Patent GB-1020509-A (GB)
Title: Fluorine containing sulphonamido polyols
IPC: C08G63/688
Filed: 1962-08-07
Abstract: Coating compositions consist of solutions of compounds of the formula RfSO2N(R1)Z, where Rf is a C1- 18 perfluorinated aliphatic or cycloaliphatic radical, R1 is hydrogen or C1- 12 alkyl, and Z is a monovalent organic radical having at least 2 hydroxy groups (see Division C2).  In an example the solvent is ethyl acetate-trichloroethylene.ALSO:The invention comprises compounds of the formula RfSD2N(R1)Z, where Rf is a C1- 18 perfluorinated aliphatic or cycloaliphatic radical, R1 is hydrogen or C1- 12 alkyl and Z is a monovalent organic radical having at least two hydroxy groups.  Z may be low-molecular (see Division C2) or high-molecular (see methods of preparation below).  These compounds may be prepared by reacting an alkali metal salt of a compound RfSO2N(R1)H with (1) a halohydrin, e.g. one derived from propylene oxide adducts of dipropylene glycol, 1,2,6-hexanetriol or glycerol; (2) a polyepoxy compound, e.g. epoxylated novolac resins; epoxy resins derived from epichlorohydrin and bisphenol A; and epoxidized polybutadienes; followed by hydrolysis; or (3) an unsaturated halide, followed by epoxidation and hydrolysis (for low-molecular reactants in these processes (see Division C2).  The above compounds may be reacted to form acrylate and methacrylate half-esters which undergo vinyl-type polymerization; the products may be cross-linked, cured or modified via the hydroxyl groups by reaction with carboxylic, isocyanate, epoxy or azirane compounds.  The monomeric compounds of the invention may be used as components in polyester, polyisocyanate, epoxy resin or other polymerization system.  Both monomers and polymers may be used in solution to form protective coatings on various materials (see Divisions B2, D1).  In examples, the 2:1 molar adduct of 2,4-toluenediisocyanate with <FORM:1020509/C3/1> is reacted with (5) trimethylolpropane, (6) polyethylene glycol and (7) polypropylene glycol; <FORM:1020509/C3/2> is reacted with (8) N,N1-bisethylene-isosebacamide and (9) ClCO(CF2)3COCl, followed by hydrolysis of excess -COCl and heating with N,N1-bis-ethyleneisosebacamide; <FORM:1020509/C3/3> is reacted with (10-(12) isosebacic acid and in (12) the product is cured with N,N1-bis-ethyleneisosebacamide; (13) <FORM:1020509/C3/4> is reacted with phthalic anhydride, soybean acids and glycerol, in xylene, and cobalt and lead naphthenates added; melamine-formaldehyde resin may also be added; <FORM:1020509/C3/5> is reacted with (14) phthalic anhydride, dehydrated castor oil and glycerol; (15) phthalic anhydride, linseed oil acids and glycerol; (16) pyromellitic dianhydride and ethyl "Cellosolve" (Registered Trade Mark) acetate, followed by mixing with an epoxy resin; and (18) phthalic anhydride, maleic anhydride and propylene glycol, followed by copolymerization of the product with styrene in the presence of benzoyl peroxide; (17) <FORM:1020509/C3/6> is reacted with toluene diisocyanate, a polyether triol and later castor oil; and (19) <FORM:1020509/C3/7> is reacted with phthalic anhydride, soybean acids and glycerol, followed by dilution and addition of metallic driers; melamine-formaldehyde resin may also be added.ALSO:The invention comprises compounds of the formula RfSO2N(R1)Z, where Rf is a perfluorinated aliphatic or cycloaliphatic radical of 1-18 carbon atoms, R1 is hydrogen or C1-12 alkyl, and Z is a monovalent organic radical having at least 2 hydroxy groups, and their preparation by reacting at elevated temperature an alkali metal salt of RfSO2N(R1)H with a suitable halohydrin, e.g. one derived from glycerol, sorbitol, 1,2,3 - butanetriol, pentaglycerol, 1,2,3,4 - butanetetrol, 1,2,3,4,5 - pentanepentol, mannitol, pentaerythritol, 1,2,6-hexanetriol, and propylene oxide addition products of dipropylene glycol, 1,2,6-hexanetriol or glycerol. The compounds of the invention may also be prepared by adding a solution of an alkali metal salt as above to a molar excess of a suitable epoxy compound, such as diglycidyl ethers, glycidyl ethers of glycerol, bisphenol F or tetrakis (hydroxyphenyl) ethane, butadiene dioxide, 3,4 - epoxy - 6 - methylcyclohexylmethyl 3,4 - epoxy - 6 - methylcyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane, followed by refluxing with water; or by reacting an alkali metal salt as above with an unsaturated halide, epoxidizing and hydrolysing; alcohols from which the halide may be prepared include 2-ethylidene-1-heptanol, 1-phenyl - 2 - hydroxybut - 3 - ene, 3 - phenyl-2 - hydroxypent - 3 - ene, 2 - phenyl - 2 - hydroxypent - 4 - ene, 2 - methyl - 2 - hydroxypent - 4 - ene, 5 - hydroxyhex - 1 - ene and 11 - hydroxyundec - 1 - ene. Other higher-molecular reactants are also specified (see Division C3).  In examples, Rf is C8F17, and (1) R1 is propyl, Z is CH2OH.OHOH-; (2) R1 is ethyl and Z is HO(CH2)4CHOHCH2-; (3) R1 is ethyl and Z is HOCH2(CHOH)2CH2-; and (4) R1 is ethyl and Z is HOCH2CHOHCH2-, and also the compound C6F13SO2N(C3H7)CH2CHOHCH2\t OH The compounds of the invention can react with isocyanates or acids to give urethanes or esters, e.g. acrylate and methacrylate half-esters; and the product of Example 1 is reacted with 2,4-toluenediisocyanate to give a diisocyanate-diol 2: 1 molar adduct.  The compounds of the invention, and polymers derived from them (see Division C3) may be used for imparting water and oil-repellent coating to various materials (see Divisions B2, C7, D1).  Chlorination of 1,2,6-hexanetriol gives a mixture of ClCH2CHOH(CH2)4OH and HOCH2 CHOH(CH2)4Cl; treatment with aqueous HIO4 destroys the 1,2-diol.ALSO:Paper, cloth and leather are rendered water- and oil-repellent by impregnating with a solution of a compound of formula RgSO2N(R1)Z, where Rg is a perfluorinated C1-13 aliphatic or cycloaliphatic radical, R1 is hydrogen or C1-12 alkyl, and Z is a monovalent organic radical having at least 2 hydroxy groups (see Division C3).  Examples treat leather, a worsted fabric and cotton, the solvent being carbon tetrachloride, trichloroethylene or ethyl acetate.ALSO:Surfaces such as that of paper, cloth, leather, wood, metals, ceramic articles and glass are coated by treatment with a solution of a compound RgSO2N(R1)Z, where Rg is a C1-18 perfluorinated aliphatic or cycloaliphatic radical, R1 is hydrogen or C1-12 alkyl, and Z is a monovalent organic radical having at least 2 hydroxy groups (see Division C2) or a polymer derived from such a compound (see Division C3).  The coatings are water- and oil-repellent.  The polymer may be a polyester or polyurethane : melamine-aldehyde resins may be added thereto.  The compounds may be applied by brushing, spraying, dipping or doctor blade.