POSS基两亲性嵌段共聚物的合成及自组装行为  

Synthesis of POSS-based Amphiphilic Block Copolymers and Their Self-assembly Behavior

作　　者：李东霞 薛雨欣[1,2,4] 孙祥峰 桂雪峰 许凯 LI Dongxia;XUE Yunxin;SUN Xiangfeng;GUI Xuefeng;XU Kai(Guangzhou Institute of Chemistry,Chinese Academy of Sciences,Guangzhou 510650,China;University of Chinese Academy of Sciences,Beijing 100049,China;CAS Engineering Laboratory for Special Fine Chemicals,Guangzhou 510650,China;CASH GCC Shaoguan Research Institute of Advanced Materials,Shaoguan 512400,China;CASH GCC Fine Chemicals Incubator(Nanxiong)Co.,Ltd,Nanxiong 512400,China)

机构地区：[1]中国科学院广州化学研究所,广东广州510650 [2]中国科学院大学,北京101408 [3]中国科学院新型特种精细化学品工程实验室,广东广州510650 [4]国科广化韶关新材料研究院,广东韶关512400 [5]国科广化(南雄)新材料研究院有限公司,广东南雄512400

出　　处：《广州化学》2024年第2期1-5,I0001,F0003,共7页Guangzhou Chemistry

基　　金：中国科学院科技服务网络计划(No.20211600200052)。

摘　　要：用不同结构三乙氧基硅烷为原料,通过水解缩合和环氧化的方法合成了环氧基苯基低聚笼型倍半硅氧烷,再利用胺基和环氧开环反应与聚醚胺反应合成POSS基嵌段共聚物(PEA-POSS),最后将苯基结构羧酸化合成两亲性嵌段共聚物(PEA-POSS-COOH)。利用傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征了PEA-POSS-COOH的化学结构。采用溶剂挥发诱导法促使PEA-POSS-COOH自组装,形成以疏水POSS为核、亲水PEA链为壳的球形胶束。利用扫面电子显微镜(SEM)、能量分散型X射线光谱(EDS)、动态激光光散射(DLS)、小角X射线散射仪(XRD)和差示扫描量热仪(DSC)表征了组装体的形貌与结构性能。结果表明,POSS基两亲性嵌段聚合物可组装成粒径约1.14μm的球形胶束,且POSS结构中的π-π堆叠作用使得球形胶束具有较为稳定结构,熔点提高。Epoxy-based phenyl polyhedral oligomeric silsesquioxanes(POSS)were synthesized by hydrolytic condensation using different structures of triethoxysilanes as raw materials,and then POSS-based block copolymers(PEA-POSS)were synthesized by reaction of the amine group and epoxy ring-opening reaction with the polyether amine(PEA),and finally amphiphilic block copolymers(PEA-POSS-COOH)were synthesized by carboxylating the phenyl structure.The structural compositions of PEA-POSS-COOH were characterized using Fourier-transform infrared(FT-IR)and nuclear magnetic resonance hydrogen spectroscopy(1H-NMR).The PEA-POSS-COOH were self-assembled to form spherical micelles with hydrophobic POSS as the cores and hydrophilic PEA chains as the shell by the solvent evaporation-induced method.The morphology and structure properties of the assemblies were investigated by scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),dynamic light scattering(DLS),small-angle X-ray scattering(XRD),and differential scanning calorimetry(DSC).These results show that the POSS-based amphiphilic block polymers can be assembled into spherical micellar structures with a particle size of about 1.14μm,and theπ-πstacking effect in the POSS structure makes the spherical micelles have a more stable structure with an increased melting point.

关 键 词：笼型倍半硅氧烷 聚醚胺 有机/无机纳米杂化材料 自组装 球形胶束 

分 类 号：TQ314[化学工程—高聚物工业]