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）。酪氨酸衍生物（其酚基部分为3,5 -二羟甲基化）和四羟甲基化双酚在固体状态和溶液中均发生热缩聚。在铜催化下，环上含有苯酚的冠醚氧化偶联聚合得到独特的聚环氧苯，其冠醚侧链垂直排列在主链上。发现对溴化单体不能产生卤素置换聚合的均聚物，而能与2,6 -二甲基-4-溴苯酚产生共聚物。以含两个酚残基的冠醚为原料，采用williamson型逐级缩合法合成冠醚管低聚物。所得二聚体与铵盐形成包合物。采用williamson型缩聚法聚合了四对氯甲基化硫杯芳烃。在适当的反应条件下，成功地获得了可溶性聚合物。6 .三对溴化均羟基芳烃在碱的存在下进行卤素置换聚合，得到管状聚环氧苯，但并不完美。硫杯芳烃的氧化偶联聚合未发生，而二邻甲基化或苯甲酰化衍生物的氧化偶联聚合可生成聚环氧苯乙烯。二邻苯甲酰化杯芳烃在无保护的酚基团上进行二对溴化，然后进行卤素置换聚合；发现反应的程度为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%.