Linear Addition Polymers and Cyclic Oligomers of N,N‐Diglycidyl Aniline and Amines. Uncrosslinked Epoxide–Amine Addition Polymers, 46

The addition polymerization of N,N‐diglycidyl aniline (DGA) and disecondary diamines leads to linear addition polymers with molecular weights ranging from 2 500 to 9 100 Da respectively. Their relatively broad molecular weight distribution (M̄_w /M̄_n = 5.5 to 17) is caused by the formation of small amounts of cyclic oligomers. Surprisingly, the addition polymerization of primary monoamines and DGA results in the formation of oligomers only. These oligomers have molecular weights between 684 and 1 165 g·mol^–1. ¹³C NMR spectra proof that during addition reaction no side‐reaction took place and that the epoxide end groups were completely consumed. Obviously, the addition products mainly consist of cyclic oligomers. In the MALDI‐TOF mass spectra cyclic oligomers of repeat units between n = 1 and n = 7 were observed. The kinetics of the addition polymerization can be described by both a formal model and the smallest necessary set of elementary reactions. In order to find the optimum parameters, the set of differential equations was solved numerically by multivariate non‐linear regression. The perfect agreement between model calculations and experimental curves allows reliable predictions of the reaction behavior for arbitrary temperature–time profiles.