Crystallization behavior of poly(β-propiolactone)-block-polyethylene copolymers with varying polyethylene crystallinities

The crystallization behavior of poly(beta-propiolactone)-block-polyethylene (PPL-b-PE) copolymers with high PE crystallinities chi(PE) (>0.30) has been examined using time-resolved synchrotron small-angle X-ray scattering and Fourier transform infrared spectroscopy, where the PE block crystallized first and subsequently the PPL block crystallized on quenching from a strongly segregated melt. The crystallization of PE blocks destroyed the lamellar microdomain structure (LMS) existing in the melt to form the crystalline lamellar morphology (CLM), and then PPL blocks crystallized within CLM. This morphology formation was compared to our previous results for the crystallization of PPL-b-PE copolymers with low xpE (0.12 < chi(PE) < 0.26), where the crystallizability of PE blocks was not sufficiently large to destroy LMS. As a result, PE blocks crystallized promptly within LMS to reinforce and stabilize it against the subsequent crystallization of PPL blocks, yielding the confined crystallization of both blocks within LMS. We summarize these results including the case of chi(PE) = 0, and propose three mechanisms of morphology formation occurring in PPL-b-PE copolymers according to chi(PE) (i.e., high, low, or zero). (C) 2014 Elsevier Ltd. All rights reserved.