Stereospecific polymerization of 9‐fluorenyl methacrylate: Tacticity effects on the thermal and photophysical properties of the polymers

Abstract

Abstract Poly(9‐fluoreneyl methacrylate) was obtained through anionic polymerization with t ‐BuLi and t ‐BuMgBr and through radical polymerization with α,α′‐azobisisobutyronitrile. Anionic polymerization with t ‐BuLi in tetrahydrofuran and radical polymerization afforded syndiotactic polymers ( rr ∼ 90%), whereas anionic polymerization with Li and Mg initiators in toluene and CH 2 Cl 2 led to isotactic polymers. The thermal and photophysical properties of the polymers were examined. A syndiotactic polymer tended to show higher glass transition and decomposition temperatures than an isotactic polymer. However, polymers with different tacticities were not likely to assume specific, distinctive conformations such as a helix or a π‐stacked conformation in solution. An isotactic polymer showed stronger interactions in a CH 2 Cl 2 solution with 2,4,7‐trinitro‐9‐fluorenylidenemalononitrile, an electron‐acceptor molecule, than a syndiotactic polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4656–4665, 2004