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were detected with a flame ionization detector operating at
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250 C. Monomer conversion was determined using the peaks
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area ratio of monomer and diphenyl ether.
Size Exclusion Chromatography
3
Moszczynski, P.; Kalita, M.; Parzuchowski, P.; Siekierski, M.;
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SEC was carried out in water at 20 C, at a flow rate of
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mL min using a TSK PW 500 column of 30 cm and a
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mass equivalent to pullulan standards.
6 Hadjichristidis, N.; Pitsikalis, M.; Iatrou, H. Adv Polym Sci
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SEC was carried out in NMP (containing 10
M LiBr) at
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7 Macosko, C. W.; Guegan, P.; Khandpur, A. K.; Nakayama, A.;
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C, at a flow rate of 0.5 mL min , by means of a
Viscotek TDA 302 apparatus and a set of three columns PL
Gel (Polymer Laboratories) 10 m connected in series. Mono-
dispersed (PS) standards were used for calibration. The
dried polymers were first dissolved in water. NMP (contain-
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ing 10
M LiBr) was added and water was removed by
evaporation before injection in the SEC apparatus.
1
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NMR Spectroscopy
NMR spectra were recorded on a Bruker AC-400 spectrome-
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ter for H NMR (400 MHz) and CDCl or DMSO-d as the sol-
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3 Shi, Z. Q.; Holdcroft, S. Macromolecules 2004, 37,
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CONCLUSIONS
1
5 Kostov, G.; Boschet, F.; Buller, J.; Badache, L.; Brandsadter,
The preparation of PVDF-b-PSSS block copolymer was possi-
ble through two polymerizations techniques: ITP and ATRP
and via a direct polymerization of SSS monomer. ITP of SSE,
a protected monomer, in the presence of PVDF-I macromo-
lecular CTA led to rather well-defined copolymers chains in
spite of side reactions with the ethyl sulfonate groups. This
work showed that, for the ITP of styrene sulfonate deriva-
tives, the PVDF-I macromolecular CTA is not totally efficient
because a limitation of the CTA consumption was observed.
This can be explained by both a low activity of the CTA and
a fast propagation rate of the monomer. Thus, it was possible
to obtain PVDF-based block copolymers by this technique,
but the copolymers are mixed with unreacted PVDF-I. The
use of ATRP overcomes from this drawback. Although ATRP
of SSE seemed not to be suitable to obtain block copolymers,
it was shown that the direct ATRP of SSS exhibited a con-
trolled behavior in a certain range of conversion giving the
opportunity to lead to PVDF-b-PSSS block copolymers with a
rather good control of the chain length and acceptable poly-
dispersity indices.
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The authors thank the Agence Nationale pour la Recherche
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