Effect of intermolecular hydrogen bonding strength on the dynamic fragility of amorphous polyamides.

Abstract

Small-molecular-induced intermolecular hydrogen bonding (inter-HB) interactions were reported to increase the glass transition temperature (Tg) while decrease the dynamic fragility (m) of polymers. Herein, enthalpy relaxation parameters heat capacity jump (ΔCp) at Tg and enthalpy hysteresis (ΔHR) were investigated to help clarify the effect of macromolecular-induced inter-HB on Tg and m using amorphous polyamides as model polymers. The inter-HB strength was weakened by random copolymerization with varied chain rigidity, but was enhanced by decreasing steric hindrance. It was found that Tg and m increased after copolymerization due to the increased chain rigidity. Nevertheless, increasing steric hindrance leads to an increased Tg while anomalously reduced m. Further results found that m can be well correlated to Tg·ΔCp/ΔHR. ΔCp increases more significantly than ΔHR in co-polyamides, and thus the entropy change dominates the activation free energy of cooperative rearrangement. By contrast, ΔHR increases more significantly than ΔCp with increasing steric hindrance, and thus it is reasonable that Tg increases while m decreases. Most importantly, ΔCp and ΔHR decrease with increasing inter-HB strength regardless of the variation of Tg. These results indicate that the inter-HB strength may be very strong and insensitive to temperature in polyamides, thus behaving like physical cross-linking.