Vinylidene fluoride (VDF) monomer are gaseous in nature with low boiling point (-84oC), high kp which require highly pressurized and elevated temperature autoclaves for their corresponding polymer synthesis. VDF propagates with two different modes of propagation leading to head to tail (HT) (~~CF2CH2-X) or tail to head (TH) (~CH2CF2-X) additions, with varying bond dissociation energies. In order to overcome the difficulties in VDF polymerizations, a series of metal carbonyl catalyst, LzMtxCOy (Re, Mn, Fe, Cr, Mo) were used as photo-catalyst to mediate iodine degenerative transfer at room temperature under visible light irradiation to synthesize PVDF homopolymers with high chain end fidelity (~95%). Stoichiometric amount of metal carbonyl catalyst was used to simultaneously activate the dual chain ends of PVDF macroinitiator to synthesize homogenous PVDF block copolymer (BCP). A range of di, tri- BCP were synthesized with varying chain lengths. The BCP architecture was characterized by 1H, 19F, 2D {1H-19F HETCOR} Nuclear magnetic resonance, gel-permeation chromatography and differential scanning calorimetry studies. The nature of the BCP interface was tuned from highly hydrophilic to hydrophobic by using different type of monomers classes such as acrylates, dienes, main chain fluoro monomers, side chain fluorinated monomers and acrylamides. The effect of the composition, nature of the secondary monomer on the interface of PVDF-BCP were studied by small angle x-ray scattering, atomic force microscopy, sessile pendant drop contact angles.

Investigation of PVDF block copolymer architecture and their interface properties

255th National Meeting (2018)

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