含磷酰杂菲共聚酯的聚集态和热性能研究

Aggregation State and Thermal Properties of Copolyesters Containing Phosphaphenathrene

6-氧化-6-氢-二苯基(c,e)(1,2)氧杂磷酰基-1,4二羟基苯、对苯二甲酰氯(p-DC)、癸二酰氯(SB)通过溶液聚合合成含磷酰杂菲共聚酯。采用红外光谱、凝胶渗透色谱、差示扫描量热仪、热失重分析仪、热台偏光显微镜、广角 X 射线衍射等对聚酯的合成、聚集态结构、热性能等进行了研究。结果表明,可以通过调节共聚酯中 SB 与p-DC 的配比改变其结晶性和玻璃化转变温度(T_g)。SB 与 p-DC 的配比低于4:6时,共聚酯具有明显的结晶性,且其结晶能保持至355℃。随着聚酯中 p-DC 含量的增加,共聚酯的 T_g从30℃上升至172℃,600℃时共聚酯热降解的剩碳率从4.7%上升至49.3%。

Phosphorus-containing copolyesters were synthesized via solution polycondensation from 2-[ 6- oxide-6H-dibenz（c, e） （1,2） oxaphos-phorin-6-yl ] -dihydroxyphenylene, sebacoyl chloride, and p-dibenzoyl chloride. The structures and thermal behaviors were investigated by FT-IR, GPC, DSC, TGA, POM, and WXRD. The properties of the copolyesters can be adjusted by changing the mol ratio of sebacoyl to p-dibenzoyl. As the ratio was lower than 4：6, the copolyester was crystalizable with a melting point about 355 ℃. When the mol ratio changed from 10/0 to 1/9, the Tg increased from 30 ℃ to 172℃, the char yield at 600℃ increased from 4.7 % to 49.3 %.