Patent GB-941080-A (GB)
Title: Process for the manufacture of unsaturated diene adducts of low-viscosity
IPC: C07C2/72
Filed: 1961-11-03
Abstract: Compounds containing a dicarboxylic acid anhydride group are obtained by a Diels-Alder reaction of maleic anhydride with a multi-unsaturated addition product of a methyl benzene with 2-20 mols (per mol of methyl benzene) of a conjugated diene (see Divisions C4 and C5). In an Example (13) a toluene-butadiene addition product containing mono-, di- and higher-butenylated toluenes is reacted with maleic anhydride at 170 DEG C. for 3 hours.ALSO:Addition compounds of conjugated dienes with methyl benzenes containing two or more diene molecules for each benzene molecule are obtained by reacting 2-20 mols. of the diene with each mol. of methyl benzene in the presence of one or more alkali metals at at least 90 DEG C., e.g. 90-130 DEG C.  The diene may be butadiene, isoprene, piperylene, 2-methylpentadiene-1,3, pentadiene-1,3, cyclopentadiene, methylcyclopentadiene, hexadiene-1,3, 1-chloro-2-methylbutadiene-1,3 or chloroprene.  The methyl benzene may contain other substituents and may be toluene, a xylene, a trimethyl benzene, a tetramethyl benzene, cymene, 1-methyl-2 (or 3- or 4-) -ethyl benzene or commercial solvent mixtures. The products are multi-unsaturated materials; addition occurs at the methyl group(s) forming long chain unsaturated side chain(s) or some polynuclear products may be obtained.  The products are generally of low viscosity, distillable products having viscosities up to about 200 centipoises and residues up to 10,000 centipoises. They may be modified by reaction with maleic anhydride or unsaturated drying or non-drying fatty acids. Polymerization of the addition compounds occurs on heating resulting in products of high viscosity.  Polymers of higher viscosity are also obtained on further reacting the addition compounds with butadiene or maleic anhydride.  Oxidation of the addition compounds may be effected by "blowing" with air, e.g. at 120 DEG C. with or without a metal drier and a solvent and the "blown" products may be further modified by esterification.  Lacquer and paint formulations may be made from the addition compounds, their polymers and their oxidized and other modified products with solvents and metal driers, e.g. a naphthenate or octoate of cobalt, lead, manganese, iron, calcium, cerium, vanadium or zinc, and, if desired, drying oils, amine-formaldehyde resins such as melamine, urea or benzoguanamine resins, epoxy resins, phenolic resins, alkyd resins or fatty acid esters of epoxy resins. They form hard films on casting and drying in air at room or elevated temperature or on curing with a flame.  Epoxy resins are obtained by epoxidation of the addition compounds, e.g. with hypochlorous acid, an organic per-acid or hydrogen peroxide and an organic acid at -20 DEG  to 100 DEG C. Partially epoxidized products also have air-drying properties and may be mixed with drying oils and their stand oils, ethyl cellulose, ester-soluble nitrocellulose, alkyd resins, vinyl resins, fatty acid esters of epoxy resins, some epoxy resins, phenolic resins and amine resins. Completely or partially epoxidized products may be esterified with resin acids or saturated or unsaturated higher fatty acids.  The epoxidized products may also be cured with amines and amides such as butylamine, m-phenylene diamine, ethylene diamines, triethanolamine, guanidine and its derivatives, aniline-, urea-, or melamine-formaldehyde resins, polymerized amino-styrenes, or polyamides from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids, isocyanates, isothiocyanates, polyhydric phenols, phenol-aldehyde resins, reaction products of aluminium alcoholates or phenolates with acetoacetic ester, Friedel Crafts catalysts and their complexes with organic compounds, metal fluorborates, boroxines, phosphoric acid, and polybasic carboxylic acids and their anhydrides such as phthalic anhydride, dodecenyl-succinic anhydride, and hexachloroendomethylene tetrahydrophthalic anhydride; others are specified. Accelerators may also be added, e.g. tertiary amines, strong Lewis bases such as alkali metal alcoholates, hexanetriol or glycerol.  Other polyepoxides may be included in curable mixes such as mono- or poly-glycidyl ethers of mono- or poly-alcohols or -phenols or of phenol-aldehyde resins, polyglycidyl esters of polycarboxylic acids or amino-polyepoxides such as obtained by dehydrohalogenation of the reaction product of an epihalohydrin and an amine. The completely epoxidized products are suitable as lacquer raw materials in combination with methylolated acrylamide copolymers such as described in U.S.A. Specification 2,870,117.ALSO:Sheets of glass, aluminium, iron or steel may be coated by brushing, spraying or doctor machine followed by curing in air at room and/or elevated temperature or by exposure to a flame with lacquer and resin compositions based on the addition products obtained by reacting 2-20 mols of a conjugated diene with each mol of a methyl benzene, or such products modified by oxidation, heating with unsaturated acids or expoxidation (see Divisions C3, C4 and C5).  Coating compositions may also include drying oils, aminoplasts, epoxy resins, phenolic resins or alkyd resins.