PHOTOGENERATION OF POLYFUNCTIONAL AMINES AND NOVEL THERMAL CURING REACTIONS OF EPOXY-RESIN AND POLYURETHANE OLIGOMER USING THESE AMINES

Photochemical reactions of various blocked polyfunctional amines such as bis(4-formylaminophenyl)methane (FAPM), bis(4-acetylaminophenyl)met hane (AAPM), bis(4-benzoylaminophenyl)methane (BAPM), 2,4-diformylamin otoluene (DFAT), m-xylene diformamide, and is[[(2-nitrobenzyl)oxy]carb onyl]hexane-1,6-diamine were carried out to give the corresponding fre e amines in THF solution, in epoxy resin, or in polyurethane oligomer with terminal isocyanate groups. Photolysis of FAPM and DFAT to produc e the corresponding polyfunctional amines such as 4,4'-methylenedianil ine and 2,4-diaminotoluene proceeded with 80 and 75% conversions, resp ectively, in THF solution under UV irradiation at 5 h. AAPM and BAPM a lso produced the corresponding photo-Fries rearrangement products with 32 and 38% conversions, respectively, under the same irradiation cond itions. The photolysis of those compounds also occurred with similar c onversions in the epoxy resin and in the polyurethane oligomer under U V irradiation; and the thermal curing reactions of the epoxy resin and the polyurethane oligomer with photogenerated polyfunctional amines p roceeded smoothly after heating at 140-degrees-C for 2 hrs. (C) 1993 J ohn Wiley & Sons, Inc.