Patent GB-627478-A (GB)
Title: Improvements in or relating to allyl ethers of anacardic materials and compositions and products prepared therefrom
IPC: C09F5/06
Filed: 1945-07-10
Abstract: Fatty compositions comprise heat-polymerizable oils, drying oils, semi-drying oils or non-drying oils together with the allyl ethers of cashew nut shell liquid, the distillates or residues of cashew nut shell liquid, the liquid polymers of the cashew nut shell liquid, its distillates and residues, or with the heat-thickened products of these ethers or with the modified products obtained from these ethers or thickened ethers by chlorination, sulphurisation or condensation with such aldehydes as for example, formaldehyde, trioxymethylene, hexamethylene tetramine, acetaldehyde, acrolein, polymerized acrolein and furfuraldehyde (see Group IV (b)).  Typical oils mentioned are chinawood oil, oiticica oil, perilla oil, cottonseed oil, soya bean oil, linseed oil and fish oils.  The compositions may be dissolved in certain hydrocarbon solvents, turpentine and xylol. They are employed in paints and varnishes (see Group IV (a)), rubber and fibrous compositions (see Group V) and in coating and impregnating compositions (see Group VIII).ALSO:Thickened or polymerized products are obtained from allyl ethers of one or more anacardic materials selected from cashew nut shell liquid, distillates and residues from said liquid, and liquid polymers of these materials (see Group IV (b)).  Fusible thickened products may be obtained by agitating the ethers in the open air at room temperature, but are preferably prepared by application of heat, desirably in the presence of a peroxide as promoter and in the presence or absence of a free oxygen-containing gas; by continuing the heating solid infusible resins are obtained.  The allyl ethers or thickened products therefrom may be condensed with aldehydes such as formaldehyde, hexamethylene tetramine, trioxymethylene, glyoxal, acetaldehyde, acrolein, polymerized acrolein, and furfuraldehyde; this condensation, preferably effected with heat in the presence of acid or alkaline condensation catalysts, yields fusible thermo-setting resins which on further heating are rendered infusible.  The allyl ethers and thickened allyl ethers may be modified; thus they may be halogenated, for example, with chlorine directly or in solution or may be sulphurized with, for example, sulphur, sulphur dichloride or sodium polysulphide, and the modified products may also be condensed with aldehydes as described above.  Allyl ethers of said anacardic materials, heat-thickened products therefrom, said chlorinated or sulphurized ethers or thickened ethers and the resinous aldehyde condensates of the allyl ethers, the thickened ethers and the chlorinated or sulphurized compounds may be used alone or in combination with other substances in varnishes, paints, electrical insulations, coatings, laminations, braking linings, moulding, natural and synthetic rubber, adhesives, inks and the like.  For example, in paints and varnishes they may be used with a heat-polymerizing oil such as chinawood oil, oiticica oil or perilla oil, or with a semi-drying or non-drying oil such as cottonseed oil, soya bean oil, linseed oil, fish oils and the like and be heat-bodied to desired consistency.  They may be used in coating or impregnating bases such as paper, metal, wood, glass, cork, regenerated cellulose film, asbestos or cotton, with, for example, natural, reclaimed or synthetic rubbers, especially 2-chlor-butadiene polymers and copolymers of butadiene and styrene or acrylonitrile and styrene, methyl methacrylate and the like.  Other coating or impregnating compositions comprise the products obtained by heating said allyl ethers, heat-thickened fusible products therefrom and fusible aldehyde condensates of these fusible products modified or not by the addition of one of the above-mentioned oils, a metallic drier, an oil-soluble phenol-aldehyde resin, a normally solid polyvinyl acetal such as polyvinyl formal or butyral, and/or ethyl cellulose, thinners being added if required (see also Group VIII). Friction materials comprise heat-resistant fibres, such as asbestos, and the above-mentioned allyl ethers, the thickened products therefrom and the aldehyde condensates of both these materials, if desired, in association with phenolic resins, heat-polymerizable and drying oils, natural or reclaimed rubber or the synthetic rubbers mentioned above, normally solid polyvinyl acetals, ethyl cellulose, barytes and carbon black.  