Patent GB-1003549-A (GB)
Title: A process for the preparation of alkyd resins
IPC: C08G63/46
Filed: 1963-12-18
Abstract: An alkyd resin is prepared from a polyhydroxy compound or epoxy-compound a polycarboxylic acid or anhydride and 3-phenylisovaleic acid. Either acid may be present as an epoxyalkyl ester.  Epoxyalkyl groups specified are 2,3-epoxy-butyl, 3,4-epoxybutyl, 2,3-epoxyhexyl, 2,3-epoxy - 4 - phenyl - octyl, 1 - ethyl - 2,3 - epoxyhexyl, 2,3 - epoxy - 4,5 - diethyldodecyl, glycidyl and epoxycyclohexyl groups.  Polyvalent alcohols specified are glycerol, trimethylol methane, trimethylol ethane, trimethylol propane, hexane-1,2,6-triol, pentaerythritol, sorbitol, inositol, tetramethylolhexanol, dierythritol, polyerythritol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, polyoxymethylene glycols, polyoxypropylene glycols, 1,2-butylene glycol, 1,4-butylene glycol, 1,5-pentane diol, 2,4-pentane diol, 1,4-hexane diol, 1,5-hexane diol, 1,6-hexane diol, 2,5-hexane diol, 3-methyl-1,5- pentane diol, 2,2-dimethyl-1,3-propane diol, 2-ethyl-1,3-hexane diol, 2,5-dimethyl-2,5-hexane diol, 1-butene-3,4-diol, 2-butene-1,4-diol, glycerides of monocarboxylic saturated or unsaturated, branched or unbranched acids and adducts of bisphenols and glycidyl esters of monocarboxylic acids in which the carboxyl group is directly attached to a tertiary or quaternary carbon atom. Polybasic acids specified are 1,2,3-, 1,2,4- and 1,3,5-benzene tricarboxylic acid, 1,2,3,4-, 1,2,3,5- and 1,2,4,5-benzene tetracarboxylic acid, benzene pentacarboxylic acid, benzene hexacarboxylic acid, propane-1,2,3-carboxylic acid, propene-1,2,3-carboxylic acid, 2-propanol-1,2,3-tricarboxylic acid, malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, adipic acid, azeleic acid, sebacic acid, mesaconic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, diglycolic acid, tetrahydrophthalic, glutaric and dimerized drying oil fatty acids, e.g. that from soyabean oil.  Either acid component may be added to the polyol first or both may be added together.  The condensation may be at 130-270 DEG  C. and may be a batch or continuous process.  There may also be present monocarboxylic acids or their epoxyalkyl esters in which the carbonyl group is directly attached to a tertiary or quaternary carbon atom. These may be produced by treating olefins, e.g. cracked petroleum fractions, or paraffins to which an H2 acceptor, e.g. an olefin, alcohol or alkyl halide has been added with CO/H2O or HCOOH in the presence of an acid catalyst, e.g. H2SO4, H3PO4 and complexes of H3PO4, BF3 and H2O.  Othe monocarboxylic acids which may be present may be saturated or unsaturated, aliphatic, alicyclic or aromatic, e.g. capric, lauric, maleic, myristic, palmitic, benzoic, p-tert-butylbenzoic, acrylic, methacrylic and fatty acids derived from linseed, chinawood, soyabean, fish, cottonseed, oiticica, perilla, sunflower and dehydrated castor and tall oils.  Other additives may be solvents, e.g. xylene, pigments, thickeners, driers, e.g. Co, Mn and Pb organic salts, and other resins, e.g. phenol, urea and melamine/formaldehyde resins. Where unsaturated acids are present the product may be cured by adding a catalyst, e.g. benzoyl, di-tert-butyl, dicumyl peroxides, cumyl hydroperoxide, azoisobutyronitrile and Lewis acids.  The products may be used as paints lacquers, varnishes and stove enamels.  In examples, the reactants are (II) 3-phenylisolvaleric acid, lauric acid, glycerol, phthalic anhydride and xylene, (III) 3-phenylisovaleric acid, glycerol, phthalic acid and xylene, (V) the glycidyl ester of lauric acid, the glycidyl ester of 3-phenylisovaleric acid, phthalic anhydride, glycerol and xylene, and (VI) the glycidyl ester of 3-phenylisovaleric acid, phthalic anhydride, glycerol and xylene.ALSO:Glycidyl 3-phenyl isovalerate may be prepared by interacting 3-phenyl isovaleric acid or an alkali metal or quaternary ammonium salt thereof and epichlorohydrin.  The salt may be added dry or in aqueous solution to the epichlorohydrin or an alkali metal hydroxide solution may be added to a mixture of the acid and epichlorohydrin.  If acid itself is added to the epichlorohydrin, excess acid or equivalent quantities of reactants will yield a chlorohydrin from which the ester may be produced by adding alkali. A 2: 1 excess of epichlorohydrin over acid will produce the ester directly.  Both reactions are catalysted by tertiary amines and quaternary ammonium salts.  Water added or produced may be removed azeotropically.