Patent FR-1451295-A (FR)
IPC: C07D303/26
Filed: 1965-05-18
Granted: 1966-01-07
Abstract: A polyester is the reaction product of (I) a monoepoxy alcohol which is a 4-oxatetracyclo [6.2.1.02'7.O3'5] undecane substituted in the 9, or 9, 10 or 10, 11 positions by hydroxy, hydroxyalkoxy, polyhydroxyalkoxy, or hydroxy-(polyalkyleneoxy) groups, or a 10-oxapentacyclo [6.3.1.13'6.O2'7.O9'11] tridecane substituted in the 4 or 4,5 positions by the above groups or by hydroxylkyl, hydroxyalkoxymethyl, polyhydroxyalkoxymethyl or hydroxy-(polyalkyleneoxy) alkyl groups; (II) a saturated or unsaturated fatty acid or oil sufficient to provide 0.1 to 1.0 carboxy groups per hydroxy group of (I); and (III) a polycarboxylic acid or anhydride sufficient to provide 0.2 to 3.0 carboxy groups per epoxy group of (I).  Coating compositions contain the polyester preferably dissolved in an inert solvent, e.g. an aromatic cycloaliphatic or paraffin hydrocarbon or a ketone or ether, which may have been used as a medium for the polyesterification.  Preferred monocarboxylic acids (II) include hexanoic, caprylic, lauric, capric, myristic, palmitic, stearic, arachidic, palmitoleic, oleic, linoleic, linolenic, eleostearic, licanic, ricinoleic, hexenoic hexadienoic, and octenoic acids, and mixtures derived from castor, dehydrated castor, coconut, cottonseed, linseed, oiticica, perilla, olive, safflower, sardine, soybean, tung or tall oils. Suitable polycarboxylic acids (III) include oxalic, malonic, succinic, adipic, pimelic, suberic, sebacic, alkyl- and alkenylsuccinic, maleic, fumaric, glutaconic, isopropylidene-malonic, muconic, diglycollic, dilactic, 2-carboxy - 2 - methyl - cyclohexaneacetic, phthalic, 1:2 - naphthalene dicarboxylic, 5 - octene-3:3:6 - tricarboxylic, 1:2:4 - benzene - tricarboxylic, 1:2:3:4 - benzene - tetracarboxylic acids and polymerized fatty acids and polycarboxy polyesters.  A large number of suitable anhydrides are also listed.  These include glutaric, succinic and alkylsuccinic, maleic and chloromaleic, itaconic, citraconic, phthalic and various hydro- and halophthalic, chlorendic and other Diels Alder anhydrides, and polymeric iso- and terephthalic anhydrides.  A preferred component (III) comprises a major amount of tetrahydrophthalic anhydride and a minor amount of maleic anhydride.  Suitable catalysts include HClO45H2SO4, H3PO4, alkyl an aryl sulphonic acids, tetraalkyl titanates, NaOH, KOH, Li acetate, and tertiary amines.  The product solutions may be used as paints and may have added thereto driers e.g. Co naphthenate or Co or Pb octoate, fillers and pigments e.g. Fe oxides, chrome green, chrome yellow, white lead, talc, SiO2, TiO2, PbO or ZnO, and other resins e.g. aminoplasts, acrylics, urethanes, epoxy resins, vinyl resins and nitrocellulose. Examples 1-10 describe the preparation of epoxy compounds.  In Examples 11-17 4 - oxatetracyclo [6.2.1.02'7.O3'5] undecan - 9-ol or -9-oxyethanol is condensed with soya fatty acids, linseed oil, lauric acid or tall oil acids and phthalic/maleic anhydride mixture, sebacic acid, phthalic anhydride or tetrahydrophthalic/maleic anhydride mixture.  The product is thinned with xylene or mineral spirit, an MF resin may be added, a drier is added and the solution is used to coat steel panels or glass.ALSO:The preparation is described of monohydroxy and polyhydroxy monoepoxy compounds which are (a) 4-oxatetracyclo[6.2.1.02'7.03'5]undecanes substituted in the 9 or 9:10 or 10:11 positions by hydroxy, hydroxyalkoxy, polyhydroxyalkoxy or hydroxy(alkyleneoxy or polyalkyleneoxy) groups or (b) 10-oxapentacyclo[6.3.1.13'6.02'7. -09'11]tridecanes substituted in the 4 or 4:5 positions by the above substituents or by hydroxyalkyl, hydroxyalkoxymethyl, polyhydroxyalkoxymethyl, or hydroxy(alkyleneoxy or polyalkyleneoxy)alkyl groups.  They are prepared by treating tetracyclo[6.2.1.13'6.02'7]-dodeca-4:9-diene with a polyol or H2O2 or by reacting dicyclopentadiene with aqueous H2SO4, H2O2, Pb(OAc)4, or a polyol, or by reacting 2 mols of cyclopentadiene with vinyl acetate (later hydrolysed), an alkenol, allyl hydroxyalkyl ether, allyl polyhydroxyalkyl ether or alkenediol.  The products may be reacted with an alkylene oxide, if desired, and finally in all cases the remaining double bond is epoxidized. Such procedures are described in Examples 1-10. In Examples 3 and 8 the unsaturated precursor of the epoxy compound is isolated.ALSO:Coating compositions contain dissolved in an inert solvent the alkyd resin produced by reacting together (I) a monoepoxy alcohol which is 4-oxatetracyclo [6.2.1.02,7.O3,5] undecane substituted in the 9 or 9:10 or 10:11 positions by hydroxy, hydroxyalkoxy, polyhydroxyalkoxy, or hydroxy (polyalkyleneoxy) groups or a 10- oxa pent a cyclo [6.3.1.13,6.02,7.09,11] tridecane substituted in the 4 or 4 : 5 positions by the above groups or by hydroxyalkyl hydroxyalkoxymethyl, polyhydroxyalkoxymethyl or hydroxy (polyalkyleneoxy) alkyl groups, (II) a saturated or unsaturated fatty acid or oil sufficient to provide 0.1-1.0 -COOH groups per hydroxy group of (I), and (III) a polycarboxylic acid or anhydride sufficient to provide 0.2-3.0 -COOH groups per epoxy group of (I).  (see Division C3).  There maybe added driers, fillers, pigments and other resins, e.g.:-Co and Pb octoates and naphthenates; ZnO, PbO, TiO2, SiO2, Feoxides, chrome green, white lead, talc, chrome yellow; aminoplasts, acrylics, urethanes, epoxy resins, vinyl resins and nitrocellulose.  In Examples [11-17] alkyd resins of the above type are thinned with xylene or mineral spirits, driers and optionally an MF resin are added, and the resulting paints are dipped, sprayed or cast onto metal (steel) or glass panels.