The relative reactivity of primary and secondary amine hydrogen atoms of aromatic amines with epichlorohydrin and N‐ and O‐glycidyl compounds

Abstract

The relative value of the rate constants for the reactions between the secondary and primary amine hydrogen atoms of 3‐trifluoromethylaniline with epichlorohydrin, and of aniline with phenyl glycidyl ether and with some N‐alkyl‐N‐glycidylanilines were determined by HPLC analysis. Values ranged from 0.14 to 0.24 and are in agreement with the findings of earlier workers for the reactions of aromatic amines with O‐glycidyl compounds but in direct conflict with the claim of a recent publication. The value for the reaction between 3‐trifluoromethylaniline and epichlorohydrin was unaffected by the nature of the catalyst, which covered a wide range of strengths and steric requirements.

Reaction thermodynamics of amine‐cured epoxy systems: Validation of the enthalpy and heat capacity of reaction as determined by modulated temperature differential scanning calorimetry

“…The product was recrystallized from hexane/ether (needles, mp: 60 °C). The 13 C NMR spectrum confirmed the structure 26. The tertiary amine N , N ‐di[(hydroxy‐phenoxymethyl)ethyl]aniline (A 3 ) was obtained from reaction of a stoichiometric mixture of PGE+aniline until completion at 120 °C.…”

“…The 13 C NMR spectrum of A 3 agrees with the literature. It shows splitting of similar intensities for the carbon atoms near the central nitrogen atom because of the presence of the diastereoisomeric pair 26. Infrared spectra on both A 2 and A 3 further confirm their structure.…”

Epoxy-Aromatic Diamine Kinetics. Part 1. Modeling and Influence of the Diamine Structure

“…The chemical rate constants, which have an Arrhenius temperature dependence, were determined for DDS and MCDEA from kinetic results at 30, 80, 135, and 160 °C. For this purpose, the Runge-Kutta method was applied with the differential equations (15) and (16). The average values r = 0.45 for DDS and r = 0.65 for MCDEA were considered.…”

Mechanism and kinetics of curing of epoxides based on diglycidylamine with aromatic amines. 1. The reaction of diglycidylaniline with secondary amines

“…Etherification. In the reaction between DGA and NMA and with epoxide in excess etherification takes place and the formation of both linear and cyclic products was observed (Figure lb, chromatographic peaks [7][8][9][10][11]. The reaction begins after almost the whole amount of amine has been consumed, as illustrated by Figure 2b.…”