Patent GB-810570-A (GB)
Title: Hydroxylated benzophenone ethers
IPC: C07C49/84
Filed: 1956-07-12
Abstract: The invention comprises compositions of ultra-violet absorbers of general formula <FORM:0810570/III/1> in which X is hydrogen or hydroxyl and R is alkyl, aralkyl, substituted alkyl or alkenyl, with a polish or wax containing a silicone resin, and/or a natural ester wax (carnauba, candelilla, montan) and/or paraffin wax, or natural resins and gums such as Damar, Eleric, shellacs or Manila with an organic solvent.  The compositions may be used to coat stained or unstained, varnished or unvarnished wood, or incorporated in light and white paints and enamels.  Reference has been directed by the Comptroller to Specification 738,096, [Group IV (a)].ALSO:The invention comprises compositions containing ultra-violet absorbers of the general formula <FORM:0810570/IV (a)/1> where X is hydrogen or hydroxyl and R may be alkyl, aralkyl, substituted alkyl or alkenyl. The compounds may be dissolved or dispersed in various organic carriers.  Carriers specified are polyethylene glycols, polypropylene glycols, methyl methacrylate, polyethylene glycol terephthalate, polymers of methyl acrylate, acrylamide, methylol acrylamide, acrylonitrile, and acrylic copolymers with styrene, and vinyl pyridines.  Also nylon, neoprene, paraformaldehyde and hexamethylene tetramine condensates with urea, thiourea, melamine, benzoguanamine, methanol or butanol, condensates of phenol or resorcinol with the aforementioned aldehydes, dimethyl and methyl hydrogen polysiloxanes, polymers of ethylene, propylene and isobutylene, polyvinyl butyral, chloride, and acetate and the hydrolysis product of the latter, polyvinyl chloride-acetate, styrene and substituted styrenes such as o-, m- and p-methyl styrene, and polymers and copolymers with acrylonitrile, copolymers of vinylidene chloride with vinyl chloride, ethyl and methyl cellulose, cellulose nitrate, acetate and propionate, regenerated cellulose, lacquers containing nitrocellulose, Damar, Elemi, shellacs or Manila gums, polytetrafluoroethylene, polytrifluorochlorethylene, rubber hydrochloride, chlorinated rubber, and condensates of epichlorohydrin with bis-phenol, diphenylol propane, polyurethane or isocyanate resins, and homo- and co-polymers of any two or more of the epoxy resins.  The ultra-violet absorber may be dissolved in a solvent before it is incorporated into a carrier, and the solvent may be present in the final composition, e.g. such non-volatile solvents as di-2-ethyl hexylphthalate, tricresyl phosphate, tri-2-ethylhexyl phosphate and di-2-ethylhexyl sebacate.  The compositions may contain between about 0.001 and about 15 per cent, based on the total weight of solids in the final product, of the ultra-violet absorber.  The absorber may be incorporated into the carrier by various methods. Unsaturated polyester resins which may be used as carriers are those prepared from, e.g. maleic, fumaric, aconitic, and itaconic acid and monochloromaleic anhydride.  These unsaturated acids should be present in at least 20 per cent by weight of the total polycarboxylic acid present.  Saturated carboxylic acids which may also be used are phthalic, malonic, succinic, glutaric, sebacic, tetrachlorophthalic anhydride, hexachloroendomethylene tetrahydrophthalic acid or the corresponding anhydrides.  Suitable polyhydric alcohols for the preparation of the resins are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediols, hexanediol-1,6, glycerol, pentaerythritol and dipentaerythritol. The unsaturated linear alkyd component of the polyester should have an acid number below about 55.  