Patent GB-714856-A (GB)
Title: Production of compositions of matter from anacardic material
Filed: 1951-08-23
Abstract: A new composition of matter is obtained by heating a mixture of an anacardic material, as defined below, and an unsaturated fatty acid having at least 15 carbon atoms in the molecule, the mole ratio of the anacardic material to the unsaturated fatty acid being in the range of 2-1 to 2-4 and maintaining said mixture at an elevated temperature under reflux conditions while removing water of reaction as it is formed until the number of anacardic hydroxy groups, as defined below, present in the mass is between 85 per cent. and 50 per cent. of the number of anacardic hydroxy groups present in the original mixture.  The term anacardic material is defined as any substantially decarboxylated cashew nut shell liquid, liquid polymers thereof, and mixtures of the decarboxylated cashew nut shell liquid and these polymers.  The cashew nut shell liquid may be decarboxylated by heating either cold or hot extracted cashew nut shell liquid at 250-325 DEG  F. until substantially all of the carboxyl groups present in the anacardic acid component have been driven off.  The cashew nut shell liquid employed may have had the more volatile constituents removed by heat and if desired the nitrogenous and mineral components, e.g. the natural sulphide-sulphur combination therein, may be removed to provide the so-called treated cashew nut shell liquid, e.g. by the method disclosed in Specification 664,169, [Group IV (b)], and U.S.A. Specification 2,128,247.  The liquid polymers of the substantially completely decarboxylated cashew nut shell liquid may be produced by heat alone or in the presence of an acidic or alkaline catalyst.  When liquid polymers obtained by heating in the presence of an acidic catalyst are employed it is preferable to render them slightly alkaline by treatment with an alkali before mixing them with the unsaturated fatty acid.  By "anacardic hydroxy group" is meant a free hydroxy group which is part of an anacardic material molecule.  Specified fatty acids are palmitoleic, oleic, linoleic, linolenic, arachidonic, clupanodonic, elaeostearic, licanic and ricinoleic acids.  The fatty acids may be derived from various sources, e.g. tall oil and other oils such as chinawood, fish, hempseed, linseed, oiticica, perilla, poppyseed, safflower, soya-bean, sunflower, walnut, cottonseed, peanut, cocoanut, palm kernel, palm and castor, and commercial mixtures containing them, e.g. tall oil, linseed oil fatty acids, and dehydrated castor oil fatty acids are preferably employed.  The process is generally effected at between 450 DEG  and 650 DEG  F. and with or without a mild esterification catalyst such as lime, magnesia, zinc oxide, potassium acetate or pyridine.  After esterification the mass may be thickened to the desired viscosity by heating and whether or not such thickening has been carried out, it may then be reacted at an elevated temperature, e.g. at about 600 DEG F. with an aliphatic polyhydric alcohol such as glycerol, pentaerythritol, diethylene glycol, ethylene glycol, tetraethylene glycol, propylene glycol, butylene glycol or a polypropylene glycol. Mixtures of the polyhydric alcohols may also be used.  Also after esterification, whether or not it has been reacted with a polyhydric alcohol, the mass may be reacted with 0.05-8 per cent. of a reagent containing a reactive methylene group, such as hexamethylene tetramine, trixoymethylene, formaldehyde, paraformaldehyde, trioxane, glyoxal, and acrolein, as well as polymeric compounds which break down to give such reagents under the reaction conditions employed. The latter reaction may be carried out with or without an alkaline curing catalyst, the mixture being heated to 300-600 DEG F. to convert the mass to the dry, hard, and infusible state.  Suitable curing catalysts include sodium hydroxide, ammonia, hexamethylene tetramine, potassium acid sulphate, sulphuric and hydrochloric acids. The products when spread in the form of a thin film will dry on exposure to air or when baked in an oven at 285 DEG  F. and whether modified or unmodified may be applied as coating materials, electrical insulating materials, and as components of friction elements such as brake linings and clutch facings.  The products, whether or not reacted with a polyhydric alcohol, may also be modified by sulphurization or halogenation. Sulphurization may be effected by heating at 250-400 DEG  F. with a sulphurizing agent such as sulphur, sulphur chloride, or sodium polysulphide, preferably under alkaline conditions, e.g. after the addition of lime. Halogenation may be effected by passing chlorine into the products in the presence or absence of a solvent, at from room temperature to 150 DEG  F. until the quantity of chlorine absorbed is between 1 and 25 per cent. of the unchlorinated product.  