Patent GB-977361-A (GB)
Title: New copolymers, process for their preparation and their use
IPC: C08F220/28
Filed: 1962-10-18
Abstract: Esters of the formula <FORM:0977361/C1/1> in which R1 stands for H or a lower alkyl radical and R2 stands for an aliphatic, cycloaliphatic araliphatic, or aromatic hydrocarbon residue which may be substituted by halogen atoms or interrupted by oxygen atoms, are made by reacting acrylic or alkacrylic acids with monoglycidyl ethers of phenols or alcohols. In the examples: (1) 3-n-butoxy -2- hydroxypropyl acrylate is made by reacting acrylic acid and butyl glycidyl ether; (3) as in (1) but employing methacrylic acid in place of acrylic acid; (4) 3-ethoxy -2- hydroxypropyl acrylate is made by reacting acrylic acid with ethyl glycidyl ether; (5) 3-n-dodecyloxy-2-hydroxypropyl acrylate is made by reacting acrylic acid and lauryl glycidyl ether; and (6) 3-tolyloxy -2- hydroxypropyl acrylate is made by reacting acrylic acid with o-cresyl glycidyl ether.ALSO:Esters of the formula: <FORM:0977361/C3/1> in which R1 stands for H or a lower alkyl group and R2 for an aliphatic cycloaliphatic, araliphatic or aromatic hydrocarbon residue, are copolymerized with at least one other ethylenic monomers.  Preferred esters of the above formula are 3-n-butoxy-2-hydroxypropyl acrylate and methacrylate, 3-ethoxy-2-hydroxypropyl acrylate, 3-n-dodecyloxy -2- hydroxypropyl acrylate and 3-tolyloxy -2- hydroxypropyl acrylate.  Specified comonomers are acrylonitrile, methacrylonitrile, ethyl, n-butyl and 2-ethylhexyl acrylates, ethyl methacrylate, vinyl chloride, chlortrifluoroethene, 1, 1-difluoroethene, acrylamide and methacrylamide and N-alkyl derivatives thereof, vinyl acetate and propionate and vinyl alkyl ethers, and mixtures thereof, e.g. a mixture of n-butyl acrylate and vinyl acetate.  Polymerization may be carried out in bulk, suspension, emulsion or, preferably, in solution in a solvent such as ethyl acetate, benzene, acetone or dichloroethane, in the presence of a catalyst, e.g. benzoyl peroxide, lauroyl peroxide or azodiisobutyronitrile.  During the course of polymerization further quantities of monomer, catalyst and solvent may be added. The resulting copolymers may be cross-linked by reaction with compounds containing a plurality of groups reactive with hydroxyl groups, such as di- and poly-isocyanates, e.g. the reaction product of trimethylol propane and toluylene diisocyanate, soluble aminoplasts, e.g. condensation products of formaldehyde with ureas, dicyandiamide, melamine and guanamines, and ethers thereof with alcohols such as methanol and n-butanol, and esters thereof with acids such as palmitic and stearic acid, boroxines, titanic acid esters, alkyl-orthosilicates polyglycidyl ethers, formaldehyde, phenoplasts and poly-(2, 3-dihydro-1, 4-pyranyl) compounds.  The copolymers are used to provide coatings, particularly water-repellent coatings, to metals and fabrics, for which purpose solutions containing copolymer, solvent and cross-linking agent may have added thereto waxes, e.g. carnauba, Japan, palm, bees, opal and paraffin waxes, and pigments, e.g. talc, kaolin, lampblack, titanium dioxide and bronze powder. Specified solvents for the composition are ethyl acetate and a mixture thereof with n-butyl, benzyl, ethyl and diacetone alcohols, xylene, methyl ethyl ketone and ethylene glycol monoethyl ether.  The Specification describes also:  (a) the etherification of hexamethylol melamine with methanol, the recovery of the resulting ether, and its esterification with stearic acid; and (b) the esterification of acrylic acid with butyl glycidyl ether in which the residue after the monomeric ester has been removed consists of the acrylate of poly (butyl glycidyl ether), which may be polymerized.ALSO:Surfaces of metal sheets or fabrics are coated by applying thereto compositions comprising a copolymer of an ester of the formula:  <FORM:0977361/B1-B2/1> in which R1 stands for H or a lower alkyl radical and R2 for an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue which may be substituted by halogen atoms or interrupted by oxygen atoms (see Division C3), a cross-linking agent therefor, e.g. a polyisocyanate or an aminoplast, and a solvent.  Also present in the compositions may be pigments and, when a water-repellent effect is desired, waxes.  After application the coatings are dried and cured.  Fabrics to which the coatings may be applied are those of cotton, rayon, acetyl-cellulose, polyester, polyamide and polyacrylic fibres.  In the examples: (7) aluminium sheets are coated with a solution containing the butyl ether of a melamine-formaldehyde condensation product, and a copolymer of n-butyl acrylate and 3-n-butoxy-2-hydroxypropyl acrylate, the solvent being a mixture of n-butyl, ethyl, benzyl and diacetone alcohols, ethyl acetate, xylene, methyl ethyl ketone and ethyleneglycol monomethyl ether, followed by curing at 180  DEG C.; (8) nylon fabric is coated twice, with intermediate drying, with an ethyl acetate solution containing a copolymer of n-butyl acrylate and 3-n-butoxy-2-hydroxypropyl acrylate, and a polyisocyanate made by reaction between trimethylol propane and toluylene diisocyanate; and (9) nylon fabric is coated twice, with intermediate drying, with an ethyl acetate solution containing a copolymer of n-butyl acrylate vinyl acetate and 3-n-butoxy-2-hydroxypropyl acrylate, a methylol melamine etherified with methanol and esterified with stearic acid and a methylol melamine etherified with n-butanol. Both treated nylon fabrics exhibit water repellency.