Suitable cross-linking monomers for the polyester resin are styrene, alpha-methylstyrene, alpha-ethylstyrene, o-methyl styrene, p-ethyl styrene, metapropylstyrene, 2,4-dimethylstyrene, 2,5-diethylstyrene, and allyl compounds of which many are specified, including methallyl alcohol, allyl acetate, allyl acrylate, diallyl gluconate, diallyl chlorophthalate, triallyl cyanurate and tetraallyl silicate. Examples are given of compositions of 2-hydroxy-41-methoxybenzophenone with (1) polymethylmethacrylate powder; (2) polyvinylchloride, dioctyl phthalate, barium cadmium laurate and a triarylphosphite; and (3) a polyester resin from phthalic anhydride, fumaric acid and propylene glycol, of acid number 30-40, styrene, ditertiarybutylhydroquinone, and lauryl mercaptan, and compositions of 2-hydroxy-4-methoxy-41-tertiary-butyl benzophenone and 2,21-dihydroxy-4-methoxybenzophenone with polyethylene; nitrocellulose, coconut oil modified phthalic glyceride, dioctyl phthalate, n-butyl acetate, methyl isobutyl ketone, n-butanol, xylene and 2-hydroxy-41-dodecyloxy-benzophenone; polyvinyl butyral resin and 2-hydroxy-41-butoxybenzophenone; cellulose acetate, an organic maroon pigment, and 2 - hydroxy - 41 - benzyloxy - benzophenone; a cellulose acetate-butyrate resin and 2 - hydroxy - 41 - (2 - hydroxyethoxy) - benzophenone; nylon and 2-hydroxy-41-carboxymethoxybenzophenone, a copolymer of vinylidene chloride and vinyl chloride and 2-hydroxy-41-allyloxybenzophenone; a mixture of o-, m-and p-methyl styrene, titanium dioxide and 2,21 - dihydroxy - 4 - butoxybenzophenone, viscose and 2,21-dihydroxy-4-(2-hydroxy ethoxy)-benzophenone; a polyvinyl butyral resin, trioctyl phosphate, and 2,21-dihydroxy-4-allyloxybenzophenone; 2,21 - dihydroxy - 4 - methoxy benzophenone, or 21-hydroxy-4-methoxybenzophenone in (1) an acrylonitrile modified styrenated alkyd resin and xylene; (2) polyvinyl chloride, dioctyl phthalate, barium cadmium laurate and a triarylphosphite; (3) styrene, alkyd resin, propylene glycol, phthalic anhydride, maleic anhydride, hydroquinone, and copper naphthenate.  Reference has been directed by the Comptroller to Specification 738,096.ALSO:The invention comprises compounds of the formula <FORM:0810570/IV (b)/1> where X is hydrogen or hydroxyl, and R is alkyl, aralkyl, substituted alkyl or alkenyl group.  The compounds may be prepared either by Friedel-Crafts type of reaction where the appropriate alkoxy benzene is reacted with the appropriate acid chloride in the presence of a Friedal-Crafts' catalyst or by selectively etherifying polyhydroxy benzophenones with e.g. dialkyl sulphates, dialkyl halides, aralkyl halides, substituted alkyl halides, halogenated compounds with a carbonyl group such as chloracetic acid bromoacetonitrile, chloracetaldehyde, chloracetone, chloracetophenone, and alkenyl halides.  Examples are given of the preparation of 2 - hydroxy - 41 - methoxybenzophenone, 2,21 - dihydroxy - 4 - methoxybenzophenone, 2 - hydroxy - 41 - butoxybenzophenone, 2 - hydroxy - 41 - dodecyl oxybenzophenone, 2 - hydroxy - 41 - benzyloxy benzophenone, 2 - hydroxy - 41 - (2 - hydroxyethoxy) benzophenone, 2 - hydroxy - 41 - carboxymethoxybenzophenone, 2 - hydroxy - 41 - allyloxybenzophenone, 2,21 - dihydroxy - 41 - butoxy benzophenone, 2,21 - dihydroxy - 41 - benzyloxybenzophenone, 2,21 - dihydroxy - 41 - hydroxy ethoxybenzophenone, 2,21 - dihydroxy-41-allyloxy benzophenone. Reference has been directed by the Comptroller to Specification 789,070.ALSO:Compositions of the general formula <FORM:0810570/IV (c)/1> in which X is hydrogen or hydroxyl and R is alkyl, aralkyl, substituted alkyl, or alkenyl, which absorb ultra-violet light, are applied to textile fabrics.  The textile fibres may be coated by dispersing a concentrated solution of the absorbing agent in xylene in an aqueous bath containing methylated trimethylol melamine, using sodium sulphosuccinate di-2-ethyl hexyl ester or sodium lauryl sulphate as an emulsifier.  Alternatively a dilute solution of the ultraviolet absorber in xylene is applied first to the fabric which is then dried, and then treated in the aqueous resin solution and finally cured.  An example is given of the treatment of nylon with 2 - hydroxy - 41 - carboxymethoxybenzophenone.  Reference has been directed by the Comptroller to Specification 789,070, [Group IV (b)].