Patent GB-1128054-A (GB)
Title: Polyester adducts and water-based coating compositions containing them
IPC: C08G63/42
Filed: 1965-09-27
Abstract: 1,128,054. Polyesters. UNION CARBIDE CORP. 27 Sept., 1965 [5 Oct., 1964], No. 40957/65. Headings C3B and C3R. A polyester-carboxylic acid adduct is made by reacting (I) an α,#-ethylenically unsaturated dicarboxylic acid or anhydride with (II) a polyester containing less than 20% oxygen which is the reaction product of (a) a polycarbocyclic compound having a ring structure containing at least one bicyclo-[2.2.1]-heptanoid ring and at least three hydroxyl equivalents in the form of hydroxyl groups and/or vicinal epoxy groups forming part of the ring structure, (b) a polycarboxylic acid or anhydride and (c) an unsaturated fatty acid or fatty oil; ingredients (b) and (c) being present in a combined amount sufficient to provide at least 0À9 carboxyl equivalents per hydroxyl equivalent of (a). The polycyclic compound may be a tri- or higher polyhydric alcohol, a monoepoxide containing one or more alcoholic hydroxyl groups or a diepoxide which may contain one or more alcoholic hydroxyl groups and preferably contains one of the ring structures The alcoholic groups may be bonded to the polycyclic ring directly or through an alkylene, alkyleneoxy or poly(alkyleneoxy) group. The polycarboxylic acid may be aliphatic, aromatic or alicyclic, may contain 2-6 carboxyl groups and may be in the form of a carboxyl terminated polyester. The unsaturated monocarboxylic acid may contain 4-22 carbon atoms. The polyester preferably has an acid number of less than 20 and prior to its adduction with the unsaturated dicarboxylic acid may have an additional amount of unsaturated monocarboxylic acid added to it. Adduction is preferably effected at 175 to 250 C. in the presence of iodine as a catalyst and an organic phosphite as a stabilizer. The adduct is then rendered water-compatible by forming a salt of it with an ammonia or a water-soluble primary, secondary or tertiary amine (including alkanolamines, polyamines and cyclic amines), possibly in admixture with a minor amount of an alkali metal hydroxide. Coating compositions are made by dissolving these salts in a mixture of water and a water-soluble organic solvent, preferably a glycol or a monoalkyl or dialkyl ether thereof. The coating compositions may also contain a pigment (e.g. titanium dioxide, ferric oxide, carbon black, silica, talc, clay or phthalocyanine green), a vinyl type latex (e.g. butadiene/styrene copolymer, polystyrene or polyvinyl acetate) or a metallic drier (e.g. a naphthenate, linolate, tallate or octoate of cobalt, manganese or zirconium). A very large number of reactants suitable for making the salts of the polyester adducts are specified but those, i.e. in the actual examples are: Polycyclic compounds.-4 - Oxatetracyclo [6.2.1.0<SP>2</SP>'<SP>7</SP>.0<SP>3</SP>'<SP>5</SP>]undecan - 9-(10) - ol; 4 - oxatetracyclo [6.2.1.0<SP>2</SP>'<SP>7</SP>.0<SP>3</SP>'<SP>5</SP>] undec - 9(10) - oxyethanol; 5 - oxapentacyclo[6.6.1.0<SP>2,7</SP>.0<SP>4,6</SP>.0<SP>9,14</SP>] pentadec - 11 - ylmethyleneoxyeth anol; 10 - oxapentacyclo[6.3.1.1<SP>3,6</SP>.0<SP>2,7</SP>.0<SP>9,11</SP>]- tridec - 4,5 - di(oxyethanol); tricyclo[5.2.1. 0<SP>2</SP>'<SP>6</SP>]decan - 4,5,8,9 - tetrol; 5 - oxaheptacyclo- [7.6.1.1<SP>3,7</SP>.1<SP>11,14</SP>.0<SP>2,8</SP>.0<SP>10,15</SP>]octadecane - 12,13- diol; 10 - oxapentacyclo[6.3.1.1<SP>3,6</SP>.0<SP>3,7</SP>0.<SP>9,11</SP>]- tridecane - 4,5 - diol; 5 - oxapentacyclo[7.6.1. 0<SP>2</SP>'<SP>8</SP>.0<SP>4,6</SP>.0<SP>10,15</SP>]hexadec - 12 - ylmethyleneoxyhexanediol; 5,10 - dioxapentacyclo[6.3.1.0<SP>2,7</SP>. 0<SP>4</SP>'<SP>6</SP>. 0<SP>9</SP>'<SP>11</SP>]dodecane; Polycarboxylic acids.-Tetrahydrophthalic anhydride, adipic acid, succinic acid or anhydride, 1:2:4-hexanetricarboxylic acid, bicyclo[2.2.1]- 5-heptene-2,3-dicarboxylic acid, a mixture of phthalic anhydride and maleic anhydride; Monocarboxylic acids.-Soya acids, tall acids, safflower acids; Unsaturated dicarboxylic acids.-Maleic anhydride, glutaconic acid, ethylidene malonic acid, fumaric acid, itaconic acid; Salt forming reactants.-N,N - Dimethylethanolamine, ammonia, N-methylmorpholine, piperidine, triethylamine, morpholine.