Patent GB-652415-A (GB)
Title: Improvements in or relating to hydrogenated furane derivatives and method of producing same
IPC: C07D307/46
Filed: 1948-01-20
Abstract: Thermosetting synthetic resins are manufactured from hydrogenated furane derivatives, obtained by subjecting the alkaline condensation products of furfural with one or more ketones having two hydrogen atoms on an a -carbon atom to partial hydrogenation until the amount of hydrogen absorbed is 50-100 per cent of that required to saturate the unsaturated carbon atoms outside the ring (and, if desired, fractionating the product), by the following methods: (1) the hydrogenated furane derivatives, or bodied products obtained therefrom by treating them with a free oxygen containing gas (e.g. air, oxygen or ozone, preferably at an elevated temperature, e.g. 150-250 DEG  C.) may be polymerized under acidic conditions (e.g. by heating to 220-350 DEG  F. with sulphuric, phosphoric or hydrochloric acid, diethyl sulphate or zinc chloride); (2) the hydrogenated furane derivatives, the bodied products or the polymerization products of (1) may be reacted in the presence of a condensing agent (e.g. sodium or potassium hydroxide or the acidic agents specified in (1) above) with agents containing a reactive methylene group (e.g. formaldehyde, paraformaldehyde, glyoxal, acrolein, aldol and hexamethylenetetramine).  The products, with or without other components, may be used in coating compositions and as binders and friction augmenting materials in brake linings and clutch facings (which may have a basis of asbestos and/or natural or synthetic rubber).  The hydrogenated furane derivatives, the bodied products and the polymerization products of (1) may also be used as plasticizers for normally solid polymers and copolymers of vinyl esters (e.g. polyvinyl chloride, acetate or chloride/acetate), solid polyvinyl acetals (e.g. the butyral, formal or acetal), natural or reclaimed rubber, rubbery polymers of chloroprene and rubbery copolymers of butadiene and styrene or acrylonitrile.  The hydrogenated furane derivatives and the bodied products may also be used for plasticizing cellulose derivatives (e.g. cellulose nitrate or acetate, or benzyl, methyl or ethyl cellulose), whilst the condensation products of (2) may be used as plasticizers for resins such as phenolaldehyde or alkyd resins (for use in the lamination of paper, wood, cork, metal or glass), or for coumarone-indene polymers.ALSO:Hydrogenated furane derivatives are manufactured by subjecting the reaction products obtained by condensing furfural under alkaline conditions with one or more ketones having two hydrogen atoms on an a -carbon atom to partial hydrogenation until the amount of hydrogen absorbed is 50-100 per cent of that required to saturate the unsaturated carbon atoms outside the ring, and, if desired, fractionating the product.  Preferably, the completion of the initial condensation (which may be effected in the presence of aqueous sodium or potassium hydroxide) is followed by addition of acid (e.g. hydrochloric, sulphuric or lactic) to pH 6.7-7.4 and dehydration of the mass (preferably by heating under a high vacuum), after which (and if necessary after dissolving the mass in a solvent, e.g. a high molecular weight ketone) the hydrogenation is advantageously effected at 120-250 DEG  C. and 25-200 (preferably 30-60) lbs. per sq. inch pressure in the presence of finely divided nickel, which may be suspended in a carrier such as a hydrogenated vegetable oil or hydrogenated cardanol.  Examples describe the hydrogenation of the reaction products of furfural with: (1) acetone, (2) methyl ethyl ketone, and (3) diacetone alcohol.  Additional ketones specified are acetonyl acetone and cyclohexanone.  U.S.A. Specification 2,363,829 is referred to.ALSO:Coating compositions (e.g. paints, varnishes, lacquers, electrical insulating coatings, and rust-proofing agents) contain hydrogenated furane derivatives obtained by subjecting the alkaline condensation products of furfural with one or more ketones having two hydrogen atoms on an a -carbon atom to partial hydrogenation until the amount of hydrogen absorbed is 50-100 per cent of that required to saturate the unsaturated carbon atoms outside the ring and, if desired, fractionating the products. These products may be used alone or in combination with other materials (e.g. drying oils such as linseed or chinawood oil, or other oils of animal, vegetable or marine origin such as perilla, rape seed, cottonseed, soya bean or fish oils), and with or without driers (e.g. manganese resinate, copper oleate or the driers known under the Registered Trade Mark "Soligen").ALSO:Friction materials (e.g. brake linings and clutch facings) containing as binding medium a mixture of natural or synthetic rubber and a thermosetting synthetic resin obtained by subjecting the alkaline condensation products of furfural with one or more ketones having two hydrogen atoms on an a -carbon atom to partial hydrogenation until the amount of hydrogen absorbed is 50-100 per cent of that required to saturate the unsaturated carbon atoms outside the ring, and condensing the product, as such or after fractionation and/or bodying or polymerization, with agents containing a reactive methylene group. In an example, 100 parts of rubber are milled with 10-200 parts of one or more of said resins, the mixture is cut into small pieces and swelled with toluene to a fluid gelatinous mass to which is added asbestos in the proportion of 3 parts to one of the other solids present, together with sulphur and a vulcanization accelerator, after which the toluene is removed and the residue cured in a mould.  The toluene may be replaced by xylene and the rubber by the material sold under the Registered Trade Mark "Bune-S" or "Bura-N," whilst fillers and modifying agents such as barytes, cork or carbon black may also be added.