The asbestos fibre or woven material is impregnated, shaped and cured. Alternatively, the allyl ether products may be prepared in the form of comminuted materials and then incorporated in a binder for the asbestos such as rubber, phenol-aldehyde resins, heat-polymerized drying oils and the like (see also Group V). According to typical examples: (1) allyl ether of cashew nut shell liquid is heated at between 500 DEG  and 600 DEG  F. to give a fusible product having a viscosity of upwards of 5000 cps. at 25 DEG C.; (10) allyl ether of cashew nut shell liquid is heated with sulphur at about 425 DEG  F., yielding a solid mass which on further heating becomes rubbery and millable alone or with natural or synthetic rubber; (11) one of the allyl ethers or thickened ethers is heated at 100 DEG  C. with 10 per cent sulphuric acid or 15-20 per cent diethyl sulphate to form an infusible resin; (15) one of said allyl ethers is heated with ethyl cellulose and the resulting gel milled into a natural or synthetic rubber mentioned above and cured, or dissolved in a solvent such as alcohol/xylol to form a coating or impregnating composition; (19) a product obtained as in (1) is mixed with petroleum spirits and an aldehyde, preferably hexamethylene tetramine, then asbestos fibres are added and the resulting mix is heated to remove solvent, extruded and cured to provide a brake lining; (20) allyl ether of cashew nut shell liquid is heat-thickened, mixed with paraformaldehyde and some diethyl sulphate, heated to the infusible state and ground to a fine dust for incorporation in a friction material as described above or (21) the thickened product is similarly heated to the infusible state in admixture with a fusible tertiary butyl phenol-formaldehyde resin, linseed oil and sulphur, and ground as above.  According to further illustrations, a paint or vanish vehicle comprises allyl ether of cashew nut shell liquid, chinawood oil, gilsonite, lead and manganese soligen driers and kerosene, while a soft rubber stock comprises a butadiene-acrylonitrile copolymer, zinc oxide, carbon black, an accelerator, an antioxidant, sulphur, and the allyl ether of cashew nut shell liquid, which are mixed together and cured.ALSO:Allyl ethers of anacardic materials are prepared by reacting an allyl ester of an inorganic acid with one or more anacardic materials selected from cashew nut shell liquid, distillates and residues therefrom and the liquid polymers of these materials. Generally, a mixture of the reactants is heated with an alkali under reflux and, if desired, in the presence of water or an inert solvent.  Suitable allyl esters are the chloride, bromide, iodide and sulphate.  The products, stated to be novel, may be thickened or polymerized to give fusible and infusible resins, and similar resins may be obtained by condensing the allyl ethers or their thickened products with aldehydes (see Group IV (a)).  The allyl ethers and their thickened products may also be halogenated, for example, directly or in solution with chlorine, or may be sulphurized, for example, with sulphur, sulphur dichloride or sodium polysulphide and the modified products obtained may also be reacted with aldehydes.  The various products may be employed in paints and varnishes, and synthetic rubbers (see Group IVa), in coating and impregnating compositions (see Group VIII), in natural rubber and in friction materials suitable for brake linings in conjunction with, for example, asbestos (see Group V), and in fatty oil compositions (see Group III).  In typical examples: (1) cashew nut shell liquid or a distillate therefrom, allyl chloride and aqueous sodium hydroxide are heated under reflux, the resultant mixture neutralized, and an oily layer comprising the desired allyl ether is separated off and dried; (2) polymerized cashew nut shell liquid (viscosity 60,000 cp. at 25 DEG  C.) or a residue from the distillation of cashew nut shell liquid, is heated under reflux with allyl chloride, xylol and aqueous sodium hydroxide and the mixture then neutralized: (3) the allyl ether of cashew nut shell liquid is heated at about 425 DEG  F. with sulphur to give a solid sticky mass which may be converted into a dry rubbery mass by prolonged heating. The Specification as open to inspection under Sect. 91 includes the use of any allyl compound in the preparation of the allyl ethers. This subject-matter does not appear in the Specification as accepted.ALSO:Rubber compositions comprise allyl ethers of various cashew nut shell liquids, heat-thickened products thereof, the chlorinated or sulphurised products of said ethers and thickened ethers and the fusible aldehyde condensates produced from said thickened ethers and chlorinated or sulphurised products (see Groups IV(a) and IV(b)), and natural, re-claimed, or synthetic rubber, especially the polymers of 2-chlorbutadiene and co-polymers of butadiene and acrylonitrile or styrene, or methyl-methacrylate or styrene.  For example, a soft-rubber stock comprises the allyl ether of cashew nut shell liquid, the co-polymer of butadiene and acrylonitrile, sulphur, carbon black, zinc oxide, an antioxidant and an accelerator.  Fibrous compositions for brake linings, clutch facings and the like, comprise heat-resistant fibres such as asbestos fibres, and said allyl ethers, the heat-thickened ethers or the aldehyde condensates obtained from said heat-thickened ethers and, if desired, phenolic resins, heat-polymerising and drying oils, natural and synthetic rubbers, normally solid polyvinyl