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shoulder was clearly visible on the low molar mass side cor-
responding to the presence of a certain proportion of dead
chains in the starting VB10. Chain extension of P(VAc-co-
BMDO) was nevertheless possible.
Universitaire de France) for her nomination as senior member.
The authors would like to thank O. Boyron (UMR 5265 C2P2,
LCPP Team, Villeurbanne) for SEC analyses.
Hydrolysis of P(VAc-co-BMDO) Copolymer
REFERENCES AND NOTES
A preliminary study on the hydrolytic degradation of P(VAc-
co-BMDO) (VB10) copolymer was performed under alkali con-
ditions at 60 ꢀC during 2.5 h. Under these conditions, both the
VAc units and the ester links between BMDO and VAc units
should be hydrolyzed. This should result in the formation of
species including short segments of poly(vinyl alcohol).
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After hydrolysis reaction, the solubility properties of VB10
changed completely, the hydrolysis product being not soluble
in THF, unlike the starting copolymer. As the residue was,
however, soluble in DMF, SEC-DMF analysis was possible. The
complete disappearance of the main molar mass distribution
originally observed for VB10 showed that the copolymer was
hydrolytically degraded as expected. The 1H-NMR analysis of
the final residue was additionally performed in DMSO-d6 (Sup-
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spectrum compared to the spectrum of VB10, notably the
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CONCLUSIONS
With the view of targeting degradable poly(vinyl acetate) based
macromolecules, the RAFT copolymerization of BMDO and VAc
was successfully carried out using MEA as a controlling agent.
The copolymerization reactions were performed in toluene at
80 ꢀC in the presence of AIBN as an initiator. Monomer mix-
tures with low BMDO contents (lower than 30 mol %) were
used. In all the cases, well-defined P(VAc-co-BMDO) exhibiting
molar masses from 1300 to 3000 g mol21 were obtained with
molar mass dispersities lower than 1.26. The livingness of the
obtained chains was shown by successful chain extension
experiments with VAc, although the presence of dead chains
was also evidenced. The final P(VAc-co-BMDO) was shown to
degrade when treated by a mixture of KOH/MeOH in reflux dur-
ing 2.5 h, confirming that ester groups were successfully intro-
duced in the main chain. This is the first study on RAFT
copolymerization of VAc and BMDO additionally demonstrated
that the manipulation of BMDO and the design of macromolecu-
lar architectures obtained by radical ring opening copolymeriza-
tion of BMDO is not trivial and requires fine tuning of the
reaction conditions, particularly to reach higher molar masses.
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ACKNOWLEDGMENTS
GGA is grateful to CNR-DSCTM for the support in the frame of
Short Term Mobility Program. BC is grateful to the IUF (Institut
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