| Research Abstract |
The monomer with cyclic imide structure shows unusual anionic polymerization reactivity which the acyclic one does not have. N-substituted maleimides could be polymerized with relatively weak initiators such as alkali metal alcoholates and ate complexes. Specially, N-phenylmaleimide, one of the N-substituted maleimides, was polymerized with living nature with alkali metal tert-butoxides. Several N- (p-substituted-phenyl) maleimides possessing electron donating or electron withdrawing groups were synthesized. The investigation of the anionic polymerization reactivity of such monomers revealed that the anionic polymerization reactivity is lowered for either monomer with electron donating or withdrawing group compared with that of non-substituted N-phenylmaleimide. Combined with the results from molecular orbital calculation, it was concluded that the anionic polymerization reactivity is determined by the shapes and densities of both HOMO of the growing species and LUMO of the monomer.
Various N-substituted maleimides having functional groups at N-substituents were also synthesized and polymerized. For N- (p-vinylphenyl) maleimide, group selective polymerization could be acheved. In this polymerization, the control of molecular weight of the polymer was also succeeded in by living polymerization. Anionic polymerization of N- (2,3,4,5,6-pentafluorophenyl) maleimide and copolymerization of N-phenylmaleimide with a fluorine containing epoxide gave novel polymers with unusual properties.
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