Patent GB-758599-A (GB)
Title: Process for the production and use of co-polymerizable unsaturated polyesters
IPC: C08L67/06
Filed: 1954-05-24
Abstract: A copolymerizable unsaturated polyester is made by condensing at 150 DEG  C. or less and in presence of an acid catalyst (a) a ketone, an aromatic hydrocarbon or ether, or a halogenated aromatic hydrocarbon; (b) formaldehyde or a polymer thereof; and (c) an alpha-beta-unsaturated carboxylic acid or anhydride; dissolving the unsaturated polyester formed in an organic solvent so as to separate it from water and water-soluble products, and finally removing the solvent.  Specified reactants are (a)-toluene, ethyl benzene, xylene, mesitylene, diphenyl, diphenylmethane, diphenyl oxide, tetralin, naphthene, anisole, alkyl benzene ethers, resorcinol dialkyl ethers, cyclohexanone, acetophenone, methyl isobutyl ketone and o-dichlorobenzene; (c) maleic, fumaric, itaconic, aconitic and crotonic acid or their anhydrides.  Part of the unsaturated acid may be replaced by a saturated carboxylic acid or anhydride, e.g. adipic, azelaic, sebacic, phthalic, iso-phthalic, terephthalic, tetrachlorophthalic, 1-ethyl pentane carboxylic acid-1 or pelargonic. The unsaturated polyester may be copolymerized with another unsaturated compound, e.g. styrene, 2,5-dichlorostyrene, diallyl phthalate, triallyl cyanurate, vinyl formate, vinyl acetate, vinyl trichloroacetate, vinyl propionate, vinyl benzoate; also the mono-, di-, tri- and tetraallyl esters of polybasic acids, e.g. diallyl maleate, dialkyl diglycol carbonate, triallyl phosphate and tetra-allyl silicate, the corresponding esters of crotyl alcohol, alpha-methyl allyl alcohol, methallyl alcohol, beta-chloroallyl alcohol or beta-methyl crotyl alcohol; acrylic, chloro-acrylic and methacrylic esters; acrylamide and methacrylamide; acrylonitrile; alpha-methyl styrene, vinyl toluene, di- and trivinyl phenol ethers, vinyl anisole, acenaphthylene and divinyl benzene.  Copolymerization may be effected with ultra-violet light, by heating in presence of a polymerization catalyst, e.g. a peroxide, hydroperoxide, ozonide or azo compound, or at normal temperatures in presence of a polymerization catalyst and polymerization activator, e.g. dimethyl aniline, diethyl aniline, hexamethylene tetramine, triethanolamine, cobalt naphthenate or cobalt heptenate. Copolymers from low molecular weight polyesters are rubbery whilst those from high molecular weight polyesters are hard. Copolymerization may be effected in presence of glass powder or fibres, quartz, mica powder, clay, asbestos, calcium sulphate, titanium dioxide, antimony trioxide, cellulose powder or fibres, chlorinated diphenyls, tricresyl phosphate and chloroparaffins. The copolymers may be reinforced with tissues or fibres of glass, polyamides, polyvinylidene chloride, polyvinyl chloride or polyglycol terephthalate.  The polyesters may be used as bonding agents in lacquers, e.g. in combination with wood oil, castor oil or styrenized alkyds.  The polyesters dissolved in a monomer may be used (a) as a casting resin, if desired with calcium carbonate, chlorinated diphenyl or antimony trioxide; (b) as an impregnant in the manufacture of laminated material, e.g. glass mats, glass fabrics, paper, rayon, cotton, sisal, jute, linen, polyamides, polyglycol terephthalate, asbestos and polyacrylonitrile, if desired with calcium carbonate, calcium sulphate, pigments or dyes; (c) as a moulding substance, the solution being mixed with a filler (e.g. clay, alpha-cellulose, asbestos or short glass fibres) and a lubricant (e.g. zinc or aluminium stearate) to give a putty-like mass which may be pre-polymerized or mixed with a preservative, e.g. thiophenol, quinone monooxime, 2,6-dichloro quinone, the imine chloride of quinone or 2,6-dichloroquinone, dihydroxydiphenyl or N - phenyl - 2 - hydroxy - 3 - naphthamide. In examples, the following were condensed in presence of an acid catalyst: (1), (6), (12), (13), (14), (16), (17), (18), (24) xylene, maleic acid or anhydride and formalin or paraformaldehyde; (2) toluene, maleic anhydride and paraformaldehyde; (3) anisole, maleic anhydride and formalin; (4) o-dichlorobenzene, maleic anhydride and paraformaldehyde; (5) xylene, adipic acid, maleic anhydride and formalin; (7) xylene, fumaric acid and paraformaldehyde; (8) tetraline, maleic anhydride and paraformaldehyde; (9) ethyl benzene, maleic anhydride and paraformaldehyde; (10) cyclohexanone, maleic anhydride and paraformaldehyde; (11) diphenyl, diphenyl oxide, maleic anhydride and paraformaldehyde; (15) acetophenone, maleic anhydride and paraformaldehyde; (19) xylene, aconitic acid and paraformaldehyde; (20) methyl isobutyl ketone, maleic anhydride and paraformaldehyde; (21) xylene in n-butyl ether as solvent, maleic anhydride and paraformaldehyde; (22) xylene, crotonic acid and paraformaldehyde; (23) xylene, itaconic acid and paraformaldehyde.  The reactants are heated together at 100-120 DEG  C. for 1-15 hours, benzene or carbon tetrachloride added to dissolve the polyester, and the solvent subsequently distilled off.  In further examples: (25) a xylene-maleic anhydride-formaldehyde polyester is copolymerized with styrene; (26) the polyester of Example 25 is heated with castor oil and copolymerized with styrene; (27) layers of glass fibres are impregnated with a mixture of a xylene-maleic anhydride-formaldehyde polyester, styrene, tricresyl phosphate and dibenzoyl peroxide and then heated; (28)-(30) a mixture of a xylenemaleic anhydride-formaldehyde polyester, styrene and/or diallyl phthalate, tricresyl phosphate, dibenzoyl peroxide, bentonite, asbestos and zinc stearate is rolled to produce a sheet which is granulated if desired and pressed into a sheet; (31)-(32) a lacquer is made by heating a xylene-maleic anhydride-formaldehyde polyester with wood oil or castor oil and adding styrene or white spirits and, if required, a peroxide or Co, Ca, Mn or Zn drier; (33) a varnish is made by dissolving a xylene-maleic anhydride-formaldehyde polyester in a solution of a styrenized alkyd in xylene and adding a Co, Mn, or Ca drier, di-tertiary butyl peroxide and tertiary butyl hydroperoxide.