Multifunctional Porous Poly(vinylidene fluoride)‐graft‐Poly(butyl methacrylate) with Good Li⁺ Ion Conductivity

Abstract

PnBMA is grafted on PVDF using ATRP in NMP solution at 90 °C and characterized by means of 1D and 2D NMR. 19F NMR spectra clearly reveal that the attack occurs on the head‐head >CF2 groups. Cast PB films show a honeycomb‐patterned porous microstructure, and the “breath‐figure” model is used to explain pore formation. FT‐IR spectra suggest a supramolecular interaction between >CO groups of PnBMA and >CF2 groups of PVDF. Storage modulus, loss modulus and stress at break decrease with graft conversion, but the strain at break increases significantly. The toughness of the copolymers also increases dramatically (882%). The porous materials can be applied as solid‐state electrolytes (Li+‐doped) with good ionic conductivity (10−5 S · cm−1). magnified image

Breath Figures: Fabrication of Honeycomb Porous Films Induced by Marangoni Instabilities

“…Apart from CdSe nanoparticles, other groups employed alternative metals. This is the case of Hao's group [147,171] who described how gold nanoparticles accumulate at the water-chloroform interface or metal oxide nanoparticles such as ZnO or SiO 2 previously modified by surface initiated polymerizations [170]. The inorganic particles require an organic coating, mostly a polymer layer, to be stable in solution..…”

“…Thus, with an appropriate design of the polymer, a desired functionality can be homogeneously distributed in the entire film, exclusively inside the cavities, both inside/outside the pores or on the top surface (Scheme 10.1). A variety of techniques have been employed to analyze the chemical distribution of the surfaces, such as fluorescence microscopy [114,140], transmission electron microscopy [75], atomic force microscopy [144], time-of-flight secondary-ion mass spectrometry [145], X-ray photoelectron spectroscopy [146], energy-dispersive X-ray (EDX) measurements [147] and Raman microscopy [148].…”

Surface-Functionalized and Surface-Functionalizable Poly(vinylidene fluoride) Membranes via Controlled/Living Radical Polymerization and Click Chemistry

“…ATRP of styrene, PEGMA, NaSS, poly(oxyethylene methacrylate) (POEM), butyl methacrylate (BMA) and 2-vinylpyridine (2VP) initiated directly from the secondary -CF 2 -groups of PVDF main chains have been reported (40)(41)(42)(43)(44)(45)(46)(47)(48)(49)(50)(51)(52). PVDF with poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA) side chains were synthesized via vinylidene fluoride-initiated ATRP of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) (53).…”

Direct polymer brush grafting to polymer fibers and films by surface-initiated polymerization

“…On the other hand, direct 'grafting-from' surface modification of fluoropolymers without any pretreatment by means of C-X bond activation has been proposed. [50][51][52][53] Because C-F bonds are too stable (ca. 486 kJ mol −1 ) to initiate polymerization, VDF-based fluoropolymers have been used to initiate ATRP.…”