Patent GB-1132881-A (GB)
Title: Polyether polyester adducts and their use in coating compositions
IPC: C08G59/42
Filed: 1966-01-06
Abstract: 1,132,881. Ester polyol-carboxylic acid adducts. UNION CARBIDE CORP. 6 Jan., 1966 [7 Jan., 1965], No. 577/66. Heading C3R. An ester polyol-carboxylic acid adduct having pendant carboxyl groups comprises the reaction product of (1) an α,#-ethylenically unsaturated polycarboxylic acid or anhydride and (2) a polyester containing less than 20% by weight oxygen which is the reaction product of (a) a polycyclic polyether polyol obtained by polymerizing, in the presence of a non-epoxy hydroxyl compound as a chain length modifier, a polycarbocyclic compound containing at least one bicyclo-[2,2,1]-heptanoid ring, alone or as part of a fused polycarbocyclic ring system having up to 6 carbocycles, at least one cyclic vicinal epoxy group whose vicinal carbon atoms form part of the polycarbocyclic ring structure, and at least one additional hydroxyl equivalent in the form of hydroxyl groups or cyclic vicinal epoxy groups, said polycyclic polyether polyol containing a minimum of 8 repeating units and at least one hydroxyl group per repeating unit, and (b) an unsaturated monocarboxylic compound which is a fatty acid or oil and which is present in an amount sufficient to provide at least 0À9 carboxyl equivalents per hydroxyl equivalent of said polycyclic polyether polyol. The production of the adduct is effected at 175-250 C., generally in the presence of an organic phosphite stabilizer and preferably in the presence of a catalytic amount of iodine. The α,#-unsaturated polycarboxylic acid should be added in such an amount as to give an adduct having an acid number of at least 35. Specified carboxylic acids and their anhydrides are maleic, fumaric, itaconic, glutaconic, citraconic, mesaconic, α-hydromuconic, 1,6-hex-2-enedioic, 1,6-hexa-2,4-dienedioic, alkylidene malonic acids and dialkylmaleic acids. The adducts may be rendered water compatible, i.e. neutralized, by modifying the pendant carboxyl groups in aqueous solution with a water soluble cation to form a hydrophilic carboxylic acid salt. Specified water soluble cations are those derived from ammonia, primary, secondary and tertiary amines, alkanolamines, dialkanolamines, polyamines and cyclic amines and an alkali metal hydroxide may be present. The neutralized resin which contains water may be mixed with an organic cosolvent and subsequently modified with pigments, colorants, driers &c., to produce coating compositions. Specified organic cosolvents are alkylene glycol monoalkyl and dialkyl ethers, the alkyl and dialkyl ethers of diethylene glycol, cyclic ethers, e.g. tetrahydrofuran and dioxane, and diacetone alcohol. Specified opacifying pigments are titanium dioxide, ferric oxide and carbon black; specified extending pigments are silica, talc and clay; a specified colorant is phthalocyanine green. Specified metallic driers are cobalt, manganese and zirconium carboxylic acid salts. The polycyclic polyether polyol starting material of component (2) above which preferably contains an average of 8 to 25 repeating units is obtained by polymerizing a polycyclic epoxy compound in the presence of a non- epoxy hydroxyl-containing chain length modifier and a catalyst. The epoxy monomer may be a monoepoxy polycyclic alcohol or polyol, a diepoxy polycyclic compound, or a diepoxy polycyclic alcohol or polyol, and it may be substituted, preferably with a C 1-6  alkyl group. The additional hydroxyl equivalent of the monomer may be bonded to the polycyclic ring through a bivalent organic radical, e.g. an alkylene, alkyleneoxy or poly(alkylene oxy) radical. The preferred epoxy monomers are characterized by the following carbocyclic ring systems: and those employed in the examples are 5-oxatetracyclo - [6,2,1,0<SP>2,7</SP>,0<SP>4,6</SP>] - undecan - 9,(10) - ol and - 9,10 - diol, 5 - oxatetracyclo - [7,2,1,0<SP>2,8</SP>, 0<SP>4</SP>'<SP>6</SP>]  -  dodecan - 10,(11) - ol, 5 - oxatetracyclo- [6,2,1,0<SP>2,7</SP>,0<SP>4,6</SP>] - undec - 9,(10) - oxyethanol, 10 - oxatetracyclo - [6,3,1,1<SP>3,6</SP>,0<SP>2,7</SP>0<SP>9,11</SP>]- tridecan - 4,(5) - ol, and 10 - oxapentacyclo - [6, 3,1,1<SP>3,6</SP>,0<SP>2,7</SP>,0<SP>9,11</SP>]-tridecane-4,5-diol. Specified chain length modifiers are those of formula ROH where R is hydrogen or a monovalent organic radical free from substituents other than alcoholic hydroxy groups. The esterification of the polycyclic polyether polyol may be effected at an elevated temperature in an inert solvent, preferably under an inert atmosphere and using a catalyst, e.g. a tetraalkyl titanate or a basic catalyst such as an alkali metal hydroxide, lithium acetate, calcium naphthenate or an amine and the product preferably has an acid number less than 20. The unsaturated monocarboxylic acids used in the examples are soya, tall and safflower acids.