化工学报 ›› 2008, Vol. 59 ›› Issue (6): 1556-1564.

• 材料化学工程与纳米技术 • 上一篇    下一篇

相转移催化法合成新型金刚烷基聚芳酯

刘卅; 郭建维   

  1. 华南理工大学材料科学与工程学院; 广东工业大学轻工化工学院
  • 出版日期:2008-06-05 发布日期:2008-06-05

Synthesis of novel polyarylates based adamantane via phase transfer catalysis

LIU Sa;GUO Jianwei   

  • Online:2008-06-05 Published:2008-06-05

摘要:

金刚烷基聚合物是一类高性能聚合物,本文对新型金刚烷基聚芳酯的合成和性能进行了探索研究。以金刚烷为原料合成了4-(1-金刚烷基)-1,3-二苯酚(ADRL)和1,3-二(4-苯酚)-金刚烷(BHAD)单体。以苄基三乙基氯化铵为相转移剂,通过水/有机两相界面缩聚法使ADRL与对苯二甲酰氯、BHAD与对苯二甲酰氯分别缩聚合成了新型金刚烷基聚芳酯(P1、P2)。所得聚合物为无定形聚合物,可溶于DMSO 、NMP、DMF、DEC等多种溶剂。采用DSC和TG等方法分析了聚合物的热性能,P1和P2的玻璃化转变温度Tg分别为214℃和189℃,10%热分解温度高于400℃。对反应条件研究表明,BHAD比ADRL易溶于氢氧化钠溶液中,相同条件下更易获得高分子量聚合物,在30℃、NMP溶剂中P1和P2系列聚芳酯最高特性黏度分别为43 ml·g-1和76 ml·g-1。

关键词:

金刚烷, 聚芳酯, 相转移催化, 合成, 热性能

Abstract:

Polymers containing adamantane moieties are a kind of high performance materials.This work concentrates primarily on the synthesis and properties of polyarylates based adamantane.New adamantylhydroxybenzene monomers, 4-(1-adamantyl)-1,3-benzenediol(ADRL) and 1,3-bis(4-hydroxyphenyl) adamantane (BHAD) were synthesized from adamantane and characterized by means of IR, H NMR, 3C NMR and elemental analysis.Novel polyarylates (P1,P2) were synthesized from terephthalyl chloride and ADRL, BHAD as diphenols by aqueous/organic two-phase interfacial polycondensation, using benzyltriethylammonium chloride as phase transfer catalyzer.The synthesized polyarylates containing adamantane moieties were amorphous, and dissolved in a variety of solvents such as DMSO, NMP, DMF and DEC.The thermal properties were measured by DSC and TG.The results showed that glass transition temperatures were respectively 214℃(P1) and 189℃(P2).The 10% mass loss temperatures of polyarylates were above 400℃.Investigation of reaction conditions revealed that BHAD was easier to dissolve in sodium [JP+4]hydroxide solution and obtain high molecular weight polyarylates than ADRL under the same conditions.Inherent viscosities were measured in NMP at 30℃.The maximum inherent viscosities of P1 and P2 were 43 ml·g-1 and 76 ml·g-1, respectively.

Key words:

金刚烷, 聚芳酯, 相转移催化, 合成, 热性能