Patent GB-1011976-A (GB)
Title: Fluorine-containing resins
IPC: C08G59/44
Filed: 1962-05-10
Abstract: Resins soluble in xylene or methyl ethyl ketone and having a fluorine content of 0.5 to 20% by weight are made by modifying a polyester, polyurethane or epoxy resin, during or after manufacture with a fluorochemical compound of formula Rf(X)mZ or a partial ester thereof where Rf is a perfluorinated aliphatic radical having from 1 to 18 carbon atoms, RfX is a group of formula <FORM:1011976/C3/1> where m is 0 or 1, R1 is hydrogen or an alkyl radical containing 1 to 12 carbon atoms, and Z is a group of formula R2CH2OH or R2COOH where R2 is a substituted or unsubstituted aliphatic radical having 1 to 18 carbon atoms.  The fluorochemical is bonded to the resin by an ester, ether, amide or urethane linkage.  The polyester may be linear or branched and may be modified by monocarboxylic acids. Those fluorinated polyesters containing the residues of unsaturated mono- or di-carboxylic acids may be reacted with unsaturated monomers (e.g. styrene, methyl methacrylate or fluorinated acrylates or methacrylates).  The polyurethane may be linear or branched and hydroxylated oils may be included in the polyurethane-forming reaction mixture.  The epoxy resin may be based on the diglycidyl ether of bisphenol A or on 3,4-epoxy-6-methylcyclohexylmethyl - 3,4 - epoxy - 6 - methylcyclohexane carboxylate and may be further modified by bisphenol A, a dicarboxylic acid (e.g. diphenic, adipic, maleic or phthalic) or a vegetable acid. In examples, resins were made by reacting (1) phthalic anhydride, glycerol, dehydrated castor oil acids and N-ethyl perfluorooctanesulphonamido ethanol; (2) a coconut oil modified alkyd and N-ethyl perfluorooctane sulphonamido ethanol; (3) phthalic anhydride, maleic anhydride and N-propyl perfluorooctanesulphonamido ethanol-the resin was dissolved in styrene or methyl methacrylate and catalysed with benzoyl peroxide; (4) the resin of Example (1) and styrene or methyl methacrylate; (5), (6) and (7) the 3,4-epoxy-6-methylcyclohexylmethyl - 3,4 - epoxy - 6 - methyl cyclohexane carboxylate, soyabean acids or dehydrated castor oil acids and N-ethyl perfluorooctanesulphonyl glycine or its half-ester with succinic acid, the resin being catalysed by a BF3-etherate and water; (8) a polyoxypropylated 1,2,6-hexanetriol, toluene diisocyanate and N - ethyl perfluorooctanesulphonamido ethanol followed by castor oil; (9) the fluorinated alkyd of Example (1), N-ethyl perfluorooctanesulphonamidoethyl methacrylate and cumene hydroperoxide; (10) maleic anhydride, phthalic anhydride, propylene glycol and N-ethyl perfluorooctane sulphonamido ethanol-the resin being dissolved in N-ethyl perfluorooctanesulphonamidoethyl methacrylate and catalysed with benzoyl peroxide; (11)-(13) phthalic anhydride, glycerol, linseed fatty acids or dehydrated castor oil fatty acids and C18F17(CH2)10COOH, C7F15.CO.NH.(CH2)3 COOH, C7F15.CO.NH.CH2CH2OH or C8F17 CH = CHCH2OH.  All of the resins were made into lacquers, usually with the addition of a hydrocarbon solvent (ethylacetate in Example (8)) and possibly with the addition of a lead or cobalt naphthenate or a butylated melamine formaldehyde condensate (Examples (1), (2) and (5)).  In Example (14) an alkyd made by reacting phthalic anhydride, pentaerythritol, polyethylene glycol (M.W. 1540) and linseed acids in the presence of xylene was reacted with C8F17SO2N(C2H5)CH2CH2OH and the resin poured into hot water to form an aqueous dispersion which was catalysed with cobalt and manganese naphthenates. Specifications 857,335, 857,336, 857,689, 896,615, 904,111 and 904,263 are referred to.ALSO:The compound <FORM:1011976/C2/1> is prepared by reacting a compound of formula C7F15COOC2H5 with ethyl gamma-aminobutyrate and hydrolysing the resulting ester. Specifications 857,335, 857,336, 857,689, 896,015, 904,111 and 904,263 are referred to.