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

分子主链各向同性的光学活性芳香族聚酮的合成研究

基本信息

批准号：
05650891
负责人：
YONEZAWA Noriyuki
金额：
$ 1.47万
依托单位：
Gunma University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

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.

单体设计与高分子合成[亲电芳香取代反应] 首先研究了苯甲醚与苯甲酸衍生物的直接酰化反应和傅克酰化反应。进行了两种酰基受体单体2,2'-二甲氧基联苯和2,2'-二甲氧基二苯醚与二羧酸（对苯二甲酸、间苯二甲酸、萘二甲酸和氧基双苯甲酸）的芳香族亲电取代聚合反应。通过2,2'-二甲氧基联苯和对苯二甲酸的快速聚合得到非晶态高分子量芳香聚酮。 [芳香偶联反应] 在阐明了酮羰基对卤代二苯甲酮芳香偶联反应的延迟作用后，确定了该偶联反应的优选条件。根据上述模型反应程序，使用镍络合物/锌还原剂催化剂体系，通过芳香族偶联聚合反应合成了新型全芳香族聚联苯酮。功能性侧链基团的构建[含有氨基酸单元的锚定化合物的合成] 作为将光学活性氨基酸部分插入聚合物链中的构建单元，三种新的通过控制双键的反应性和假顺反异构化，合成了丙烯酰-L-丙酰胺衍生物。[共聚物的合成及侧链基团的官能团互变] 合成了具有烷氧基、具有高耐热性的高分子量芳香族共聚酮。阐明了聚合物中保护性醚键的断裂方法。芳香族聚酮合成最新进展综述检索并介绍了芳香族聚酮的合成、结构分析和物理性能的最新进展（3年），特别是微观结构与物理/化学性能之间的关系分析。