Radical copolymerization of 1fluoromethylvinylbenzene with chlorotrifluoroethylene

1
Radical copolymerization of 1-fluoromethyl)vinyl
benzene with chlorotrifluoroethylene M.
Tredwell,1 G. Kostov,2 V. Gouverneur,1 B.
Ameduri2 1University of Oxford, Chemistry
Research Laboratory, Mansfield Road, Oxford, OX1
3TA, UK 2Laboratory of Macromolecular Chemistry,
UMR-CNRS 5076, Ecole Nationale Supérieure de
Chimie de Montpellier, 8 rue de lEcole Normale
34296 Montpellier Cedex 05, France
1. Introduction Why use fluorinated polymers?1
Applications -Low refractive index -Optical
fibres -High thermal, chemical, oxidative
stability -Protective coatings -Low surface
energy -Lubricants -Highly oil, water and soil
repellent -Textiles protection -Strong organic
acids -Catalysts, fuel cells
2. Objectives
3. Synthesis of 1-fluoromethyl)vinylbenzene(FMB)
Monomer ratio (mol)
in the feed
in copolymer
The fluorinated monomer was synthesized via the
electrophilic fluorodesilylation of the
corresponding organosilane2 using SelectfluorTM
to give the desired monomer in quantitive yield.
The allylsilane good be easily obtained from a
Heck coupling of phenyl triflate and
allytrimethylsilane.
5. Kinetics of radical copolymerization
Table 1.Radical copolymerization of CTFE with FMB
at different initial molar ratios in the feed and
the resulting copolymers
6. Experimental Conditions Reactions were
performed in borosilicate Carius tubes.
Introduction of the initiator (tert-butyl
peroxypivalate 1-3 mol versus the monomer) FMB
(ca 0.1 to 0.8) and C4F5H5 (1.5g-2g) as solvent.
The obtain the desired CTFE quantities a
calibration was performed where the gas pressure
was correlated to the introduced weight. The tube
was sealed while immersed in liquid N2, placed in
a metal container and then allowed to stir in a
shaken oven at 74C for 5hrs. The products were
analysed by 19F and 1H NMR.
Figure 1. 19F NMR spectrum (d6 acetone) of
poly(CTFE-co-FMB)
Figure 2. Polymer/monomer distribution in the
radical copolymerization of CTFE/FMB
Figure 3. Determination of reactivity ratios by
Kelen Tudos method
Table 2. Reactivity ratios of CTFE and comonomers
in radical coploymerization
7. Conclusion - original fluorinated comonomer
incorporated in poly-CTFE
- determination of the microstructure
- Assessment of the
reactivity ratios rCTFE0.40.1 and rFMB3.71.2
at 74C
References 1 B. Ameduri, B. Boutevin, Well
Architectured Fluoropolymers, Elsevier,
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