Patent GB-1049100-A (GB)
Title: Plasticized acrylic ester resins
IPC: D06M15/263
Filed: 1963-08-19
Abstract: Epoxy fatty acid esters are prepared by treating with a 40% solution of peracetic acid in acetic acid the esters obtained by:-  (a) Heating benzyl alcohol with the methyl ester of safflower oil or soybean oil fatty acids in xylene containing sodium methoxide and removing the methanol evolved by distillation;  (b) Adding the chloride of tall oil, soybean oil or linseed oil fatty acids to phenol in chloroform and pyridine;  (c) Heating oleic acid, linseed oil fatty acids or tall oil fatty acids with benzyl chloride and potassium carbonate in xylene;  (d) Heating tetrahydrofurfuryl alcohol with tall oil, soybean oil or linseed oil fatty acids in xylene in the presence of zinc dust and removing the water of reaction by distillation;  (e) Heating under similar conditions as in (d) above cyclohexanol with tall oil, safflower oil or linseed oil fatty acids;  (f) Heating tall oil fatty acids with the monobutyl ether of ethylene glycol or diethylene glycol in xylene in the presence of zinc oxide and removing the water of reaction by distillation.ALSO:Resins comprising or consisting of units of at least one ester of acrylic or methacrylic acid and having a solubility parameter d  (as defined in the Specification) from 8:4 to 9.7 are plasticized with one or more epoxy esters of the formula RCOOA where R represents the residue of an epoxidized fatty acid and A represents the residue, after removal of a hydroxyl group, of a phenol or an alcohol which is not acyclic, except that A can represent (a) an ether group of the formula R1(OCH2CH2)nOCH2CH2\t where R1 is a C1-C4 alkyl group and n is 0 or an integer from 1 to 4 or (b) a chloroalkyl group containing one or more chlorine atoms. Apart from the specified groups (a) and (b), A generally represents a hydrocarbon group, such as aryl, alkaryl, aralkyl and cycloalkyl, or derivatives thereof containing, for example, halo or hydroxy substituents; A may also represent a heterocyclic group, e.g. furfuryl and derivatives thereof.  The residue R of the epoxy ester may contain from 11 to 22 carbon atoms and is typically derived from vegetable or animal oils; for example, R may be derived from oleic acid or safflower oil, soybean oil, linseed oil or tall oil fatty acids.  The ester resin is preferably derived from monomeric material containing at least 50% by weight of one or more alkyl or cycloalkyl esters of acrylic or methacrylic acid in which the alkyl or cycloalkyl group contains up to 18 carbon atoms; the resin may also comprise units of vinyl-pyridines, acrylonitrile, methacrylonitrile, acrylic or methacrylic acid and amides and salts thereof, itaconic or citraconic acid and their derivatives, e.e. esters, maleic anhydride, maleic, chloromaleic or fumaric acid and esters of these acids, vinyl ethers, vinyl esters, e.g. vinyl acetate, vinylidene chloride, vinyl sulphides, styrene and its derivatives and analogues thereof, vinylcarbazole, ethylenically unsaturated urea derivatives, allyl esters of monocarboxylic acids, aminoalkyl esters of acrylic and methacrylic acids, hydroxy alkyl esters or amides of acrylic and methacrylic acids, and acrylyl and methacrylyl dicyandiamides.  The plasticized compositions may contain other polymers in addition to the acrylic ester resin and may also contain additional plasticizers, e.g. phthalate and phosphate esters, mixed benzoic acid and fatty oil acid esters of pentaerythritol, poly-(propyleneadipate) dibenzoate, diethylene glycol dibenzoate, tetrabutyl thiodisuccinate, butyl phthalyl butyl glycolate, acetyl tributyl citrate, dibenzyl sebacate, toluene ethyl sulphonamide, the di-2-ethylhexyl ester of hexamethylene diphthalate and di(methylcyclohexyl) phthalate. The plasticized composition may be incorporated in a solvent for coating or impregnating purposes and a pigment may also be included, e.g. titanium dioxide, carbon black, iron blues, phthalocyanine blues and greens, metal oxides, hydroxides, sulphides, sulphates, silicates and chromates, aluminium flake, bronze powders, and also a filler or extender, e.g. talc, barytes, china clay and diatomaceous earth.  