含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环液晶共聚酯的合成与表征  

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTALLINE COPOLYESTERS WITH X-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS AND CROWN ETHER CYCLE OF cis-4,4′-BIS(4-HYDROXY PHENYLAZO)DIBENZO-18-CROWN-6

作　　者：张晓静[1] 张淑媛[2] 杨海隆[2] 贾天刚[1] 牛英英[2] 王世银[1] 李自法[3] 

机构地区：[1]郑州轻工业学院材料与化学工程学院河南省表界面科学重点实验室,郑州450002 [2]郑州大学化学系,郑州450052 [3]郑州大学材料工程学院,郑州450052

出　　处：《高分子学报》2008年第8期765-770,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号29974026);河南省自然科学基金(基金号0211021100);河南省教育厅自然科学基金(基金号20021500004)资助项目

摘　　要：以4，4’-（a，ω-辛二酰氧）二苯甲酰氯（M1）、2，5-双[4-’（对癸氧基苯基）苯甲酰氧基]对苯二酚（M2）和顺式-4，4＇-双（4-羟基苯基偶氮）二苯并-18-冠-6（M3）为单体，通过溶液共缩聚反应，合成了一系列新的含x-型二维液晶基元和顺式-4，4＇-双（4-羟基苯基偶氮）二苯并-18-冠-6冠醚环的主链型液晶共聚酯。单体1（M1）由对羟基苯甲酸和辛二酰氯，通过酯化和取代反应制备，单体2（M2）由2，5-二羟基苯醌和对癸氧基苯基苯甲酰氯通过酯化和还原反应制备，单体3（M3）由顺式-二氨基二苯并-18-冠-6和苯酚通过重氮化和偶联反应制备。共聚酯的分子量不高，[η]在0.30-0.39之间。单体的化学结构通过IR、UV、^1H-NMR、MS和元素分析等方法确证。共聚酯的外观为黄色粉状固体，除共聚酯CP9外，室温下不溶于CHCl3和THF溶剂。共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究，发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态，在液晶态可以观察到近晶相和向列相的典型织构。共聚酯的熔融温度（Tm）和各向同性温度（Ti）随共聚酯分子中顺式-4，4＇-双（4-羟基苯基偶氮）二苯并-18-冠-6用量的改变呈规律性变化。WAXD研究进一步证实了共聚酯的液晶性。A series crown ether cycles of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic units and of cis-4, 4＇-bis （4-hydroxyphenylazo） dibenzo-18-crown-6 was synthesized via solution cocondensation polymerizations from 4, 4＇-（ a, ω-octanedioyloxy ） dibenzoyl dichloride （M1）, 2, 5-bis （ pdecyloxyphenylbenzoyloxy） hydroquinone （ M2 ） and cis-4,4＇-bis （4-hydroxyphenylazo） dibenzo- 18-crown-6 （ M3 ） as the monomers. Monomer M1 was synthesized by esterification and substitution reactions of p-hydroxybenzoic acid and oetanedioyl chloride. Monomer M2 was synthesized by esterfieation and reduction reactions of 2, 5- dihydroxybenzoquinone and p-deeyloxyphenylbenzoyl chloride. Monomer M3 was synthesized by diazotization and coupling reactions of cis-diaminodibenzo-18-erown-6 and phenol. The molecular weights of eopolyesters were not high,and the [η] of the eopolyesters was in the range the of 0.39-0.30 dL/g. The monomer structures were identified by using elementary analysis, IR, UV, ^1H-NMR and MS etc. All the copolyester samples were yellowish powders and insoluble at room temperature in THF and CHC13 except the sample CP9. The properties of copolyesters were investigated by using GPC, [η], DSC, TG, WAXD and POM. It was found that all the eopolyesters went into liquid crystal phase when they were heated over their melting temperature （Tm）. CP2 - CP8 can exhibit both smeetie and nematie phases, and the typical liquid crystal textures of smeetic and nematie phases can be observed. CP1 and CP9 only have nematie phase. The melting temperature and isotropie temperature （ Ti ） of all eopolyesters increased regularly with increasing the cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-erown-6 unit content in the eopolyesters for the reason that the flexibility of-OCH2OCH2-chains in eomonomer M3 rendered the eopolymer to build up regular structure easily and increase its degree of ordered arrangement. The temperatures of 5 % weight loss, （Td） in TG exp

关 键 词：x-型二维液晶基元 顺式-4 4'-双(4-羟基苯基偶氮)二苯并-18-冠-6 液晶共聚酯 合成与表征 

分 类 号：O633.14[理学—高分子化学]