In an attempt to develop structural characterisation of polymers from
fluorinated acrylic derivatives, a detailed C-13 NMR analysis of free
radical and anionic poly(2,2,2-trifluoroethyl methacrylate) (poly(TFEM
)) was performed as compared to relevant literature studies concerning
the corresponding methyl methacrylate (MMA) polymers. On the other si
de, the moderately syndiotactic microstructure of the poly(TFEM) sampl
es fits very well with that of corresponding poly(MMA) samples and can
be interpreted on the basis of the same statistical distribution of t
riads. Thus it appears that the presence of the -CH2-CF3 group does no
t affect in a determining way the stereochemistry of the polymerizatio
n. According to this final statement, anionic initiators give prevaili
ngly isotactic poly(TFEM) as detected by C-13 NMR.