From Telomerization to Controlled Radical Polymerization ofVinylidene Fluoride and Applications Therefrom
Bruno AMEDURI
Ingénierie & Architectures Macromoléculaires
Institut Charles Gerhardt ; UMR (CNRS) 5253 – E.N.S. Chimie Montpellier
34296 MONTPELLIER Cedex 5 (France)
e-mail : bruno.ameduri@enscm.fr
Fluoropolymers [1] exhibit remarkable properties, which enable them to find out a wide rangeof High-Tech applications (cladding and cores of optical fibers, thin films for microelectronics,
repellent coatings, lubricants, surfactants, fire fighting agents, membranes for fuel cells anddielectric films). Various strategies of syntheses from original telomers toward controlled
fluoropolymers are depicted in this presentation.
1) First, telomerization [1] involves a telogen or a transfer agent (X-Y), and one or more (n)molecules of a polymerizable compound M (called taxogen or monomer), under radical
polymerization conditions, leading to X-(M)n-Y telomers, as follows:
XY + nM

free radicalsX(M)n Y

Various examples of telomerization of vinylidene fluoride, VDF (H2C=CF2) involving
different X-Y transfer agents (hydroxylated [2], phosphonated [3], halogenated [4]) have been
investigated. The kinetics of telomerization enabled us to assess the transfer constants to thetelogens [1] and an increasing series regarding the efficiency of these transfer agents is
supplied, correlated with the bond dissociation energy of the cleavable bond of the telogens[1]:
CF3CH2OH<CH3OH<CCl3H<CCl4<(EtO)2P(O)H<BrCF2CFClBr<CCl3Br<RSH<ICl2) The second part deals with the applications of these functional telomers as potential
intermediates for the synthesis of well-architectured fluoropolymers including telechelics[1,5], block copolymers [1,6-9], macromonomers [1,10], graft copolymers [11]. Various
examples are supplied to understand the wide potential of applications of these
fluoropolymers and examples concern the use of novel oligo(VDF)-containing acrylates as
surface modifiers [11,12], potential non-bioaccumulable surfactants,[13] or original telomers
based on VDF, TFE and HFP for hybrid fluorosilicones [1,14].
3) Third, Iodine transfer polymerization (ITP [14]) and MADIX polymerization ofvinylidene fluoride (VDF) [9,15] have been used for the controlled radical polymerization(CRP) of VDF.
Industrial applications from CRP of fluoroalkenes (e.g., surface modifiers, solvents for
Lithium ion batteries, fluorosilicones, and thermoplastic elastomers) will illustrate thispresentation.
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