In examples, treated decarboxylated cashew nut shell liquid is reacted with (1) commercial linseed oil unsaturated fatty acids at 570 DEG  C.; (2) tall oil; (8) tall oil in the presence of potassium acetate as catalyst; (9), (10) and (12) tall oil in the presence of pyridrine as catalyst, the product of (10) being further treated by reacting with pentaerythritol at 600 DEG  F. and the resulting polyhydric alcohol modified product treated with hexamethylene tetramine at 350 DEG  F. to give a substantially infusible solid resin.  The polyhydric alcohol modified product of (10) may be thickened to a viscous mass by heating to 600 DEG  F., and a solution thereof in mineral spirits containing a copper drier may be coated on a base; (11) distilled linseed oil fatty acids at 600 DEG  F.; in other examples-(3), (5), (6) and (7)-decarboxylated cashew nut shell liquid is reacted with linoleic acid, fish oil, unsaturated fatty acids (chiefly palmitoleic, oleic, linolenic, arachidonic, and clupanodonic), commercial oiticica oil unsaturated fatty acids (oleic and licanic), and tung oil unsaturated fatty acids (oleic and elaeostearic), respectively, whilst in (4) polymerized decarboxylated cashew nut shell liquid is reacted with oleic acid. Any of the products obtained in the examples or the polyhydric alcohol modified products obtained therefrom may be reacted with an agent containing a reactive methylene group and heat converted at 300-600 DEG  F. to the substantially solid and infusible state and the primary products or the modified products may be used as components of asbestos brake linings and clutch facings of either the woven or matted type and may be used to coat various bases (see Group VIII), e.g. they may be used alone or in combination with other materials for the production of flexible cable cloth. They may also be further modified by employing them with drying, semi-drying or non-drying oils with or without resinous materials such as the oil soluble phenol-aldehyde resins, terpene resins, alkyd resins, formaldehyde-ketone resins, furfuraldehyde-ketone resins, phenolic ether resins, asphalt, gilsonite, vegetable, mineral and animal pitches and pitchy residues. They may also be p  used with metallic driers and the various compositions are generally thinned with a solvent and then deposited on the base material which is passed through an oven to drive off the solvent and convert the material to the substantially dry state. Specified coating compositions are:-(1) The product of Example (2) which is heated to 600 DEG  F. to increase the body thereof and is then cooled to 400 DEG  F. and mixed with mineral spirits and copper naphthenate drier; (2) the product of Example 1 or 2 mixed with phenol-formaldehyde resin (oil-soluble) and asphalt, the mixture heated to 580 DEG  F., dehydrated castor oil added, the mass heated to about 580 DEG  F. linseed oil added, and the mass cooled and mixed with mineral spirits and a metallic drier containing lead and manganese.ALSO:A new composition of matter is obtained by heating a mixture of an anacardic material, as defined below, and an unsaturated fatty acid having at least 15 carbon atoms in the molecule, the mole ratio of the anacardic material to the unsaturated fatty acid being in the range of 2-1 to 2-4, and maintaining said mixture at an elevated temperature under reflux conditions while removing water of reaction as it is formed until the number of anacardic hydroxy groups, as defined below, present in the mass is between 85 and 50 per cent of the number of anacardic hydroxy groups present in the original mixture.  The term anacardic material is defined as any substantially decarboxylated cashew nut shell liquid, liquid polymers thereof, and mixtures of the decarboxylated cashew nut shell liquid and these polymers.  The cashew nut shell liquid may be decarboxylated by heating either cold or hot extracted cashew nut shell liquid at 250-325 DEG  F. until substantially all of the carboxyl groups present in the anarcadic acid component have been driven off.  The cashew nut shell liquid employed may have had the more volatile constituents removed by heat and if desired the nitrogenous and mineral components, e.g. the natural sulphide-sulphur combination therein, may be removed to provide the so-called treated cashew nut shell liquid, e.g. by the method disclosed in Specification 664,169 or U.S.A.  Specification 2,128,247.  The liquid polymers of the substantially completely decarboxylated cashew nut shell liquid may be produced by heat alone or in the presence of an acidic or alkaline catalyst.  When liquid polymers obtained by heating in the presence of an acidic catalyst are employed it is preferable to render them slightly alkaline by treatment with an alkali before mixing them with the unsaturated fatty acid.  By "anacardic hydroxy group" is meant a free hydroxy group which is part of an anacardic material molecule.  Specified fatty acids are palmitoleic, oleic, linoleic, linolenic, arachidonic, clupanodonic, elaeostearic, licanic and ricinoleic acids.  The fatty acids may be derived from various sources, e.g. tall