Patent GB-779838-A (GB)
Title: Ethylenically unsaturated polyhydroxy-substituted polyesters, their preparation and compositions containing the same
IPC: C08G63/58
Filed: 1954-12-21
Abstract: Ethylenically unsaturated polyhydroxy substituted polyesters are made by esterifying an aliphatic polyhydric alcohol containing from 2 to 6 esterifiable hydroxyl groups in the molecule with a dicarboxylic acid or anhydride thereof containing not more than 18 carbon atoms in the molecule in a chemically equivalent ratio of 1 : 1 to 1 : 3, the resultant acid ester being reacted with a chemically equivalent ratio of from 1 : 1 to 1 : 8 of a monoepoxide containing not more than 16 carbon atoms in the molecule, the epoxy group being in a terminal position; the dicarboxylic acid or anhydride and/or the monoepoxide and/or the polyhydric alcohol being ethylenically unsaturated.  Many polyalcohols, which may contain oxygen, sulphur or nitrogen atoms between the carbon atoms are specified, examples being glycerol, pentaerythritol, glycerol allyl ether, 3,5-dithiahexanediol-1,6, 1,2,6-hexanetriol and polymers of ethylenically unsaturated monohydric alcohols, e.g. polyallyl alcohol and polyvinyl alcohol. Specified dicarboxylic acids include maleic acid, phthalic acid, fumaric acid, 3,31-thiodipropionic acid, 1,4-cyclohexadiene-1,2-dicarboxylic acid and 3-methyl-5-decenedioic acid.  The esterification is effected at temperaperatures below 200 DEG  C., suitable solvents being benzene, toluene, methyl ethyl ketone, ethyl acetate, glycol monoacetate and dioxane. Polymerization inhibitors, e.g. sulphur, hydroquinone and tannic acid may be present if the acid and/or the base are unsaturated.  Many epoxides are specified, examples being allyl glycidyl ether, epichlorhydrin, ethylene oxide, glycidyl methacrylate, butyl glycidyl sulphone, styrene oxide and compounds of the formula: <FORM:0779838/IV(a)/1> where X is hydrogen, R, -R1OR, OR,-R1SR, SR, R1SO2R, SO2R, <FORM:0779838/IV(a)/2> , <FORM:0779838/IV(a)/3> , <FORM:0779838/IV(a)/4> and <FORM:0779838/IV(a)/5> where R1 is a bivalent and R a monovalent hydrocarbon radical, the acid ester and the monoepoxide being reacted at temperatures below 200 DEG  C.  In the examples: (1) an acid ester prepared from a polyallyl alcohol of molecular weight 650, containing approximately 5.5 hydroxyl groups per molecule and maleic acid is reacted with allyl glycidyl ether; (2) the polyalcohol as in (1) is esterified with phthalic, anhydride, the product being reacted with allyl glycidyl ether; (3) glycerol is esterified with a mixture of phthalic and maleic anhydrides, the product being reacted with allyl glycidyl ether; (4) glycerol beta-allyl ether is esterified with phthalic anhydride, the product being reacted with allyl glycidyl ether and polymerized in the presence of di-tertiary butyl peroxide; (5) as in (4) but using glycerol monoacetate and a -ethyl ether instead of the glycerol beta-allyl ether; (6) glycerol is esterified with maleic anhydride, the product being reacted with phenyl glycidyl ether; (7) 1,2,6-hexanetriol is esterified with maleic anhydride, the product being reacted with styrene oxide; (8) polyallyl alcohol (as in Example (1)) is esterified with phthalic anhydride and the product reacted with glycidyl acrylate in the presence of hydroquinone.  The substituted polyesters containing ethylenically unsaturated linkages may be polymerized with ethylenically unsaturated monomers, e.g. styrene, methyl acrylate, allyl acetate, vinyl chloride, acrylonitrile, cyclopentadiene and vinyl ethyl ether by heating in the presence of a peroxide catalyst, e.g. benzoyl peroxide, lauryl. peroxide and tertiary-butyl hydroperoxide, The polyesters may also be reacted with polyisocyanates and polycarboxylic acids to form hard products suitable for use as castings; they may also be suspended in a liquid vehicle, e.g. methyl ethyl ketone for use as coating or impregnating compositions.