Patent GB-465148-A (GB)
Title: Improvements in or relating to the manufacture of resin-like products
IPC: C08G8/28
Filed: 1935-03-06
Abstract: Resinous compounds containing at least three carbocyclic rings are prepared by the catalytic hydrogenation of products formed by the condensation of (a) aromatic or aromatic-alicyclic hydrocarbons, or their mono-or polyoxy derivatives which may be etherified, or condensation products of the latter with aldehydes or ketones, with (b) mono- or polyvalent alcohols of the alicyclic, alicyclicaromatic or fatty-aromatic series or their halides or the corresponding unsaturated hydrocarbons.  The high-molecular hydrogenated products are colourless resins which are spring hard when cold and liquefy when warmed, the low-molecular products are viscous liquids at normal temperature, and both are soluble in most organic solvents; they are more resistant to light, air and chemical agents than the non-hydrogenated compounds.  The low-molecular products may be used for paper sizing and for glueing leather and wood; as constituents of cements, anti-slipping agents, adhesive fats and waxes, medicinal plasters and insect-trapping limes; as softeners for cellulose ester and ether compositions; in varnish, oilcloth and linoleum manufacture; in the preparation of printing colours and pastes; in the production of lubricants; as additions to soap, perfumes, explosives and flotation agents; as froth stabilizers and as dispersion stabilizers for oils, fats and waxes; for the impregnation of textiles, leather and wood; in the manufacture of caoutchouc and the preparation of active carbons.  The high-molecular products are also useful as a substitute for colophony and in the manufacture of insulating materials and other plastic or moulded masses, if desired in combination with casein or other artificial resins.  As components (a) of the initial condensation products are specified: benzene hydrocarbons, di- and poly-cyclic hydrocarbons containing at least one aromatic ring, phenol, cresol, chlor- and nitro-phenols, o- and p-cyclohexylphenol, resorcinol, 1- and 2-naphthol, 5- and 6-tetrahydronaphthol, 4 : 4<1>-dioxydiphenylmethane, 4 : 4<1>-dioxydinaphthyl-1 : 1<1> methane, o- and p-oxydiphenyl, anisole, phenetole, diphenyl ether, cresol and naphthol ethers, guaiacol and diphenylene oxide.  Mention is made of the following components (b): menthol, terpineol, terpin, terpin hydrate, borneol, isoborneol, fenchyl alcohol, cyclohexanol, methyl-and dimethyl-cyclohexanols, o- and p-ethyl- or butyl-cyclohexanols, octylcyclohexanols, o- and p-cyclohexyl-cyclohexanols, 2 : 6-dicyclohexyl-cyclohexanol, o- and p-phenyl- or benzyl - cyclohexanols, quinite, 1- and 2-decahydronaphthol, 1- and 2-tetrahydronaphthol, benzyl alcohol, 1- naphthylcarbinol, b -phenylethyl alcohol, 1-(b -oxyethyl)-naphthalene, pinene, limonene, dipentene and other terpenes and sesquiterpenes, as well as the oils, e.g. turpentine oil, containing them.  The condensation is effected in the presence of such catalysts as sulphuric acid, phosphoric acid, halogen hydracids, perchloric acid, chlorides of magnesium, calcium, zinc, boron, aluminium, iron, antimony and tin, bleaching earths, active carbons and zinc dust.  Examples are given of the hydrogenation of compounds prepared by condensing (1) tetrahydronaphthalene with 2-decalol (decahydro-2-naphthol); the product comprises 6-(decalyl-2<1>)-tetrahydronaphthalene and a didecalyl-tetrahydronaphthalene; (2) o-cresol with 2-decalol, forming mono- and di-decalyl-o-cresols; (3) tri-cresol with o-methylcyclohexyl - methylcyclohexanol, which is obtained together with the methyl-cyclohexanols by the hydrogenation of tri-cresol; (4) 6-tetrahydronaphthol-ar with 2-tetrahydronaphthol-ac, the main product being (tetrahydronaphthyl - 2<1>) - tetrahydronaphthol 6; (5) 1-naphthol with a technical mixture of the 3-methylcyclohexanols, the main product being 2 : 4-di(methylcyclohexyl) - 1 - naphthol; (6) 2-naphthol with p-cyclohexyl-cyclohexanol, giving 1-(4<1>-cyclohexyl-cyclohexyl)-naphthol-2; (7) resorcinol with 1-naphthyl-carbinol, to form di-(1-naphthylcarbinyl)-resorcinol; (8) tri-cresol with p : p<1> - dioxydiphenylmethane; (9) benzene with bornyl chloride; (10) xylene with 1-chlormethylnaphthalene, giving a naphthyl-xylyl-methane; (11) phenol with methyl cyclohexene, which is obtained by splitting off water from a technical mixture of the three methylcyclohexanols; the product contains at least two cyclohexyl rings; (12) tri-cresol with balsam turpentine, which contains pinene as main constituent.  In each case the hydrogenation is effected at elevated temperature and pressure; a typical instance requires a temperature of 230 DEG  C. and a pressure of 35 atmospheres using a nickel catalyst and decahydronaphthalene as solvent.  