Influences of pre‐ordered melt structures on the crystallization behavior and polymorphic composition of β‐nucleated isotactic polypropylene with different stereo‐defect distribution

As part of continuous efforts to understand the surprising synergetic effect between β‐nucleating agent and pre‐ordered structures of isotactic polypropylene (iPP) in significant enhancement of β‐crystallization (Ordered Structure Effect, OSE), two β‐nucleated iPP with different uniformities of stereo‐defect distribution (WPP‐A and WPP‐B) were prepared, their crystallization behaviors with variation of melt structures were studied in detail. The results revealed that β‐phase can hardly form in WPP‐A (whose stereo‐defect distribution is less uniform) because of its strong tendency of α‐nucleation caused by its less uniform stereo‐defect distribution, while WPP‐B is more favorable for β‐crystallization; As fusion temperature decreases, similar variation trends of crystallization temperature and β‐phase proportion can be observed from WPP‐A and WPP‐B, indicating the occurrence of OSE behavior, which provides unsurpassed β‐nucleation efficiency and induces β‐crystallization even in WPP‐A which is less favorable for β‐crystallization; moreover, the upper and lower limiting temperatures of Region II of WPP‐A and WPP‐B are identical, suggesting the uniformity of stereo‐defect distribution has little influence on temperature window for OSE (denoted as Region II). To explore the physical nature of Region II, self‐nucleation behavior and equilibrium melting temperature of PP‐A and PP‐B were studied. The lower limiting temperatures of exclusive self‐nucleation domain of both PP‐A and PP‐B are identical with the lower limiting temperatures of Region II in OSE (168°C); moreover, the T_m⁰ of both PP‐A and PP‐B are close to their upper limiting temperatures of Region II in OSE behavior (189°C). The possible explanation was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42632.