Thermally cured coil-coatings utilizing novel resins and fatty acid methyl esters as reactive diluents
Solvent-borne thermally cured coil-coating resins contain large amounts of volatile organic solvents in order to obtain suitable flow for film application. This work describes how the expensive and environmental hazardous volatile organic solvent content of a solvent-borne thermally cured polyester/melamine coil-coating system can be reduced by introduction of fatty acid methyl esters (FAMEs) as reactive diluents and modification of the polyester binder resin. The evaluated reactive diluents, two rape seed methyl esters (RMEs), two linseed oil methyl esters (LMEs), and a tall oil methyl ester (TOME) have been evaluated both in a fully formulated clear-coat system and via model studies. Viscosity measurements of wet paint mixtures showed that formulations with hyperbranched polyester binder hold lower viscosity than conventional polyester binder resins and that FAME works as a diluent. Fully formulated clear-coats were cured under simulated industrial coil-coating cure conditions and in a convection oven at lower temperatures respectively. FAME increases the mobility of the system enhancing the film formation process. Free-standing clear-coat films were analyzed with Raman, carbon-14 dating, extraction, dynamic mechanical analysis, and visual observation. Incorporation of FAME could not be confirmed by Raman analysis. However, carbon-14 dating indicated the presence of FAME that could not be extracted from the films. The mechanical properties of the films were also affected by the addition of FAMEs, oven temperature, choice of co-solvent, and flash-off period. Conventional film characterization tests on substrate supported coatings indicated that binder resin structure and cure conditions affect the final film properties. Model studies were performed to clarify how FAME can chemically react through transesterification with the hydroxyl-groups of the polyester. The transesterification reaction between different FAMEs and primary alcohols with and without tertiary hydrogen was monitored with 1H-NMR and real time IR. Evaporation and side reactions, e.g. alkene reactions, are competing factors to the transesterification reaction. The study showed that fatty acid structure, reaction time, and temperature affect the transesterification conversion, degree of side reactions, and choice of catalyst. A pigmented fully formulated polyester/melamine formulation with a reactive diluent was cured at full scale in an industrial coil-coating production facility. Evaluation of the final film properties showed that the coating fulfills the specification of conventional polyester/melamine coil-coating systems.
School:Kungliga Tekniska högskolan
Source Type:Doctoral Dissertation
Keywords:NATURAL SCIENCES; Chemistry; Organic chemistry; Polymer chemistry; Coatings; Coil-coatings; Thermal cure; Reactive diluents; Fatty acids; Transesterification; Hyperbranched polyester resins; Film properties
Date of Publication:01/01/2008