A novel vinylbiphenyl monomer, 2-methoxy-5-phenylstyrene
(MOPS), was designed and efficiently synthesized to investigate the
stereospecific polymerization of bulky and polar styrenic derivative.
Regardless of its large side group and electron-donating o-methoxy substituent, this compound showed a high polymerizability
and was readily converted to the corresponding polymers with moderate
to high molecular mass through radical, anionic, and coordination
polymerizations. The resultant polymers were characterized by a combination
of 1H/13C NMR spectrometry, thermal analysis,
and wide-angle X-ray diffraction. Radical polymerization initiated
by AIBN in toluene at 60 °C produced a syndiotactic-rich (rr = 0.37) polymer as most bulky vinyl monomers, whereas
anionic polymerizations induced by n-BuLi yielded
only isotactic-rich polymers no matter if polar tetrahydrofuran (−78
°C, mm = 0.54) or apolar toluene (−40
°C, mm = 0.78) was employed as the solvent.
The isotactic-rich microstructure obtained by anionic polymerization
in polar solvent at low temperature, the condition that usually leads
to syndiotactic-rich polymer, manifested the strong interactions between
the o-methoxy groups of the growing chain end and
the penultimate unit with the lithium counterion. Highly isotactic
(mm = 0.95) and perfect syndiotactic (rr > 0.99) polymers were obtained via coordination polymerizations
in toluene at ambient temperature with the β-diketiminatoyttrium
precursor (I) and the heterocyclic-fused cyclopentadienylscandium
complex (III) as the catalytic precursor, respectively.
All the polymers were thermally stable with 5% weight loss temperatures
above 360 °C. They underwent glass transitions in the temperature
range of 124–140 °C depending on the tacticity, much higher
than polystyrene, implying the dominant role of congestion effect
of large side groups on the segment movement restriction of polymer
chain. Both isotactic and syndiotactic polymers were crystalline and
had melting points higher than 300 °C, although the atactic and
less stereoregular polymers were amorphous. The facile synthesis in
conjunction with stereostructure tailorability, high thermal stability,
glass transition temperature, and melting point makes the polymer
a promising candidate for not only helical functional material but
also engineering plastics.