相转移催化法合成新型金刚烷基聚芳酯

Synthesis of novel polyarylates based adamantane via phase transfer catalysis

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43ml·g-1和76ml·g-1。

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, 1H NMR, 13C 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 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.