Patent GB-651334-A (GB)
Title: Preparation of ethers of anacardic materials
Filed: 1947-07-28
Abstract: Ethers of anacardic material are prepared by reacting a mono- or poly-hydroxylated primary alkyl halide, preferably having 2-12 carbon atoms, with one or more anacardic materials selected from cashew nut shell liquid and polymers thereof, distillates of cashew nut shell liquid and polymers thereof and residues of cashew nut shell liquid and polymers thereof and hydrogenated distillates of cashew nut shell liquid, in the presence of an alkali and preferably with aid of external heat.  Alternatively, in place of the hydroxylated reactants, corresponding epoxides may be used and the products resulting may be hydrolysed to hydroxylated alkyl ethers.  The cashew nut shell liquid employed may be the raw liquid obtained from the nuts by extraction with solvent or hot cashew nut shell liquid as described in U.S.A. Specification 2,058,456, the raw liquid treated to reduce the vesicant action and remove naturally occurring metals as described in U.S.A.  Specifications 2,067,919 and 2,128,247 or the raw or treated liquid which has been steam distilled to remove volatiles. The distillates and residues may be obtained by gas, steam or reduced pressure distillation, the distillates amounting to 25 to 75 per cent of the initial liquid.  The polymerized forms of starting material may be prepared as described in U.S.A. Specifications 2,128,247, 2,240,038, 2,292,611 and 2,317,585.  The ethers may be sulphonated to yield wetting agents, nitrated, or further etherified by reaction under alkaline conditions with alkyl halides.  The ethers may be admixed with such resins as phenol- and urea-formaldehyde resins when the latter are in the fused condition, thereby imparting improved impact strength to the final infusible products.  They may be used as plasticizers for cellulose nitrate and normally solid polyvinyl alcohol. Complex condensation products may be obtained by reacting the ethers with phenols such as phenol, anthranol, cresols, xylenols and their homologues in the presence of a cationic condensing agent.  Condensation products suitable for use in varnishes are obtained by reacting the ethers derived from hydrogenated distillates of cashew nut shell liquid with polybasic acids or anhydrides such as phthalic anhydride and maleic acid. Examples describe the preparation of ethers from glycol chlorhydrin, glycerol monochlorhydrin, chlorinated lauryl alcohol and epichlorhydrin, and cashew nut shell liquid, a distillate and a residue therefrom and a hydrogenated distillate of cashew nut shell liquid (see Group IV (b)).  Specification 645,062, [Group IV (b)], is referred to.  The Specification as open to inspection under Sect. 91, relates to the preparation of hydroxylated hydrocarbon ethers of the above-mentioned anacardic materials by any method of etherification and mentions the reaction of the materials with hydroxylated hydrocarbon esters of mineral acids, e.g. hydrochloric and sulphuric acids; hydroxylated C2-C12 secondary and tertiary alkyl ethers are referred to.  This subject-matter does not appear in the Specification as accepted.ALSO:Ethers of anacardic material are prepared by reacting a mono- or poly-hydroxylated primary alkyl halide, preferably having 2 to 12 carbon atoms, in the presence of an alkali, with one or more anacardic materials selected from cashew nut shell liquid and polymers thereof, distillates of cashew nut shell liquid and polymers thereof and residues of cashew nut shell liquid and polymers thereof, and hydrogenated distillates of cashew nut shell liquid.  Alternatively, instead of using the hydroxylated reactants, corresponding epoxides may be utilized, in which case the resulting products may be subjected to hydrolysis so yielding hydroxyalkyl ethers.  The cashew nut shell liquid employed may be the raw liquid obtained from the nuts by solvent extraction or by extraction by hot cashew nut shell liquid as described in U.S.A. Specification 2,058,456, the raw liquid treated to reduce its vesicant action and remove naturally occurring metals as described in U.S.A.  Specifications 2,067,919 and 2,128,247, or the raw or treated liquid which has been steam distilled to remove volatile constituents.  The distillates and residues may be obtained by gas, steam or reduced pressure distillation, the distillates being about 25 to 75 per cent by weight of the initial liquid.  The hydrogenated distallates may be prepared by catalytic hydrogenation at from about room temperature to 180 DEG  C., using, for example, a comminuted platinum black as catalyst; the unsaturated side chains of the phenolic constituents are reduced. The polymerized forms of starting material may be prepared as described in U.S.A.  Specifications 2,128,247, 2,240,038, 2,292,611 and 2,317,585.  The ethers, which are stated to be novel, may be nitrated, or reacted with alkyl halides under alkaline conditions for further etherification, or sulphonated to yield wetting agents.  The ethers may be used as plasticizers; they may be admixed with resins in the fusible state to impart to the infusible products, improved impact strength; they may be condensed with phenols or polybasic acids or anhydrides to form novel condensation products (see Group IV (a)).  In examples: (1) glycerine monochlorhydrin is slowly added to a refluxing mixture of cashew nut shell liquid and aqueous sodium hydroxide yielding an oily water-insoluble product; (2) In the same way there is reacted a cashew nut shell liquid distillate amounting to 50 per cent of the raw liquid and having a B.P. of 225 DEG  C. at 10 mm. pressure yielding a dihydroxy alkyl ether; (3) a cashew nut shell liquid residue, amounting to 60 per cent of the raw liquid distilled, is dissolved in benzol and reacted as in (1); (4) epichlorhydrin is reacted with the cashew nut shell liquid distillate of (2) in the same manner and an oily product insoluble in alcohol is isolated and hydrolysed to an alcohol soluble product by refluxing with 10 per cent aqueous sulphuric acid; (5) lauryl alcohol is chlorinated at 50-100 DEG  C. until two mols. of chlorine are absorbed and the resulting chlorinated lauryl alcohol is reacted as in (2) to yield a product of the structural formula 1 : 3-X-C6H4-O-C12H24OH, where X is the unsaturated side chain of the anacardic phenolic starting material; (6) glycol chlorhydric replaces the glycerine chlorhydrin of (2); (7) hydrogenated distillates of cashew nut shell liquid are reacted as in (2) and (6) using alcoholic sodium hydroxide.  Any of the above ethers may be reacted with sulphuric acid and the product neutralized with a weak solution of sodium hydroxide.  The products may be used as such as wetting agents, or treated for removal of salts by alcoholic extraction or concentration followed by crystallization.  Specification 645,062 is referred to.  The Specification as open to inspection under Sect. 91 relates to the preparation of hydroxylated hydrocarbon ethers of the above-mentioned anacardic materials by any method of etherification such as the reaction with mineral acid esters of a hydrocarbon containing at least one hydroxyl group, e.g. sulphuric or hydrochloric acid esters and reference is made to the production of hydroxylated C2-12 secondary and tertiary alkyl ethers.  This subject-matter does not appear in the Specification as accepted.