Syntheses of Special Structure Polymers Using Characteristic Reactivity of Phenol Residue and Elucidation of Their Specific Characters

1. 2，6-二羟基萘在碱性水中进行氧化偶联聚合，得到聚2，6-二羟基-1，5-萘.酚基3，5-二羟甲基化的酪氨酸衍生物和四羟甲基化的双酚在固态和溶液中均发生了热缩聚反应.通过铜催化氧化偶联聚合，得到了一种独特的聚氧化苯醚，其冠醚侧链与主链垂直排列。发现对位溴化单体不生成卤素置换聚合的均聚物，而是与2，6-二甲基-4-溴苯酚生成共聚物。以含两个酚残基的冠醚为原料，通过逐步Williamson型缩合反应合成了冠醚管状齐聚物。发现所得二聚体与铵盐形成包合物。采用Williamson型缩合反应合成了四对氯甲基硫杂杯[4]芳烃。在合适的反应条件下成功地得到了可溶性聚合物.三对溴代高氧杂杯[3]芳烃在碱的存在下进行卤素置换聚合，得到了管状的聚苯醚，但并不理想.硫杂杯[4]芳烃的氧化偶联聚合没有发生，而二-O-甲基化或苯甲酰基化的衍生物的氧化偶联聚合被发现产生聚（苯醚）。8.二-O-苯甲酰基化杯[4]芳烃在未保护的酚基上进行二-对位溴化，然后进行卤素置换聚合，反应程度为60%。

1. 2, 6-Dihydroxynaphthalene underwent the oxidative coupling polymerization in basic water, producing poly(2, 6-dihydroxy-1, 5-naphthylene).2. Thermal polycondensation took place for the tyrosine derivative, whose phenolic moiety was 3, 5-dihydroxymethylated, and for tetra-hydroxymethylated bisphenols in the solid sate as well as in the solution.3. The copper-catalyzed oxidative coupling polymerization of the crown ether possessing a phenol moiety in the ring gave unique poly (phenylene oxide), whose side chains of crown ether arranged perpendicularly on the main chain. The p-brominated monomer was found to give no homopolymer for halogen displacement polymerization but to produce the copolymer with 2, 6-dimethy1-4-bromophenol.4. The crown ether tube oligomer was synthesized by the stepwise Williamson-type condensation of the crown ether containing two phenol residues. The obtained dimer was found to make an inclusion complex with ammonium salt.5. Tetra-p-chloromethylated thiacalix [4] arene was polymerized by using the Williamson-type condensation. The soluble polymers were successfully obtained under appropriate reaction conditions.6. Tri-p-brominated homooxacalix [3] arene underwent the halogen displacement polymerization in the presence of base, producing the tubular poly (phenylene oxide), however, not perfect.7. The oxidative coupling polymerization of thiacalix [4] arene did not take place, while that of the di-O-methylated or-bezoylated derivative was found to produce the poly (phenylene oxide).8. Di-O-bezoylated calix [4] arene was di-p-brominated at the unprotected phenoilc moieties and then underwent the halogen displacement polymerization; the degree of the reaction was found to be 60%.