Curing kinetics of epoxy cured by cardanol-based phenalkamines synthesized from different polyethylenepolyamines by Mannich reaction

Abstract

Phenalkamines with different structures are expected to affect the curing reaction of epoxy, yet the exact mechanism remains to be elucidated. In this study, four cardanol-based phenalkamines (named PK1, PK2, PK3, and PK4, respectively), synthesized from ethylenediamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, were used as curing agents in diglycidyl ether of bisphenol A (DGEBA) epoxy system. The phenalkamines were characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and time-of-flight secondary ion mass spectrometry. The curing behaviors and kinetics were investigated by non-isothermal differential scanning calorimetry, and the activation energies of the reactions (E α ) were determined using Kissinger–Akahira–Sunose (KAS) and Starink methods. The results indicate a similar curing mechanism for all four phenalkamines. All E α values remain almost constant in the range of 0.05 ≤ α ≤ 0.6, and increase dramatically after α > 0.6 due to greater viscosity of the reaction systems. The diffusion of reactive groups plays an increasingly important role in determining the curing kinetics. In addition, DGEBA/PK1 and DGEBA/PK2 have lower initial E α values than DGEBA/PK3 and DGEBA/PK4, because PK1 and PK2 have lower viscosity than PK3 and PK4. When α is high, DGEBA/PK1 and DGEBA/PK2 have higher E α values than DGEBA/PK3 and DGEBA/PK4, because more tertiary amine groups can be formed in the reactions between the epoxy and secondary amine groups in the DGEBA/PK3 and DGEBA/PK4 systems, which catalyze the curing reaction and it thus lowers energetic barrier.