The reaction kinetics and structure property relationships of isomeric tri‐aromatic ether‐linked amines based on the structure bis (aminophenoxy) benzene, cured with diglycidyl ether of bisphenol F (BisF) are investigated in this study. Reaction kinetics are explored using rheological and calorimetric measurements, whereas structure property relationships are determined from their flexural properties, dynamic mechanical properties (DMTA), and thermogravimetric analysis (TGA). A BisF network cured with 4,4 diamino diphenyl sulphone (44 DDS) is used as a benchmark to represent a commercially available high‐performance resin system. Varying the substitution of the ether linkages on the aromatic groups from ortho, meta to para was found to have a significant impact on reactivity and network properties after cure. The variations are explained in terms of inductive and resonance effects primarily acting on the outer aromatic rings. Interestingly, however, these same effects acting on the central aromatic ring also impact upon reactivity despite their proximity from the amines. Mechanical and thermal properties are explained by changes in the short‐range molecular mobility within the network architecture such as phenylene rotations or π flips and are experimentally validated from the breadth and position of the subambient γ relaxations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47383.

Isomeric tri‐aryl ketone amines, 1,3‐bis(3‐aminobenzoyl)benzene (133 BABB), 1,3‐bis(4‐aminobenzoyl)benzene (134 BABB), and 1,4‐bis(4‐aminobenzoyl)benzene (144 BABB) are synthesized and cured with diglycidyl ether of bisphenol A and diglycidyl ether of bisphenol F in this work. Differential scanning calorimetry and near‐infrared spectroscopy reveal higher rate constants and enhanced secondary amine conversion with increasing para substitution attributed to resonance effects and the electron withdrawing nature of the carbonyl linkages. Glass transition temperatures increase from 133 BABB to 134 BABB, but decrease modestly for the 144 BABB hardener. With increasing para substitution, the flexural modulus and strength both decrease while the strain to failure increases but all BABB amines displaying higher mechanical properties than the corresponding 4,4‐diaminodiphenyl sulfone (44 DDS) networks. The thermal stability of the BABB networks is found to be modestly lower than 44 DDS, but char yields are significantly higher. Changes in thermal and mechanical properties are described in terms of molecular structure and equilibrium packing density.