Synthetic Study of Optically Active Aromatic Polyketones having Isotropic Property at Right Angles to the Molecular Main Chain

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Monomer design and Macromolecule Synthesis[Electrophilic Aromatic Substitution reaction] Direct and Friedel-Crafts acylation reactions between anisoles and benzoic acid derivatives were investigated first. Aromatic electrophilic substitution polymerization reactions of 2 acylacceptant monomers, 2,2' -dimethoxybiphenyl and 2,2' -dimethoxydiphenyl ether, with dicarboxylic acids (terephthalic, isophthalic, naphthalenedicarboxylic, and oxybisbenzoic acids) were undertaken. An amorphous high-molecular-weight aromatic polyketone was obtained by rapid polymerization between 2,2' -dimethoxybiphenyl and terephthalic acid.[Aromatic Coupling Reaction] After elucidation of the retarding effect of ketone carbonyl group in aromatic coupling reaction of halobenzophenones, the preferred conditions of this coupling reaction were determined. According to the procedure of the model reactions described above, novel fully aromatic polybiphenylene ketone was synthesized by aromatic coupling polymerization using nickel complex/zinc reductant catalyst system.Construction of Functional Side Chain Groups[Synthesis of Anchor Compound containing Amino Acid Unit] As a building block inserting optically active amino acid moieties into the polymer chains, three new acryloyl-L-prolylamide derivatives were synthesized controlling the reactivity of the double bonds and pseudo cis-trans isomerization.[Copolymer Synthesis and Functional Group Interconversion of Side Chain Groups] High-molecular-weight aromatic co-polyketones, with high thermal resistance, having alkoxy groups was synthesized. The cleavage method for the protective ether bonding in the polymers was elucidated.Survey of Recent Advances in Aromatic Polyketone SynthesisThe recent advances (3 years) of the synthesis, structural analysis, and physical properties of aromatic polyketones were searched and presented, especially aiming in the relationship analysis between microstructure and physical/chemical properties.