Patent GB-1119667-A (GB)
Title: Novel acrylic ester polymers
IPC: C08F20/16
Filed: 1965-08-25
Abstract: Copolymers are prepared by polymerizing a mixture of ethylenically unsaturated monomers so as to provide a product comprising 0.5 to 95% by weight of units of one or more phenyl esters of the formula <FORM:1119667/C3/1> wherein m is 1 or 2, x is 1, 2 or 3, n is 1 or 2, R1 is an alkyl group and R is a C1-C4 alkyl group, and 99.5 to 5% by weight of units of one or more comonomers.  Suitable comonomers include vinyl pyridines, (meth)acrylic acid and nitriles, esters, amides and salts, maleic, chloromaleic, fumaric and itaconic acids and their esters and anhydrides, vinyl ethers, vinyl esters, vinyl sulphides, styrene and its derivatives and analogues, vinyl carbazole and allyl carboxylates; polyethylenically unsaturated monomers may also be used, e.g. di- or tri-vinyl benzene, ethylene di-(meth)acrylate, bis - (b  - vinyloxyethyl) - urea and b  - vinyloxyethyl -(meth)-acrylate. The monomers may be polymerized in bulk, solution, emulsion or suspension, or cast polymerized to produce shaped articles. Suitable cataysts for polymerization incude benzoyl, acetyl and caproyl peroxides, t-butyl hydroperoxide, t-butyl perbenzoate, azodiisobutyronitrile, azodiisobutyramide, dimethyl, diethyl or di-n-butyl azodiisobutyrate, azobis - (a ,g  - dimethylvaleronitrile) and dimethyl or diethyl azobismethylvalerate; and redox systems comprising hydrogen peroxide or ammonium, sodium or potassium persulphate together with a sulphite, bisulphite, metabisulphite, hydrosulphite or hydrazine.  A regulator such as b -mercaptoethanol may be used in the polymerization. Copolymers obtained containing carboxyl groups may be partly or completely neutralized e.g. with an alkali metal hydroxide, ammonia or an amine; and copolymers containing amine groups may be partly or completely neutralized with an acid.  The copolymers may be used in various coating or impregnating compositions (aqueous or non-aqueous), which compositions may include plasticizers, e.g. phthalates, phosphates, dihexyl adipate or glycerol monoricinoleate; pigments, e.g. carbon black, titanium dioxide, ultramarine blue, lead chromate, copper phthalocyanine blues and greens, zinc chromate, zinc oxide, blues and greens, zinc chromate, zinc oxide, clays, calcium carbonate, lead carbonate, barium sulphate, iron oxides, toluidines, Prussian blue, chrome yellow, Para Red Teners, Lithol Red, Cadmium Red, chromium oxide, ion oxides, lithopone, azo pigments and lakes, vat dyestuffs, and powdered or flaked metals; aminoplast or phenoplast resins; epoxy resins; vinyl or acrylic resins; cellulose derivatives; thickening agents, e.g. gum tragacanth, watersoluble cellulose ethers, polyvinyl alcohol or partially saponified polyvinyl acetate; and basic inorganic or organic compounds. Suitable non-aqueous solvents for the copolymers include butylacetate, toluene, xylenes, n-butanol, dimethylformamide and mixtures thereof.  The copolymer coating obtained from the above compositions can be insolubilized by drying at room or elevated temperature, optionally in the presence of a curing catalyst. Copolymers containing, for example, 75-90% by weight of acrylonitrile units can be formed into fibres or films; others containing units of (meth)-acrylic acid or a vinylpyridine can be blended (molten or in solution) with acrylonitrilevinyl chloride or acrylonitrile-vinyl acetate copolymers to modify the dyeing properties of the acrylonitrile copolymers.  