The plasticized esters may also be used in aqueous dispersion containing conventional emulsifiers (many specified) and, if desired, an aminoplast resin, particularly reaction products of aldehydes, e.g. formaldehyde, with compounds such as urea, thiourea, biuret and derivatives thereof, and triazines including melamine and derivatives thereof.ALSO:Substrates such as wood, metal, ceramics, linoleum, vinyl resin tiles and textile fabrics are coated with solutions or aqueous dispersions of plasticized resin compositions comprising an acrylic ester resin comprising or consisting of units of at least one ester of acrylic or methacrylic acid and having a solubility parameter d  (as defined in the Specification) from 8.4 to 9.7 and, as plasticizer therefor, one or more epoxy esters of the formula R C O O A where R represents the residue of an epoxidised fatty acid and generally contains from 11 to 22 carbon atoms, and A represents the residue, after removal of a hydronyl group, of a phenol or an alcohol which is not acyclic, except that A can represent (a) on ether group of the formula R1 (O CH2 CH2)n O CH2 CH2 where R1 is a C1-C4 alkyl group and n is O or an integer from 1 to 4 or (b) a chloroalkyl group containing one or more chlorine atoms.  The coating compositions may also include other polymers in addition to the aerylic ester resin, additional plasticizers (many specified), pigments, e.g. titanium dioxide, carbon black, iron blues, phthalocyanine blues and greens, metal oxides, hydroxides, sulphides, sulphates, silicates and chromates, aluminium flake, bronze powders, fillers or extenders, e.g. talc, barytes, china clay and diatomaceous earth, and aminoplast resins, particularly condensation products of various amino or amido compounds with aldehydes, e.g. formaldehyde.  The aqueous dispersions may also include an emulsifier.  Coating may be effected by air-spraying (with or without heating), steam spraying, electrostatic spraying, spraying a preheated coating composition, dipping, brushing or roller-coating.  The coatings may be dried at room or elevated temperature, e.g. from 140 DEG  to 300 DEG F.  In an Example (No. 3), "Dacron" (Registered Trade Mark) taffeta fabric is coated with an aqueous dispersion of a copolymer of methyl methacrylate, methacrylic acid and N-[b -(a -methacryloxyacetamido) ethyl]-N, N1-ethylene urea (96 : 2 : 2) plasticized with the tetrahydrofurfuryl ester of epoxy linseed oil fatty acids; a solution of the same copolymer-plasticiser combination is used to cast a film on a metal (unspecified) sheet.ALSO:The fibres of a non-woven fibrous mass are bound together by impregnating the fibrous mass of, for example, wool, silk, mohair, fur, cotton, linen, rayon, nylon, or acrylonitrile polymers, with a solution or aqueous dispersion of a plasticized acrylic ester resin and drying the impregnated mass.  The acrylic ester resin comprises or consists of units of at least one ester of acrylic or methacrylic acid, has a solubility parameter d  (as defined in the Specification) from 8.4 to 9.7, and preferably contains groups which form cross-links or can be cross-linked by reaction with aminoplast resins; such groups include amide and N-methylol groups.  The resin is plasticized with one or more epoxy esters of the formula RCOOA where R represents the residue of an epoxidized fatty acid and generally contains from 11 to 22 carbon atoms, and A represents the residue, after removal of a hydroxyl group, of a phenol or an alcohol which is not acyclic, except that A can represent (a) an ether group of the formula R1 (O CH2 CH2)n O CH2 CH2 where R1 is a C1 - C4 alkyl group and n is O or an integer from 1 to 4 or (b) a chloroalkyl group containing one or more chlorine atoms.  The binder compositions may also include other polymers in addition to the acrylic ester resin, additional plasticizers (many specified), pigments, e.g. titanium dioxide, carbon black, iron blues, phthalocyanine blues and greens, metal oxides, hydroxides, sulphides, sulphates, silicates and chromates, aluminium flake, bronze powders, fillers or extenders, e.g. talc, barytes, china clay and diatomaceous earth, and aminoplast resins, particularly condensation products of various amino or amido compounds with aldehydes, e.g. formaldehyde.  The aqueous dispersions may also include an emulsifier.  In an Example (No. 6), a non-woven carded web of 75/25 viscose (3 denier, 1 inch staple)-bleached cotton (middling 15/16 inch) is impregnated with an aqueous dispersion of an ethyl acrylate-methyl methacrylate (45:55) copolymer plasticized with the benzyl ester of epoxyoleic acids.