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

首先研究了苯甲酸衍生物与苯甲酸衍生物之间的直接酰化反应和Friedel-Crafts酰化反应。研究了2个酰基受体单体2,2′-二甲氧基联苯和2,2′-二甲氧基二苯基醚与二羧酸（对苯二甲酸、间苯二甲酸、萘二羧酸和氧二苯甲酸）的芳香亲电取代聚合反应。以2,2′-二甲氧基联苯和对苯二甲酸为原料，通过快速聚合得到了非定形的高分子量芳香族聚酮。【芳香偶联反应】在阐明了酮羰基在卤苯甲酮芳香偶联反应中的阻滞作用后，确定了该偶联反应的首选条件。根据上述模型反应的步骤，以镍配合物/锌还原剂为催化剂，采用芳族偶联聚合法制备了新型的全芳香族聚联苯酮。功能侧链基团的构建[含氨基酸单元锚定化合物的合成]作为在聚合物链中插入光学活性氨基酸基团的构建单元，合成了三个新的丙烯酰- l-丙烯酰胺衍生物，控制了双键的反应性和伪顺反异构化。[共聚物合成及侧链官能团的相互转化]合成了具有烷氧基的高分子量高热阻芳香族共聚酮。阐述了聚合物中保护醚键的解理方法。综述了近3年来芳香族聚酮类化合物的合成、结构分析、物理性质等方面的研究进展，重点分析了芳香族聚酮类化合物的微观结构与理化性质之间的关系。

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.