Patent GB-772301-A (GB)
Title: Improvements in or relating to alkali soluble synthetic resins and compositions containing same
IPC: C08G65/40
Filed: 1954-06-24
Abstract: An alkali soluble resin with an acid value between 40 and 130 and a phenolic hydroxyl value between 45 and 120 is prepared by reacting in presence of alkali (1) a dihydric phenol; (2) a bifunctional coupling agent of 2-10 carbon atoms which is an aliphatic epoxy halide, an aliphatic dihalide, an aliphatic diepoxide, or such an agent in which one of the carbon atoms is replaced by ethereal oxygen; and (3) a monohalo monocarboxylic acid with 2-8 carbon atoms or a mono-epoxy monocarboxylic acid with 3-8 carbon atoms.  The dihydric phenol used is more than equivalent to the coupling agent and part of the unreacted phenolic hydroxyl groups are etherified with the acid to yield products which are oxyaryl acids.  The molecular weight, solubility, acid and hydroxyl values of the products are controlled by selection of the starting materials and their properties. Dihydric phenols mentioned are: resorcinol, hydroquinone, catechol, p,p1-dihydroxybenzophenone, p,p1-dihydroxydiphenyl, p,p1-dihydroxydibenzyl, dihydroxy anthracenes, dihydroxy naphthalenes, and bisphenols in which the aromatic nuclei are joined by alkyl groups of 1-10 carbon atoms.  Coupling agents mentioned are: epichlorhydrin, epibromhydrin, 2,3-epoxypropyl 2-hydroxy-3-chloropropyl ether, 1,2-epoxy-3,4-epoxybutane, bis - (2,3 - epoxypropyl) - ether, 1,2- or 1,3-dichloroethane, 1,2- or 1,3-dibromethane, and 1,10-dichlorodecane.  Carboxylic acids mentioned are: chloracetic acid, 2-chlorocaprylic acid, 5-bromovaleric acid, glycidic acid, and 6, 7-epoxyheptanoic acid.  In the examples resins are prepared from the following ingredients: 1, 2 and 7-13, p,p1-isopropylidenediphenol, epichlorhydrin and chloroacetic acid.  3, p,p1-isopropylidenedi-o-cresol, epichlorhydrin and chloroacetic acid.  4, p,p1-isopropylidenediphenol, epichlorhydrin and a -chloropropionic acid.  5, p,p1-isopropylidenediphenol, bis-BETA-chloroethyl ether and chloroacetic acid.  6, p,p1 - isopropylidenediphenol, 1,4 - dichlorobutene-2, and chloroacetic acid.  In Examples 3, 4, 6 and 7-13 the reaction with the monocarboxylic acid is followed by a reaction with a further batch of coupling agent.  The proare useful for paints, varnishes, adhesives, fabric-treating compositions and particularly for floor-coatings.  They may be dissolved in alkali, either which still molten after washing with hot water or after cooling and pulverizing, and may be blended with shellac, ester gum, or terpene phenolic resins or with wax emulsions.  Examples of removable coating compositions are: (14) a solution in borax of the product of Example 7 was mixed with a borax solution of shellac and with an aqueous emulsion containing oxidized microcrystalline wax, a terpene phenolic resin, oleic acid, triethanolamine and caustic soda. (15) An ammoniacal solution of the product of Example 2 was mixed with a wax emulsion as described in Example 14.  (16 and 17) An ammoniacal solution of the product of Example 1 was mixed with an emulsion containing oleic acid, carnaubic wax, trithanolamine and caustic soda.  The waxes used in the examples may be replaced by ouricuri, candelilla or sugar cane wax or supplemented with paraffin or montan wax.ALSO:An alkali soluble resinous oxyaryl acid with an acid value between 40 and 130 and a phenolic hydroxyl value between 45 and 120 is prepared by reacting in presence of alkali (1) a dihydric phenol, (2) a bifunctional coupling agent of 2-10 carbon atoms which is an aliphatic epoxy halide, an aliphatic dihalide, an aliphatic diepoxide or such an agent in which one of the carbon atoms is replaced by ethereal oxygen, and (3) a monohalo monocarboxylic acid with 2-8 carbon atoms or a mono-epoxy monocarboxylic acid with 3-8 carbon atoms.  The dihydric phenol used is more than equivalent to the coupling agent and part of the unreacted phenolic hydroxyl groups are etherified with the acid. The molecular weight, solubility, acid and hydroxyl values of the products are controlled by selection of the starting materials and their properties. Dihydric phenols mentioned are: resorcinol, hydroquinone, catechol, p,p1-dihydroxybenzophenone, p,p1-dihydroxydiphenyl, p,p1-dihydroxydibenzyl, dihydroxy anthracenes, dihydroxy naphthalenes, and bis phenols in which the aromatic nuclei are joined by alkyl groups of 1-10 carbon atoms.  Coupling agents mentioned are: epichlorhydrin, epibromhydrin, 2,3 - epoxypropyl 2 - hydroxy - 3 - chloropropyl ether, 1,2-epoxy - 3,4 - epoxybutane, bis-(2,3-epoxypropyl) ether, 1,2- or 1,3-dichloroethane, 1,2- or 1,3-dibromoethane, and 1,10-dichlorodecane.  Carboxylic acids mentioned are: chloroacetic acid, 2-chlorocaprylic acid, 5-bromovaleric acid, glycidic acid, and 6,7-epoxyheptanoic acid.  In the Examples, resins are prepared from the following ingredients: (1), (2) and (7-13) p,p1-isopropylidenediphenol, epichlorhydrin and chloroacetic acid; (3) p,p1-isopropylidenedi - o - cresol, epichlorhydrin and chloroacetic acid; (4) p,p1 - isopropylidenedi - phenol, epichlorhydrin and a -chloropropionic acid; (5) p,p1 - isopropylidenediphenol, bis - b  - chloroethyl ether and chloroacetic acid; (6) p,p1 - isopropylidenediphenol, 1,4 - dichloro - butene-2, and chloroacetic acid.  In Examples (3), (4), (6) and (7-13) the reaction with the monocarboxylic acid is followed by a reaction with a further batch of coupling agent. The products are useful for paints, varnishes, adhesives, fabric-treating compositions and particularly for floor-coatings.