Patent GB-873561-A (GB)
Title: Unsaturated polyesters, their production and use
IPC: C08G63/91
Filed: 1959-10-27
Abstract: New unsaturated polyesters are made by polycondensing a polycarboxylic acid (or a functional derivative thereof) with an unsaturated dihydric alcohol of formula: <FORM:0873561/IV (a)/1> where R1-R8 are hydrogen atoms or monovalent substituents such as halogen atoms, alkoxy groups or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon groups. Polyesterification may be effected in the presence of a catalyst (e.g. p-toluene sulphonic acid) and an azeotropic solvent (e.g. benzene, toluene or chlorobenzene).  The acid may be oxalic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, hexahydrophthalic, tricarballylic, phthalic, isophthalic, terephthalic, 2 : 6-naphthalene dicarboxylic, diphenyl-o, o1-dicarboxylic, pyromellitic, maleic, fumaric, mesaconic, citraconic, itaconic, tetrahydrophthalic, or aconitic acid or ethylene glycol-bis-(p-carboxyphenyl)-ether.  Additional polyhydric alcohols may also be incorporated into the polyesters, such as ethylene-, diethylene-, triethylene-, 1 : 2- or 1 : 3-propylene-, 1 : 4-butylene-, 2-methyl-2 : 4-pentylene-, 1 : 5 pentylene-, or 1 : 6-hexylene-glycol; or glycerine, diglycerine, trimethylolethane, trimethylolpropane, butane1 : 2 : 4-triol, hexanetriol or pentaerythritol.  The polyesters may be stabilized by methylene blue, hydroquinone, tert-butylcatechol or copper salts.  Coating compositions are made by dissolving the polyester in a solvent (e.g. chloroform) and adding an iron, nickel or cobalt drier (e.g. cobalt naphthenate or 2-ethylhexanate) and, if desired, linseed oil an alkyd resin or a styrenated oil.  Products suitable as casting resins, laminating resins, trowelling compounds or lacquer bases are made by mixing the polyesters with a polymerizable compound (e.g. styrene, a vinyl ester, an acrylic or methacrylic acid ester, acrylonitrile or another unsaturated polyester), a polymerization catalyst (e.g. benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, methylethylketone peroxide or hydroxycyclohexylhydroperoxide) and a metal drier. Drying of the lacquers may be accelerated by the addition of a wax (e.g. paraffin wax) or a waxy substance which is also a drier (e.g. CO-, Mg-, Ca-, Pb-, Fe-, Ni-, Zn- or Al-palmitate, -stearate or -montanate).  The double bonds in the cyclohexene groups of the polyester may be converted into epoxy groups by treatment with peracetic or perbenzoic acid and such epoxidized polyesters may be cured with amines or carboxylic anhydrides.  If the polyesters are derived from unsaturated polycarboxylic acids, the double bonds of the acid component are maintained during epoxidation, so that the epoxidized polyesters may be copolymerized with styrene.  In examples polyesters are made from 1, 1-bis-[hydroxymethyl]-cyclo-3-hexene or its 6-methyl derivative and (1) and (3) adipic acid; (2) and (4) adipic acid and maleic anhydride; (5) adipic acid, maleic anhydride and phthalic anhydride; (6) adipic acid, maleic acid, phthalic anhydride, ethylene glycol and diethylene glycol; (7)-(10) fumaric acid, phthalic anhydride and ethylene glycol.  In further examples (11) lacquers comprise a polyester of Examples 1, 2 or 3, chloroform and cobalt octoate; (12) Lacquers comprise the polyester of Example 2, styrene, tert.-butyl hydroperoxide and cobalt octoate; (13)-(15) casting compositions comprise the polyester of Example 4, 5 or 6, styrene and benzoyl peroxide or methylethylketone peroxide+cobalt octoate; (16)-(17) Lacquers comprise the polyester of Examples 7 or 8, styrene, cellulose acetobutyrate, methylethylketone peroxide and cobalt octoate; (18)-(19) Casting compositions comprise the polyester of Example 9, styrene, methylethylketone peroxide and, possibly, cobalt octoate; (20)-(21) Glass fibre matting is laminated with a composition comprising the polyester of Example 9, styrene, methylethylketone peroxide and, possibly, cobalt octoate; (22) The polyester of Example 3 is epoxidized with peracetic acid and then cured with phthalic anhydride or bis-(D 3-tetrahydrobenzyl)-amine. Specification 830,794 is referred to.