How Chain Intermixing Dictates the Polymorphism of PVDF in Poly( vinylidene fluoride)/Polymethylmethacrylate Binary System during Recrystallization: A Comparative Study on Core-Shell Particles and Latex Blend

In the past few decades, Poly(vinylidene fluoride)/Polymethylmethacrylate (PVDF/PMMA) binary blend has attracted substantial attention in the scientific community due to possible intriguing mechanical, optical and ferroelectric properties that are closely related to its multiple crystal structures/phases. However, the effect of PMMA phase on the polymorphism of PVDF, especially the relationship between miscibility and polymorphism, remains an open question and is not yet fully understood. In this work, three series of particle blends with varied levels of miscibility between PVDF and PMMA were prepared via seeded emulsion polymerization: PVDF-PMMA core-shell particle (PVDF@PMMA) with high miscibility; PVDF/PMMA latex blend with modest miscibility; and PVDF@c-PMMA (crosslinked PMMA) core-shell particle with negligible miscibility. The difference in miscibility, and the corresponding morphology and polymorphism were systematically studied to correlate the PMMA/PVDF miscibility with PVDF polymorphism. It is of interest to observe that the formation of polar beta/gamma phase during melt crystallization could be governed in two ways: dipole-dipole interaction and fast crystallization. For PVDF@PMMA and PVDF/PMMA systems, in which fast crystallization was unlikely triggered, higher content of beta/gamma phase, and intense suppression of crystallization temperature and capacity were observed in PVDF@PMMA, because high miscibility favored a higher intensity of overall dipole-dipole interaction and a longer interaction time. For PVDF@c-PMMA system, after a complete coverage of PVDF seeds by PMMA shells, nearly pure beta/gamma phase was obtained owing to the fast homogeneous nucleation. This is the first report that high miscibility between PVDF and PMMA could favor the formation of beta/gamma phase.