The Effect of the Structure of Aromatic Diamine on High-Performance Epoxy Resins

Abstract

To study the influence of curing agent structure on the properties of epoxy resin, four types of aromatic diamines with the structure of diphenyl methane (4,4′-methylenedianiline (MDA), 4,4′-methylenebis(2-ethylaniline) (MOEA), 4,4′-methylenebis(2-chloroaniline) (MOCA), and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA)) and a high-performance epoxy resin, 3-(oxiran-2-ylmethoxy)-N,N-bis(oxiran-2-ylmethyl)aniline (AFG-90MH), were used in this study. The resulting resin systems were designated as AFG-90MH-MDA, AFG-90MH-MOEA, AFG-90MH-MOCA, and AFG-90MH-MCDEA. After curing, these systems were named AFG-90MH-MDA-C, AFG-90MH-MOEA-C, AFG-90MH-MOCA-C, and AFG-90MH-MCDEA-C. The influence of the structure of the diamines on the processability, curing reaction activity, and thermal and mechanical properties (including flexural and tensile properties) of the epoxy resins were investigated. These systems demonstrate excellent processability with wide processing windows ranging from 30 °C to 110–160 °C while maintaining low viscosity. Consistent apparent activation energy (Ea) trends via both Kissinger and Flynn-Wall-Ozawa methods were observed. The epoxy systems exhibit the following increasing Ea sequence: AFG-90MH-MDA < AFG-90MH-MOEA < AFG-90MH-MOCA < AFG-90MH-MCDEA. The processability and curing reaction kinetic results indicate that the reactivities of the diamines decrease in the order: MDA > MOEA > MOCA > MCDEA. Polar chlorine substituents in diamines strengthen intermolecular interactions, thereby enhancing mechanical performance. The flexural strength of cured epoxy systems decreases as follows with corresponding values: AFG-90MH-MOCA-C (165 MPa) > AFG-90MH-MDA-C (158 MPa) > AFG-90MH-MCDEA-C (148 MPa) > AFG-90MH-MOEA-C (136 MPa). Diamines with substituents like chlorine or ethyl groups reduce the glass transition temperatures (Tg) of the cured resin systems. However, the cured resin systems with the diamines containing chlorine demonstrate superior thermal performance compared to those with ethyl groups. The cured epoxy systems exhibit the following descending glass transition temperature order with corresponding values: AFG-90MH-MDA-C (213 °C) > AFG-90MH-MOCA-C (190 °C) > AFG-90MH-MCDEA-C (183 °C) > AFG-90MH-MOEA-C (172 °C).