Antiplasticization behavior of polycaprolactone/polycarbonate-modified epoxies

Antiplasticization behavior was found in the polycaprolactone (PCL)/polycarbonate (PC)-modified epoxy system, cured with an aromatic amine. The initial modulus increased and the fracture toughness and the elongation at break decreased with the addition of the PCL/PC modifier. The glass transition temperature (T-g) decreased slightly. In this system, the antiplasticization phenomenon can be explained well by the formation of hydrogen bonding between the carbonyl groups in the PCL/PC and the hydroxyl groups in the epoxy. The hydrogen bonding proportion, as analyzed from Fourier transform infrared spectra, increased with the addition of PCL/PC up to 15 parts. This is consistent with the trend observed in the mechanical properties. It was thought that for antiplasticization to occur, a strong molecular interaction is necessary for a restriction of molecular motion, in turn decreasing the free volume of the matrix and thereby causing an increase in the modulus of the material. The dynamic mechanical thermal behavior of these systems was also studied. It was found that there was no change in the molecular weights between crosslinks, which excluded the effect of crosslink density on the changes of the properties. Instead, the activation energy was increased and the peak area was decreased for the beta relaxation because of the restriction of the molecular motion by hydrogen bonding. The results indirectly support the hypothesis that the motion of the 2-hydroxypropyl ether is responsible for the beta relaxation process.