Polymerization mechanism of 4-APN and a new catalyst for phthalonitrile resin polymerization

Abstract

The widely used catalysts for phthalonitrile (PN) resin polymerization are aromatic compounds containing –NH₂ because of their high catalytic performances. However, the catalytic mechanisms of these catalysts are not very clear. To understand the mechanisms of them, the widely used autocatalytic catalyst 4-(4-aminophenoxy)-phthalonitrile (4-APN) was studied in this paper. The polymerization process of 4-APN was tracked by a multi-purpose method, and ammonia gas was detected during the cross-linking processing for the fist time. Combined with the online IR results of the curing process of 4-APN, the mechanism of ammonia generation was newly proposed. Based on this mechanism, a new catalyst selection strategy was promoted, which is different from the traditional approach to catalyst selection for PN resin polymerization. According to the new strategy, 1,3-diiminoisoindoline (1,3-DII) was selected as a novel catalyst. The results showed that the new catalyst could not only effectively catalyze the polymerization of PN resin, but also has a lower curing temperature than that of organic amine catalysts and can eliminate the release of ammonia gas and the voids in the products caused thereby. Therefore, the results of this study will give important enlightenment to the development of PN catalysts and the development of PN.