高分子学报
高分子學報
고분자학보
ACTA POLYMERICA SINICA
2009年
5期
403-408
,共6页
张淑媛%张晓静%贾天刚%郝国亮%李自法
張淑媛%張曉靜%賈天剛%郝國亮%李自法
장숙원%장효정%가천강%학국량%리자법
联苯型液晶基元%冠醚%液晶共聚酯%合成
聯苯型液晶基元%冠醚%液晶共聚酯%閤成
련분형액정기원%관미%액정공취지%합성
Biphenyl mesogenic unit%Crown ether%Liquid crystalline copolyesters%Synthesis
以4,4′-(α,ω-亚烷基二酰氧)二联苯甲酰氯(M1)、顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M2)、反式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M3)和1,10-癸二醇(M4)为单体,通过溶液共缩聚反应,合成了两个系列新的含联苯型液晶基元和偶氮型冠醚环的主链型液晶共聚酯.共聚酯的[η]在0.25~0.35和0.27~0.38之间.单体的化学结构通过IR、UV-Vis、1H-NMR、MS和元素分析等方法确证.共聚酯的性质采用[η]、DSC、TGA、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自熔融温度以上都能形成向列相液晶态,可以观察到向列相的丝状织构或纹影织构或球粒织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中柔性间隔基长度的增加而有规律地降低,含反式冠醚环的共聚酯的Tm和Ti均高于相应含顺式冠醚环的共聚酯的Tm和Ti.
以4,4′-(α,ω-亞烷基二酰氧)二聯苯甲酰氯(M1)、順式-4,4′-雙(4-羥基苯基偶氮)二苯併-18-冠-6(M2)、反式-4,4′-雙(4-羥基苯基偶氮)二苯併-18-冠-6(M3)和1,10-癸二醇(M4)為單體,通過溶液共縮聚反應,閤成瞭兩箇繫列新的含聯苯型液晶基元和偶氮型冠醚環的主鏈型液晶共聚酯.共聚酯的[η]在0.25~0.35和0.27~0.38之間.單體的化學結構通過IR、UV-Vis、1H-NMR、MS和元素分析等方法確證.共聚酯的性質採用[η]、DSC、TGA、WAXD和POM等方法進行瞭研究.髮現所有的共聚酯加熱到各自鎔融溫度以上都能形成嚮列相液晶態,可以觀察到嚮列相的絲狀織構或紋影織構或毬粒織構.共聚酯的鎔融溫度(Tm)和各嚮同性溫度(Ti)隨共聚酯分子中柔性間隔基長度的增加而有規律地降低,含反式冠醚環的共聚酯的Tm和Ti均高于相應含順式冠醚環的共聚酯的Tm和Ti.
이4,4′-(α,ω-아완기이선양)이련분갑선록(M1)、순식-4,4′-쌍(4-간기분기우담)이분병-18-관-6(M2)、반식-4,4′-쌍(4-간기분기우담)이분병-18-관-6(M3)화1,10-계이순(M4)위단체,통과용액공축취반응,합성료량개계렬신적함련분형액정기원화우담형관미배적주련형액정공취지.공취지적[η]재0.25~0.35화0.27~0.38지간.단체적화학결구통과IR、UV-Vis、1H-NMR、MS화원소분석등방법학증.공취지적성질채용[η]、DSC、TGA、WAXD화POM등방법진행료연구.발현소유적공취지가열도각자용융온도이상도능형성향렬상액정태,가이관찰도향렬상적사상직구혹문영직구혹구립직구.공취지적용융온도(Tm)화각향동성온도(Ti)수공취지분자중유성간격기장도적증가이유규률지강저,함반식관미배적공취지적Tm화Ti균고우상응함순식관미배적공취지적Tm화Ti.
Two series of novel main chain liquid crystalline copolyesters with biphenyl mesogenic units and azo type crown ether cycles were prepared via solution polycondensation from 4,4′-(α,ω-alkanedioyloxy)dibiphenylyloyl dichloride (M1),cis-4,4′-bis(4-hydroxy-phenylazo)dibenzo-18-crown-6(M2),trans-4,4′-bis-(4-hydroxy-phenylazo)-dibenzo-18-crown-6 (M3) and 1,10-decanediol (M4) as the monomers.The intrinsic viscosity [η] of the two series of copolyesters ranges from 0.25~0.35 dL/g and 0.27~0.38 dL/g,respectively.The structures of monomers were identified by elemental analysis,IR,UV-Vis,1H-NMR and MS.The properties of copolyesters were investigated by using DSC,TGA,WAXD and POM.All the copolyesters are able to form nematic mesophase after melting.The threaded texture,or ball granul texture or Schlieren texture of nematic phase can be observed on POM.Their melting temperature (Tm) and isotropic temperature (Ti) decrease regularly with increasing the length of flexible spacer in the copolyesters,and the Tm and Ti of copolyesters containing trans crown ether cycles are higher than those of the copolyesters containing cis crown ether cycles.