American Chemical Society
ma051349f_si_001.pdf (118.11 kB)

Iodine Transfer Polymerization (ITP) of Vinylidene Fluoride (VDF). Influence of the Defect of VDF Chaining on the Control of ITP

Download (118.11 kB)
journal contribution
posted on 2005-12-13, 00:00 authored by Cyrille Boyer, David Valade, Laurent Sauguet, Bruno Ameduri, Bernard Boutevin
Iodine transfer polymerization (ITP) of vinylidene fluoride (VDF) in the presence of two chain transfer agents (CTA, such as C6F13I and HC2F4CH2I) is presented. Various experimental conditions in terms of the nature of the radical initiators, time, temperature and initial [initiator]0/[VDF]0 and [CTA]0/[VDF]0 molar ratios influenced the yield of the reaction, the obtained average degree of polymerization in number, n, of PVDF−I, the defect of VDF-chaining, and the CX2I functionality (where X = H or F). The microstructures of these produced PVDF−I oligomers were characterized by 1H and 19F NMR spectroscopy which enabled one to assess the n values and to quantify the head-to-head or tail-to-tail defects of VDF-chainings. A low amount of defect of chaining in PVDF−I when C6F13I was used in contrast to a higher content from HC2F4CH2I. These PVDF−Is exhibited a favored −CH2CF2I functionality from the former CTA which was not observed in the latter one. A good agreement between the targeted and the obtained n values was noted for ITP of VDF in the presence of C6F13I (representative of normal addition) whereas that carried out from HC2F4CH2I (representative of inverse addition) led to experimental n values higher than the targeted ones in all cases. A low conversion of HC2F4CH2I was observed in contrast to that of C6F13I, which shows a better efficiency as the transfer agent.