刚柔三嵌段共聚物的柱状结构构筑  

Organization of Coil-Rod-Coil Triblock Copolymers into Columnar Aggregates

作　　者：李照华[1] 樊树峰[1] 陈铁[1] 金龙一[1,2] 

机构地区：[1]长白山生物资源与功能分子教育部重点实验室延边大学化学系,延吉133002 [2]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《高分子学报》2016年第2期204-210,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21164013;21562043);吉林省新世纪优秀人才计划(项目号201410);南开大学元素有机化学国家重点实验室开放基金(基金号201410)资助

摘　　要：合成了以酯键和醚键相连的苯和联苯作为刚棒B嵌段,以聚合度为7,12和17的聚环氧乙烷为A嵌段及辛基或十六烷基为C嵌段的ABC型三嵌段线团-刚棒-线团分子.通过核磁共振氢谱和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF MS)对其结构进行了表征,利用偏光显微镜(POM)、示差扫描量热法(DSC)和小角X射线散射实验(SAXS)对其本体状态下的自组装行为进行了研究.结果表明,聚环氧乙烷聚合度为7、烷基链分别为辛基和十六烷基的化合物1a和2a在固相和液晶态分别自组装成倾斜柱状结构和矩形柱状结构,而具有长聚环氧乙烷链的化合物2b、2c和1c在固相都自组装成倾斜柱状结构.发现聚环氧乙烷链和烷基链的长度显著地影响线团-刚棒-线团分子体系的自组装行为.通过改变线团-刚棒-线团分子体系中柔性链长度的策略,可以精确地调控刚柔三嵌段共聚物的聚集体结构.The ABC coil-rod-coil triblock molecules,consisting of biphenyl and phenyl units connected together with ether and ester bonds as a rod building block,and poly（ ethylene oxide） s with DP of 7,12 and 17 and octyl or hexadecyl alkyl chains as flexible A and C coil segments,were successfully synthesized. These molecular structures were characterized by means of1H-NMR and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry（ MALDI-TOF MS）. The self-assembling behavior of these ABC coil-rod-coil triblock molecules was studied in bulk state,using differential scanning calorimetry（ DSC）,thermal polarized optical microscopy（ POM）,and small-angle X-ray scattering（ SAXS）. The experimental results showed that molecules 1a and 2a with poly（ ethylene oxide） coil chains（ DP = 7） and linked together with octyl or hexadecyl chains,self-assemble into an oblique columnar（ Ob） and a rectangular columnar（ Rect） structure in the solid state and liquid crystalline phase,respectively. While,molecules 2b,2c and 1c containing longer poly（ ethylene oxide） coil chains than 1a and 2a self-assemble into the oblique columnar nano-structures in the solid state. It was found that the lengths of the poly（ ethylene oxide） s and alkyl chains dramatically influence the self-assembling behavior of this coil-rod-coil molecular system. Therefore,supramolecular nanostructures of coil-rod-coil triblock copolymers can be accurately controlled via tuning the length of the coil chains connected with the rigid rod building block.

关 键 词：自组装 超分子结构 刚棒-线团分子 相行为 三嵌段 

分 类 号：O631.1[理学—高分子化学]