Glycidylester-anhydride adducts, curing of epoxy resin powder coatings

Abstract: Novel curing agents for epoxy resins comprise oligomeric adducts of the glycidylester of pivalic acid and trimellitic anhydride having a melting point of from 80 to 110 °C.

Description: The present invention is concerned with adducts of a defined glycidylester of an aliphatic monocarboxylic acid and an anhydride of a defined trihydric aromatic carboxylic acid. The present invention is likewise concerned with the use of such adducts as agents for the curing of epoxy resins, particularly epoxy resin powder coating systems. Glycidyl esters of alpha-branched aliphatic monocarboxylic acids with 9 to 11 carbon atoms are known commercial products. Their use in polyester powder coating systems has been disclosed in DE-A-2558723. However, when applied in curing systems based upon epoxy resin powder coatings, they do not meet the requirement of having an adequate melting point, i.e. they melt below 65 °C, which hampers the envisaged commercialization for that purpose. The present invention centres around the finding that oligomeric adducts of trimellitic anhydride and the glycidylester of pivalic acid can be prepared to provide melting points within the range of from 80 to 110 °C. Therefore, these adducts have the potential of opening a new market in epoxy resin powder coatings. The Applicants now claim compounds having the formula: in which the value of n is such that the compound has an acid value of from 2.4 to 2.8 meq.g⁻¹ and a melting point of from 80 to 110 °C. Typical values of n are within the range of from 3 to 8, preferably 4 to 6. The compounds of this invention are obtainable by any known preparation method. Each of the starting materials trimellitic anhydride and the glycidylester of pivalic acid are known per se. The use of the oligomeric adducts as curing agents for epoxy resins generally and as curing agents for epoxy resin powder coatings particularly will present no problem to the average expert. In addition to epoxy resin based powder coatings, solvent-borne lacquers or stoving enamels can be cured with the novel adducts as well. Suitable epoxy resins are preferably selected from the multitude of commercially available polyglycidyl ethers of polyhydric phenols, most preferred are the diglycidyl ethers of dihydric aromatic phenols, particularly 2,2-di(4-hydroxyphenyl)propane. A good choice would be EPIKOTE 1055 (EPIKOTE is a Trade Mark). The curing of the epoxy resins with the novel adducts will normally proceed via prolonged heating at a temperature of at least 90 °C, preferably at least 120 °C. Example 173 g of the glycidylester of pivalic acid were reacted with 192 g of trimellitic anhydride in 156 g of methylethylketone and 0.9 g benzyldimethylamine catalyst at 70 to 90 °C. The reaction was continued until the epoxy group content of the solid in the reaction mixture had decreased to 0.05 eq.kg⁻¹ (4 hours reacting). The oligomeric adduct had a m.pt. range of 80 to 110 °C and an acid value of 2.65 eq.kg⁻¹; M z was 6700 and M w .M n ⁻¹ was 2.08, as determined by GPC analysis. The adduct was evaluated in the curing of an EPIKOTE 1055 solvent-borne lacquer. The amount of adduct was stoichiometric, the solvent was butyloxitol, 0.5 %w catalyst AMC-2 (ex AEROJET GENERAL, Inc.) was employed as curing accelerator. The lacquer was applied in a film thickness of 20 microns by bar coating on bare steel panels. Stoving for 20 minutes was effected at 120 °C, 140 °C and 160 °C respectively. stoving temperature: 120 °C 140 °C 160 °C MEK resistance, double rubs <10 50-80 100 Gloss Gardner, 45 °C 87 95 95 Koenig hardness, sec 148 158 156 Direct impact, (inch/lbs) mm/g <(10) 0,56 >(80) 4,5 >(80) 4,5 Reverse impact, (inch/lbs) mm/g <(10) 0,56 >(80) 4,5 >(80) 4,5

Claims: Claims for the following Contracting States : BE, CH, DE, FR, GB, IT, LI, NL, SE Compounds having the formula: in which the value of n is such that the compound has an acid value of from 2.4 to 2.8 meq.g⁻¹ and a melting point of from 80 to 110 °C. A process for curing an epoxy resin with a curing agent, characterized in that the curing agent is a compound as claimed in claim 1. A process according to claim 2 wherein the epoxy resin is an epoxy resin powder coating. Claims for the following Contracting State : ES A process for the preparation of a compound of the general formula in which the value of n is such that the compound has an acid value of from 2.4 to 2.8 meq.g⁻¹ and a melting point of from 80 to 110 °C, by reacting n+1 moles of the glycidylester of pivalic acid with n+1 moles of trimellitic anhydride. A process for curing an epoxy resin with a curing agent, characterized in that the curing agent is a compound prepared according to the process of claim 1. A process according to claim 2 wherein the epoxy resin is epoxy resin powder coating.

Inventors: KARZIJN WILLEM, KOOIJMANS PETRUS GERARDUS, VAN DER MARK JOHANNES MARIA C, KARZIJN, WILLEM, KOOIJMANS, PETRUS GERARDUS, VAN DER MARK, JOHANNES MARIA C/O SHELL RES.B.V.
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1991
Main classification: C08G59
IPC codes: C09D163, C08G59, C09D5, C07D307