Crystallization Behavior of Nanostructured Poly(vinylidene fluoride)/1-Vinyl-3-butylimidazolium Chloride Ionic Liquid Composites†

doi:10.7503/cjcu20150822

Abstract

Abstract:

The effect of poly(vinylidene fluoride)-graft-(1-vinyl-3-butylimidazolium chloride [VBIM][Cl])(i.e. PVDF-g-[VBIM][Cl]) nanodomains on the crystallization behavior in nanostructured PVDF/[VBIM][Cl] composite was investigated by means of differential scanning calorimeter(DSC), polarized optical microscope(POM) and wide-angle X-ray diffractometer(WAXD) measurements. ¹H nuclear magnetic resonance(¹H NMR) results confirm the successful grafting of [VBIM][Cl] onto the PVDF chains. Transmission electron microscopy(TEM) images show PVDF-g-[VBIM][Cl] nanodomains in the nanostructured PVDF/[VBIM][Cl](100/8, mass ratio) composite, which is distinct from the miscible PVDF/[VBIM][Cl] blend prepared by physically blending. The DSC results show higher crystallization temperature(T_c) and shorter crystallization time in the nanostructured PVDF/[VBIM][Cl] composite, compared with those of neat PVDF and PVDF/[VBIM][Cl] blend(100/8), respectively, indicating that nanodomains enhanced the crystallization rate of the PVDF crystals. Moreover, a larger nucleation density accompanied with smaller spherulites was observed in the nanostructured sample by POM photos. It is considered that strong thermodynamic incompatibility of nanodomains with PVDF matrix caused a large amount of partially ordered molecular chains at their interface, which favorites the nucleus formation and thus improves the entire crystallization rate of the PVDF crystals. Because of the confinement of [VBIM][Cl] within nanodomains, dominant non-polar α crystals were found in the nanostructured sample, which was the same with that of neat PVDF.

Key words: Poly(vinylidene fluoride), Ionic liquid, Nanostructure, Crystallization

CLC Number:

O631

TrendMD:

XING Chenyang, WANG Yanyuan, LI Yongjin, LI Jingye. Crystallization Behavior of Nanostructured Poly(vinylidene fluoride)/1-Vinyl-3-butylimidazolium Chloride Ionic Liquid Composites^†[J]. Chem. J. Chinese Universities, 2016, 37(4): 775.

Figures/Tables 5

Fig.1 1H NMR spectra of nanostructured PVDF/ [VBIM][Cl](100/8) composite^Inset: the possible chemical structure of PVDF-g-[VBIM][Cl].

Fig.2 TEM images of nanostructured PVDF/[VBIM][Cl](100/8) composite(A) ^ (B) Magnification of the rectangle of (A).

Fig.3 DSC curves of cooling run with a scanning rate of 10 ℃/min(A) and isothermal crystallization at 155 ℃(B) of neat PVDF(a), PVDF/[VBIM][Cl](100/8) blend(b) and nanostructured PVDF/[VBIM][Cl](100/8) composite(c)

Fig.4 POM photos of neat PVDF(A, B) and nanostructured PVDF/[VBIM][Cl](100/8) composite(C, D) at 155 ℃ ^Crystallization time/min: (A, C) 1; (B, D) 8.

Fig.5 Schematic structures of irradiated PVDF/[VBIM][Cl] sample(A), PVDF-g-[VBIM][Cl] nanodomains(B) and WAXD patterns of neat PVDF(a) and nanostructured PVDF/[VBIM][Cl](100/8) composite(b)(C)

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