08G63/137
Filed: 1934-12-29
Abstract: Resinous condensation products are prepared by heating hydroxyl-group-containing cycloaliphatic compounds which are substituted by perhydrogenated phenyl or substituted-phenyl residues containing alcoholic hydroxyl groups with polybasic carboxylic acids or their anhydrides.  The hydroxy-compounds may be obtained by condensing phenols with aldehydes or ketones, followed by hydrogenation.  There may also be used perhydrogenated di- and polyhydroxyphenyl, hydroxytolyl or hydroxyxylyl compounds, or those of the type of 4 : 4<1>-dihydroxydiphenyl. Acids specified are phthalic, naphthalic, oxalic, malonic, succinic, glutaric, adipic, methyladipic, pimelic, suberic, azelaic, sebacic, fumaric, maleic, dimalonic, aconitic, diglycollic, salicylacetic acids; thioether-dicarboxylic acids such as thiodiglycollic acid; tetrahydrophthalic, hydroxyphthalic, halogenphthalic, benzene - 1 - carboxylic - 2 - thioglycollic, trimellitic, hexahydrophthalic, naphthalene-1 : 8-dicarboxylic, diphenyldicarboxylic, benzophenone di- and polycarboxylic acids. There may also be incorporated at any stage, other synthetic resins or their raw materials, for example, phenols, aldehydes, ureas.  It is possible to work with or without the presence of inert gases such as nitrogen, hydrogen or carbon dioxide; with azeotropic media; or below, at, or above atmospheric pressure. There may be present solvents: such as benzine, naphtha, solvent naphtha, kerosene; alcohols such as methyl alcohol, ethyl alcohol, n-butyl alcohol, isobutyl alcohol; or other compounds, such as acetone, ethyl acetate, n-butyl acetate, glycol diacetate, triacetin, diethyl, n-dibutyl and iso-diamyl oxalate, ethyl lactate, esters of tartaric acid, glycol ethers, such as glycol-methyl, glycolethyl and glycol-butyl ethers, ethylene glycoldiethyl ether, ethylene chlorohydrin, vinyl chloride (with the use of pressure), vinyl acetate, benzene, toluene, xylene, cymene, naphthalene, hydrogenated naphthalene, diphenyl, anthracene, indene, turpentine, benzyl alcohol, cyclohexanol, cresol, cumarone, camphor, saccharides, polysaccharides, alkylene oxides, halogen hydrins and also other ethers and esters. Accelerators specified are sulphuric acid, hydrochloric acid, boric acid, boric anhydride, silicic acid, phosphoric acid, aqueous sodium hydroxide, aqueous or alcoholic potash, ammonia; magnesium oxide, calcium oxide, barium oxide, aluminium oxide, zinc oxide, titanium oxide, iron oxide, lead oxide, and also the hydroxides of the said metals; alkali carbonates, alkali borates, alkali sulphides, ammonium chloride, calcium chloride and other calcium salts, barium salts, aluminium salts, zinc salts, copper salts; sulphur, halogens, zinc, iron, salts of organic carboxylic acids, such as sodium, calcium, barium and strontium, acetates, iron lactate, calcium phthalates, metal soaps and resin soaps. Softening agents may be added at any stage, for example, glycerol esters of high-molecular saturated or unsaturated fatty acids, and also semi - drying and drying oils, for example, tallow, fish oil, liver oil, sardine oil, cottonseed oil, wood oil, coconut oil, linseed oil, linseed oil varnish, maize oil, stand oil, poppyseed oil, olive oil, perilla oil, castor oil, soya bean oil and palm oil.  Instead of the said oils and fats it is also possible to add the fatty acids contained in them, such as lauric, myristic, palmitic, stearic, oleic, linoleic, ricinenic, oleostearic, clupanodonic, wood oil and linseed oil acids.  Further additions are resins, colophony, resin oils, fusion residues or resins, acaroid resins, dammar resin, kauri copal, Congo copal, Manilla copal, shellac, resinic acids, abietic acid, ethereal oils, turpentine, gums, isoprene, dipentene, terpenes, terpin hydrate, pinene, cedar wood oil, citronel oil, diterpene, camphor, camphoric acids, balsams, borneol, rubber latex and guttapercha. As well as the alcohols listed above as solvents there may be added other monohydric and polyhydric alcohols such as propyl, amyl, dodecyl, cetyl, allyl, polyvinyl, oleyl alcohols, cyclic alcohols, for example, methyl-cyclohexanol. Fillers mentioned are asbestos, mica, marble dust, chalk, talc, ochre, china clay, organic products such as wood flour, saw-dust, cork meal, cotton, tannin, asphalt, fatty acid distillation residues, cellulose esters and ethers, and nitro-cellulose.  In examples: (1, 2, 3,) perhydrogenated 4 : 4<1>-dihydroxydiphenylmethane is heated with phthalic anhydride adipic acid, or a mixture of phthalic anhydride and linseed oil fatty acids, in the presence of boric acid; (4) a dihydroxydiphenylmethane prepared from phenol and formaldehyde in the presence of hydrochloric acid is hydrogenated in the presence of a catalyst containing nickel and the product heated with phthalic and boric anhydrides.  The resin obtained may be heated with linseed oil; (5, 6, 7, 8) perhydrogenated 4 : 4<1> - dihydroxy - 6 : 6<1> - dimethyl - diphenylmethane (or the corresponding compounds containing ethyl, propyl, isopropyl, n- or iso-butyl, higher alkyl, e.g. dodecyl and hexadecyl, aryl and cycloalkyl groups) is heated with adipic acid (with or without linseed oil fatty acids) with maleic anhydride, or with sebacic acid; (9) a phenol-formaldehyde resin is hydrogenated in the presence of a catalyst containing nickel and the product heated with adipic acid; (10) phenol and formaldehyde are condensed in the presence of sulphuric acid, hydrogenated, and heated with adipic and linseed oil fatty acids.  The condensation products, which have electrical-insulating and heat-resisting properties, may be used for lacquers, films, coatings for adhesives, and substitutes for natural resins.  Also, an emulsion for use as a pigment vehicle may be prepared by mixing the product of example 4 with commercial linseed oil, stand oil, cobalt linoleate and xylol, and emulsifying in an ammoniacal casein solution.  The Provisional Specification describes also as starting materials hydroxyl-group-containing cycloaliphatic compounds which are substituted by hydroxyl-containing residues in general.