Dimethyl secondary amine chain extenders: a conceptual approach to in situ generation of advanced epoxy resins for rapid cure, low VOC coatings

Abstract

Solid epoxy resin oligomers have traditionally been utilized for coatings that combine fast dry-totouch speed and good flexibility, properties greatly in demand in many applications such as marine and industrial maintenance coatings. Unfortunately, solid epoxy resins require formulation with large quantities of solvent that make the attainment of modern VOC regulations difficult or impossible. Coatings formulated from low molecular weight liquid epoxy resin (LER) on the other hand, can more easily meet VOC challenges, but dry slowly and tend to be brittle. This article explores the concept of using fast reacting, difunctional amine chain extenders to generate epoxy oligomers in situ as a means of meeting these opposing property demands. Methylamine-terminated poly(Nmethylazetidine) (p-NMAz) is prepared in a two-step process involving the Michael addition of methylamine to acrylonitrile followed by hydrogenation in a methylamine-containing atmosphere to yield an oligomer stream with an M n of about 250. Hydrogenation of isophthalonitrile in a methylamine-containing atmosphere yields N,N¢-dimethyl-meta-xylylenediamine (DMMXDA). Competitive pseudo-first-order kinetic measurements conducted in isopropyl alcohol indicate these amines react approximately 3-3.6 times faster with phenyl glycidyl ether (PGE) than the primary amine meta-xylylenediamine (MXDA). These chain extenders can be formulated with traditional multifunctional amine crosslinkers to yield coatings with lower VOC, faster dry speed, and better flexibility compared with corresponding coatings formulated without the chain extender. Consistent with their chemical structures, p-NMAz proved capable of yielding coatings with the best impact resistance and mandrel bend properties, while DMMXDA yielded coatings with better water and corrosion resistance properties.