Examples illustrate the preparation and use of aqueous dispersions of copolymers of the phenyl esters with (a) ethyl acrylate, methyl methacrylate and itaconic acid, (b) ethyl acrylate, methacrylamide and methylol-methacrylamide, (c) ethyl acrylate and methacrylamide, (d) ethyl acrylate, and methylol-acrylamide (e) ethyl acrylate, 2-ethylhexyl acrylate and methylol-acrylamide (f) methyl acrylate and methoxymethyl-methacrylamide, and a butyl acetate-xylene solution of a copolymer of a phenyl ester with (g) butyl acrylate and methoxymethyl-methacrylamide, and (h) ethyl acrylate and N-methylol-4 -pentenamide; in some cases mixtures of the copolymers are used, and other components used include an aminoplast resin, diethyl phthalate, copper phthalocyanine blue and sodium alginate.ALSO:Substituted phenyl acrylates or methacrylates of the formula <FORM:1119667/C2/1> wherein m is 1 or 2, x is 1, 2 or 3, n is 1 or 2, R1 is alkyl and R is C1-C4 alkyl, are prepared by reacting an acyl chloride or bromide of acrylic or methacrylic acid with an appropriately substituted alkali metal phenolate.  In an illustrative preparation, p-methoxyphenyl methacrylate is obtained by reacting methacrylyl chloride (in a small excess) with p-methoxy-phenol in aqueous sodium hydroxide, the precipitated product being purified by recrystallization from methanol.ALSO:Coating compositions comprise aqueous dispersions or organic solvent solutions of copolymers of 0.5 - 95% by weight of one or more phenyl acrylates or methacrylates wherein the phenyl ring contains 1 or 2 C1 - C4 alkoxy groups and, optionally, 1 or 2 alkyl groups.  Comonomers for the phenyl esters include vinyl pyridines, (meth) acrylic acid and nitriles, esters, amides and salts, maleic, chloromaleic, fumaric and itaconic acids and their esters and anhydrides, vinyl ethers, vinyl esters, vinyl sulphides, styrene and its derivatives and analogues, vinyl carbazole and allyl carboxylates, and poly ethylenically unsaturated monomers such as di- or trivinyl benzene, ethylene di (meth) acrylate, bis (b  - vinyloxyethyl) - urea and b  - vinyloxyethyl (meth) acrylate. Suitable oganic solvents include butyl acetate, toluene, xylenes, n - butanol, dimethyl formamide and mixtures thereof.  The compositions can be applied to a variety of substrates, e.g. leather, paper, textiles, ceramics, metals (untreated or primed), stone, cement, concrete, bricks, asbestos - cement shingles, cinder block and other masonry surfaces.  Coating may be effected by spraying, brushing, roller-coating, dipping or knife coating, excess material being removed, for example, by pressure rollers, air squeegeeing or by knife or doctor blade.  The coatings can be insolubilised by drying at room or elevated temperature, optionally in the presence of a curing catalyst.  Optional components of the composition include plasticisers, inorganic or organic pigments, metal powder or flakes, aminoplast, phenoplast or epoxy resins, vinyl or acrylic resins, cellulose derivatives, thickening agents, emulsifiers, basic inorganic or organic compounds and buffers.  In Examples coatings are applied to leather, chipboard, paper, wallpaper, asbestos-cement sheet, a cotton and viscose rayon - cellulose acetate pile fabric, and a nylon taffeta fabric.ALSO:Aqueous dispersions of copolymers comprising 0.5-95% by weight of units of one or more phenyl acrylates or methacrylates, wherein the phenyl ring contains 1 or 2 C1-C4 alkoxy groups and, optionally, 1 or 2 alkyl groups, which compositions may be pigmented, are used for dyeing or treating textiles, whereby the textile material is rendered resistant to U.V. light, laundering, cleaning etc., and for binding non-woven fabrics. Copolymers of the phenyl esters with, for example, ethyl or n-butyl acrylate and 1-5% by weight of a functional monomer such as N-methylol acrylamide or glycidyl methacrylate are particularly suitable for treating woollen fabrics to reduce shrinkage thereof, and for binding, e.g. by air-deposition, carding or garnetting, non-woven fabrics derived from rayon, wool, cellulose acetate, and other esters and ethers, vinyl resins, acrylonitrile polymers, polyethylene glycol terephthalate, and glass or other mineral fibres. In Examples, the compositions are applied to cotton percale, a non-woven textile fabric formed of three super-imposed carded webs of cotton fibres, and cotton sheeting; in some cases the composition is pigmented with copper phthalocyanine blue.