Patent GB-1001705-A (GB)
Title: Derivatives of 2,2-dihydroxybenzophenone
IPC: C08K5/132
Filed: 1962-03-23
Abstract: Polymers which are stable to ultra-violet light are derived from 2,21-dihydroxybenzophenones substituted in the 4-position by groups -O-CO-R-CO-X, in which R is the residue of a di-, tri- or tetracarboxylic acid and X is Br, Cl, OH or C1- 9 alkoxy, and optionally substituted in the 41, 6 and 61 positions with the same group or OH or alkoxy in which the alkyl group is 1-18 carbon atoms and may optionally be substituted with halogen, alkoxy, hydroxyalkoxy, cyano or aryloxy. The other positions in the benzene rings may be substituted by halogen, alkyl, alkenyl, cyano, hydroxyalkyl, cyanoalkyl, halo-alkyl, SO2CH3, SO2CH2Ph, alkoxy or alkaryl. The compounds are prepared from a 2,21-dihydroxy benzophenone having one or both 4 positions hydroxyl substituted and a dicarboxylic acid, halide, anhydride or ester. Many such ketones are specified. Acids specified are oxalic, malonic, succinic, glutaric, adipic, pimelic, azelaic, maleic, sebacic, suberic, hexahydrophthalic, phthalic, isophthalic, terephthalic, naphthalic, tricarbalkylic, trimesic, trimesitic, pyromellitic, malic and citric. The product of this reaction may be reacted as acid, acid chloride or ester with hydroxyl or amino groups in another monomer, a prepolymer or a polymer, e.g. monomers and polymers of phenol/formaldehyde, melamine/formaldehyde, polyamides, aniline/formaldehyde, styrene, maleic and acrylic monomers. In Examples (1), (3), (7), (9), (11) and (16) polyesters are prepared from phthalic anhydride, succinic anhydride, diethylene glycol and (1) the monosuccinate of 2,4,21-hydroxy-41-methoxybenzophenone, (3) the monooxalate of 2,4,21 - trihydroxybenzophenone, (7) the monosuccinate of 2,4,21-trihydroxybenzophenone, (9) the monosuccinate of 2,4,21-trihydroxy - 31 - allylbenzophenone, (11) the monosuccinate of 2,21,4-trihydroxy-51-benzylsulphonylbenzophenone and (16) the monosuccinates of 2,4,21-trihydroxy-51-allylbenzophenone, 2,4,21 - trihydroxy - 51 - (b  - cyano-b ,b  - dibromo - a ,a  - dichloroethyl) benzophenone, 2,4,21 - trihydroxy - 51 - b  - phenylethylbenzophenone, 2,4,21,41 - tetrahydroxy - 5-b  - methoxyethylbenzophenone and 2,4,21,41-tetrahydroxy - 5 - b  - cyanoethylbenzophenone. The products are mixed with styrene. In Examples (2), (8), (10) and (13) polyestero resins are prepared from phthalic anhydride, glycerol, styrene and (2) the monophthalate of 2,4,21-trihydroxybenzophenone (8) the diphthalate of 2,21,4,41 - tetrahydroxybenzophenone, (10) the monophthalate of 2,4,21 - hydroxy - 41 - chlorobenzophenone and (13) the diphthalate of 2,4,21,41 - tetrahydroxy - 6 - g  - chloropropylbenzophenone. In Examples (14) and (15) polyester resins are prepared from benzoyl peroxide, a styrene/maleic anhydride/phthalic anhydride/ethylene glycol polymer and (14) the monomaleate of 2,4,21-trihydroxy-41-methoxybenzophenone and (15) the monomaleate of 2,4,21-trihydroxybenzophenone. In Examples (4) and (5) melamine/formaldehyde resins are prepared from the monosuccinate of 2,4,21-trihydroxybenzophenone, melamine and formaldehyde. Specification 832,043 is referred to.ALSO:The invention comprises 2,21-dihydroxybenzophenones which are substituted in the 4-position by a group -O-CO-R-CO-X and optionally in the 6,41- or 61-positions by the same group, or by other groups such as -OH or substituted or unsubstituted alkoxy, aryloxy, aralkoxy or alkaryloxy radicals.  In the formula, R is the nucleus of a polycarboxylic acid and X is halogen, e.g. Cl or Br, -OH or -O-C1- 9 alkyl.  Other non - chromophoric groups including halogen, alkyl, cyano, hydroxyalkyl, cyanoalkyl, haloalkyl and alkyl- or aralkylsulphonyl may also be present, as substituents in the benzene nuclei.  The compounds of the invention are prepared by introducing the -O-CO-R-CO-X group by reaction of the corresponding substituted benzophenone with the appropriate polycarboxylic acid, monoester, anhydride or acid chloride, or the thus formed acid (X = OH) is converted to the ester or acid halide, e.g. chloride or bromide.  The hydroxybenzophenone starting materials are obtained by condensing the appropriately substituted salicylic acid with resorcinol in presence of phosphoric acid, zinc chloride and phosphorus oxychloride or trichloride. Specification 832,043 is referred to.