Verfahren zur Herstellung von selbstvernetzenden Polymerisaten

摘要

An addition-polymerizable monomer is prepare by esterifying a compound (I) wherein each group A is -N(CH2.O.R) or -NH.CH2.OR and R is H or a C1- 4 alkyl group, with an acrylic or methacrylic acid or ester of the formula CH2 = CR1-COOR2, wherein R1 is H or CH3 and R2 is H or a C1- 5 hydroxyalkyl group, in the presence of a solid acidic catalyst comprising a natural or synthetic cation-exchange resin, e.g. a montmorillonite-type silicate, in the acid state. The reaction may be conducted in an inert solvent, e.g. toluene or xylene, at e.g. 50-150 DEG C. The product may be copolymerized with, e.g. styrene, acrylic and methacrylic acids, esters, amides and nitriles, and maleic and fumaric acid derivatives. The products of the invention may also be mixed with alkyd, acrylic, epoxy, UF or MF resins. In examples, hexamethoxymethyl melamine or hexabutoxymethyl melamine or a commercial partly etherified methylolated melamine is reacted with acrylic acid, methacrylic acid, hydroxyethyl methacrylate or hydroxypropyl acrylate in xylene i.p.o. a trace of hydroquinone and a montmorillonite morillonite or acid cation exchanger, and the concentrated product is copolymerized in Examples 1-6 with butyl acrylate and styrene and optionally ethyl acrylate in xylene/butanol i.p.o cumene hydroperoxide and tert.-dodecylmercaptan, the products being mixed with TiO2 and used as lacquers, and in Example 7 with acrylic acid, butyl acrylate and styrene, in butanol/ethylene glycol, the product being neutralized with Et3N and mixed with TiO2 and water to give an electrocoating composition.ALSO:An electrocoating composition comprises, in Example 7, a copolymer of the reaction product of hexamethoxymethyl melamine and methacrylic acid with acrylic acid, butyl acrylate and styrene in ethylene glycol and butanol, the polymer being neutralized with tri-ethyl amine, pigmented with TiO2 and diluted with water to 10% resin solids. An anode is coated for 1 minute at 100 volts, giving a 15m film, or at 120 volts giving a 20m film (about 3 in A/cm2). The coating is stoved at 150 DEG C.ALSO:An optionally etherified polymethylol melamine where each group A is -N(CH2OR)2 or -NH.CH2OR, R being H or a C1- 4 alkyl group, is estified with an acrylic or methacrylic acid or ester CH2=CR1-COOR2, where R1 is H or CH3 and R2 is H or a C1- 5 hydroxyalkyl group, in the presence of a solid catalyst which is a natural or synthetic cation exchanger in the acid state. Suitable catalysts include montmorillonite-type silicates in the acid state. In examples hexamethoxymethylmelamine or hexabutoxymethylmelamine or a commercial partly etherified methylolated melamine is reacted with acrylic acid, methacrylic acid, hydroxyethyl methacrylate or hydroxypropyl acrylate in xylene i.p.o. a trace of hydroquinone and a montmorillonite or a commercial acid cation exchanger.