Patent GB-1028919-A (GB)
Title: Improvements relating to polyesters
IPC: C08G63/06
Filed: 1963-11-06
Abstract: Linear polyesters having units of the structure <FORM:1028919/C3/1> in which Q is an arylene, aralkylene, alkylene or cycloalkylene radical of 2-20 carbon atoms are prepared by interacting a diol or esterforming derivative thereof with bicyclo-[2,2,2]-octane - 1,4 - dicarboxylic acid or a mixture of dicarboxylic acids containing this acid. Ester-forming derivatives include acid chlorides and alkyl or aryl esters.  Such esters should be derived from alcohols or phenols of lower boiling point than the diol, e.g. CH3OH and C2H5OH.  At least 1 mole of diol or ester-forming derivative thereof should be used per mole of dicarboxylic acid.  Ester forming derivatives of diols include epoxides and lower alkyl esters, e.g. acetates.  The latter may be prepared in situ.  Reaction is effected by heating the reaction mixture above its melting-point and the boiling point of alcohol to be eliminated at atmospheric or sub- or superatmospheric pressure.  In using an acid chloride it may be dissolved in 1,1,2-trichloroethane and added to the diol in aqueous NaOH. Catalysts specified are manganous acetate, calcium acetate, litharge, sodium methoxide, sodium hydrogen hexabutoxytitanate, SbO3, zinc acetate and sodium acetate.  After the reaction heating may be continued under reduced pressure to remove the excess diol.  The product may be molten or solid.  The proportion of ester groups derived from bicyclooctane-1,4-dicarboxylic acid may vary from less than 50 to 100%.  Mixed polyesters may be produced by heating a molten mixture of homopolyesters under a nitrogen atmosphere.  The products may be made into films, fibres or shaped articles.  Diols specified are: resorcinol, 2,6-methylol-decahydronaphthalene, p - dimethylol - cyclohexane, 2,2-di - p - phenyl - propane, ethylene glycol, propylene glycol, butylene glycol, 2,2-dimethyl propylene glycol, 2,2,3,3,4,4 - hexafluoro-1,5 pentanediol, hexamethylene glycol, decamethylene glycol, diethylene glycol, ethylene thiodiglycol, quinitol, 4,41-dimethylol-dicyclohexyl, 2,2 - bis - (4 - hydroxymethylcyclohexyl) - propane, 2,3 - bis - (4 - hydroxymethylcyclohexyl) butane, 2,3-dimethyl-2,3-bis - (4 - hydroxymethylcyclohexyl) butane 1,4 - bis - (4 - hydroxymethylcyclohexyl) cyclohexyl, 1,4 - bis - (3 - hydroxypropyl) benzene, 1,4 - bis - (2 - hydroxyethyl) benzene, 2,6- bis - (2 - hydroxyethyl) naphthalene, 1,4- bis - (2 - hydroxyethoxy) benzene, bis - 4 - (2-hydroxyethoxy) phenyl sulphone, 4,41 - dihydroxybiphenyl, 3,31 - dibromo - 4,41 - dihydroxybiphenyl, 3,31 - difluoro - 4,41 - dihydroxybiphenyl, bis - (4 - hydroxyphenyl) methane, 1,1 - bis - (4 - hydroxyphenyl) ethane, 2,2 - bis - (3,5 - dichloro - 4 - hydroxyphenyl) propane, bis - (4 - hydroxyphenyl) ether, bis - (4 - hydroxyphenyl) sulphone, bis-(4 - hydroxyphenyl) ketone, bis - (4 - hydroxyphenyl) sulphoxide, 1,2 - bis - (4 - hydroxyphenyl) ethane, bis - (4 - hydroxyphenyl) oxindole, phenolphthalein and phenolphthalimidine. In addition, diols containing sulphide, sulphonyl, amide or anhydride groups may be used.  Dicarboxylic acids specified are: bibenzoic acid, 2,21- and 3,31-dimethyl-4,41-bibenzoic acid, 2,21 - dibromo - 4,41 - bibenzoic acid, bis - (4 - carboxyphenyl) methane, 1,1 - and 1,2 - bis - (4 - carboxyphenyl) ethane, 2,2 - bis - (4 - carboxyphenyl) propane, 1,2 - bis - (4 - carboxyphenoxy) ethane, bis - 4 - carboxyphenyl ether, bis - 4 - carboxyphenyl sulphide, bis - 4 - carboxyphenyl ketone, bis - 4 - carboxyphenyl sulphoxide, bis - 4 - carboxyphenyl sulphone, 2,8 - dibenzofuran dicarboxylic acid, terephthalic acid, methyl terephthalic acid, 2,5 or 2,6-dimethyl terephthalic acid, chloroterephthalic acid, 2,5-dichloroterephthalic acid, fluoroterephthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, naphthelenic dicarboxylic acids, phenylene diacetic acid, 4-carboxyphenoxyl acetic acid, m- and p-terphenyl-4,41-dicarboxylic acid, dodecahydrobibenzoic acid, hexahydroterephthalic acid, 4,41 - stilbene dicarboxylic acid, 4-(2 - hydroxyethyl benzoic acid, 4-(2-hydroxyethoxy) benzoic acid.  Halogen and dialkogen containing acids may also be used in the invention.  There may also be present minor amounts of diols or dicarboxylic acids having metallic sulphonate salt, carboxylate salt or phosphonate salt groups present. In the examples, bicyclooctane dicarboxylic acid (1 and 7) or its dimethyl ester (2-6) are treated with (1) resorcinol diacetate, (2) decahydro-2,6-bis-hydroxymethyl naphthalene, (3) and (4) hexahydro - p - xylene glycol, (5) ethylene glycol, (6) dimethylol - bicyclooctane, and (7(diphenylol propene diacetate.  Example (5) was repeated in the presence of terephthalic acid.  In Example (1) a mixture of diphenyl and diphenyl oxide was present.