The products are fully hydrogenated compounds, e.g. that of (1) is perhydro-b  : b <1>-dinaphthyl.  Specification 409,696 is referred to.  Reference has been directed by the Comptroller to Specification 446,498.ALSO:Resinous compounds containing at least three carbocyclic rings are prepared by the catalytic hydrogenation of products formed by the condensation of (a) aromatic or aromaticalicyclic hydrocarbons, or their mono- or polyoxy derivatives which may be etherified, or condensation products of the latter with aldehydes or ketones, with (b) mono- or polyvalent alcohols of the alicyclic, alicyclic-aromatic or fatty-aromatic series or their halides or the corresponding unsaturated hydrocarbons.  The high-molecular hydrogenated products are colourless resins which are spring hard when cold and liquefy when warmed, the low-molecular products are viscous liquid at normal temperature, and both are soluble in most organic solvents; they are more resistant to light, air and chemical agents than the non-hydrogenated compounds.  The low-molecular products may be used for paper sizing and for glueing leather and wood; as constituents of cements, anti-slipping agents, adhesive fats and waxes, medicinal plasters and insect-trapping limes; as softeners for cellulose ester and ether compositions; in varnish, oilcloth and linoleum manufacture; in the preparation of printing colours and pastes; in the production of lubricants; as additions to soap, perfumes, explosives and flotation agents; as froth stabilizers and as dispersion stabilizers for oils, fats and waxes for the impregnation of textiles, leather and wood; in the manufacture of caoutchouc and the preparation of active carbons.  The high-molecular products are also useful as a substitute for colophony and in the manufacture of insulating materials and other plastic or moulded masses, if desired in combinattion with casein or other artificial resins.  As components (a) of the initial condensation products are specified: benzene hydrocarbons, di- and poly-cyclic hydrocarbons containing at least one aromatic ring, phenol, cresol, chlor- and nitro-phenols, o- and p-cyclohexyl phenol, resorcinol, 1- and 2-naphthol, 5- and 6-tetrahydronaphthol, 4 : 4<1>-dioxydiphenyl - methane, 4 : 4<1>-dioxydinaphthyl-1 : 1<1>-methane, o- and p-oxydiphenyl, anisole, phenetole, diphenyl ether, cresol and naphthol ethers, guaiacol and diphenylene oxide.  Mention is made of the following components: (b) menthol, terpineol, terpin, terpin hydrate, borneol, isoborneol, fenchyl alcohol, cyclohexanol, methyl- and dimethyl-cyclohexanols, o- and p-ethyl- or butyl-cyclohexanols, octylcyclohexanols, o- and p-cyclohexylcyclohexanols, 2 : 6-dicyclohexyl-cyclohexanol, o- and p-phenyl- or benzyl-cyclohexanols, quinite, 1- and 2-decahydronaphthol, 1- and 2-tetrahydronaphthol, benzyl alcohol, 1-naphthylcarbinol, b -phenylethyl alcohol, 1- (b -oxyethyl)-naphthalene, pinene, limonene, dipentene and other terpenes and sesquiterpenes, as well as the oils, e.g. turpentine oil, containing them.  Examples are given of the hydrogenation of compounds prepared by condensing (1) tetrahydronaphthalene with 2-decalol (decahydro-2-naphthol); the product comprises 6-(decalyl-2<1>)-tetrahydro naphthalene and a didecalyl-tetrahydronaphthalene; (2) o-cresol with 2-decalol, forming mono- and di-decalyl-o-cresols; (3) tri-cresol with o-methylcyclohexyl-methylcycohexanol, which is obtained together with the methyl-cyclohexanols by the hydrogenation of tri-cresol; (4) 6-tetrahydronaphthol-ar with 2-tetrahydronaphthol-ac, the main product being (tetrahydronaphthyl-2<1>)-tetrahydronaphthol-6; (5) 1-naphthol with a technical mixture of the 3-methylcyclohexanols, the main product being 2 : 4-di (methylcyclohexyl)-1-naphthol; (6) 2-naphthol with p-cyclohexyl-cyclohexanol, giving 1-(4<1>-cyclohexyl-cyclohexyl)-naphthol-2; (7) resorcinol with 1-naphthyl-carbinol, to form di-(1-naphthylcarbinyl)-resorcinol; (8) tri-cresol with p : p<1>-dioxy diphenylmethane; (9) benzene with bornyl chloride; (10) xylene with 1-chlormethylnaphthalene, giving a naphthyl-xylyl-methane; (11) phenol with methyl-cyclohexene, which is obtained by splitting off water from a technical mixture of the three methylcyclohexanols; the product contains at least two cyclohexyl rings; (12) tri-cresol with balsam turpentine, which contains pinene as main constituent.  In each case the hydrogenation is effected at elevated temperature and pressure; a typical instance requires a temperature of 230 DEG  C. and a pressure of 35 atmospheres using a nickel catalyst and decahydronaphthalene as solvent.  The products are fully hydrogenated compounds, e.g. that of (1) is perhydro-b -b <1>-dinaphthyl.  Specification 409,696 is referred to.  Reference has been directed by the Comptroller to Specification 446,498.