Patent GB-805258-A (GB)
Title: Polyhydroxy-substituted polyethers, their preparation and resinous products preparedtherefrom
Filed: 1957-02-25
Abstract: Polyepoxyethers of polyhydric phenols having an epoxy equivalency greater than 1 are hydrogenated by passing them at 30-300 DEG  C. preferably in admixture with inert diluents, e.g. ethanol, isopropanol, ethylene glycol dioxane, over nickel or one of the metals of the platinum subgroups of Group VIII, e.g. platinum, palladium, rhodium, ruthenium, osmium or their oxides or alloys preferably supported on an inert carrier, e.g. pumice, kieselguhr, diatomaceous earth, clay, alumina, charcoal.  The hydrogenation is conducted so that the epoxy groups are converted to -C-C(OH)- or -C(OH)-C- groups and at least 50 per cent of the aromatic radicles are converted to cycloaliphatic.  The polyols obtained by the hydrogenation have from 3-10 free OH groups and are soluble in alcohols, ketones, hydrocarbons and halogenated hydrocarbons; in solution they are suitable for use as coating compositions, adhesives, sealing or impregnating compositions.  They are also useful as softening agents for synthetic rubbers, casein and other protein plastics, as textile lubricants, as lubricating oil additives, as blending agents for dyes, inks and paints as intermediates in the preparation of emulsifiers, surface-active agents, fungicides, herbicides, insecticides.  Alkyd resins suitable for use in coating compositions may be prepared from the hydrogenated products by reacting the latter with polybasic acids and with monohydric alcohols or monocarboxylic acids as modifying agents.  The polyols may be cured to infusible insoluble compositions by addition of cross linking agents, e.g. acids or methylol substituted compounds.  Esters of the polyols are useful as plasticizers for vinyl polymers, e.g. esters formed with allyl hydrogen maleate. The polyols may be converted to epoxy compounds by reaction with epihalohalohydrins in the presence of alkali or reacted with alkylene oxides to give hydroxy polyethers of formula X-[OR(OR)nOH]y where X is the residue of the hydrogenated polyether and R is the residue of the alkylene oxide, n is 0-50 and y is the number of OH group in the polyol. The polyols may also be reacted with polyisocyanates to give polyurethanes or with nitriles to give cyanoalkyl ether derivatives which may be reduced to polyamines.  In examples: (1) a polyether having an epoxy equivalent of 1.5 and m.w. 2900 was dissolved in tetrahydrofuran and hydrogenated in presence of a catalyst comprising 5 per cent rhodium on A1203 at 50-70 DEG  C. under a pressure of 250 p.s.i. the hydrogenated polyether was (a) combined with urea-formaldehyde resin in xylene and used to coat steel panels (b) with the addition of TiO2 a white baking enamel was obtained.  (4) A hydrogenated polyether was mixed with soya bean fatty acid and heated to 230 DEG  C. and was then mixed with petroleum solvent and subjected to azeotropic distillation at 230 DEG  C. for 6 hours to obtain a product of acid No. 17.9, the product dissolved in petroleum solvent was used to coat steel panels.  (5) An alkyd resin was prepared by heating a polyether hydrogenated as in (1) with hexahydrophthalic acid and dehydrated castor oil; the alkyd resin obtained was mixed with TiO2,a urea-formaldehyde resin and xylene and the mixture sprayed on steel panels.  (6) 280 Parts of the hydrogenated polyether obtained in (1) are mixed with 100 parts epichlorhydrin and reacted with cooling in the presence of anhydrous stannic chloride added slowly over 15 minutes, the product obtained was dechlorinated by addition of NaOH.  A semi-solid product having 0.28 epoxy equivalents per 100 gm. and a chlorine content of 6 per cent was obtained 20 parts of the product were dissolved in 15 parts tetrahydrophthalic anhydride and 0.5 part dimethylbenzylamine added; the mixture cured to a hard product when heated at 100 DEG  C. for hours.  (7) A polyether hydrogenated as described above when mixed with m-phenylene diisocyanate, 4,41-diphenyl diisocyanate, 4,41-diphenylene methane diisocyanate or 1,5-naphthalene diisocyanate cured to a hard resin.ALSO:Polyepoxyethers of polyhydric phenols having an epoxy equivalency greater than 1 are hydrogenated by passing them at 30-300 DEG  C. preferably in admixture with inert diluents, e.g. ethanol, isopropanol, ethylene glycol or dioxane, over nickel or one of the metals of the platinum sub-groups of Group VIII, e.g. platinum, palladium rhodium, ruthenium, osmium or their oxides or alloys, preferably supported on an inert carrier, e.g. pumice, kieselguhr diatomaceous earth, clay, alumina, charcoal.  The hydrogenation is conducted so that the epoxy groups are converted to -C-(OH)- or -C(OH)-C- groups and at least 50 per cent of the aromatic radicals are converted to cycloaliphatic radicals. The polyols obtained by the hydrogenation have from 3-10 free OH groups and are soluble in alcohols, ketones, hydrocarbons and halogenated hydrocarbons.  In solution they are suitable for use as coating compositions, adhesives, sealing or impregnating compositions.  They are also useful as softening agents for casein and other protein plastics and synthetic rubbers; as textile lubricants; as lubricating oil additives; as blending agents for dyes, inks and paints; as intermediates in the preparation of emulsifiers, surface-active agents, fungicides, herbicides and insecticides.  Alkyd resins suitable for use in coating compositions may be prepared from the hydrogenated products by reacting the latter with polybasic acids and with monohydric alcohol or monocarboxylic acids as modifying agents. The polyols may be cured to infusible insoluble compositions by addition of cross linking agents, e.g. acids, methylol substituted compounds. Esters of the polyols are useful as plasticizers for vinylpolymers.  The polyols may be converted to epoxy compounds by reaction with epihalohalohydrins in the presence of alkali or reacted with alkylene oxides to give hydroxy polyethers of formula X-[OR(OR)nOH]y, where X is the residue of the hydrogenated polyether and R is the residue of the alkylene oxide, n is 0-50 and y is an integer depending on the number of OH groups in the polyol.  In examples polyepoxyethers of m.w. from 483-2900 are subjected to hydrogenation.  In one example, a polyether having an epoxy equivalency of 1.5 and m.w. 2900 was dissolved in tetrahydrofuran and hydrogenated in presence of a catalyst comprising 5 per cent rhodium an Al2O3 at 50-70 DEG  C. under a pressure of 250 psi.