采用动态和静态光散射技术研究三嵌段共聚物在稀溶液中的自组装途径  

Study on the Self-Assembly Pathway of Triblock Terpolymers in Dilute Solution by Dynamic and Static Light Scattering Techniques

作　　者：戴学志 沈金朋[1] 田强 梁华[1] 朱杉 强晓莲 DAI Xue-zhi;SHEN Jin-peng;TIAN Qiang;LIANG Hua;ZHU Shan;QIANG Xiao-lian(State Key Laboratory of Environment-Friendly Energy Materials,School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,China;Polymer Physics Research Laboratory,Institute of Chemical Materials,China Academy of Engineering Physics(CAEP),Mianyang621900,China)

机构地区：[1]西南科技大学材料与化学学院,环境友好能源材料国家重点实验室,四川绵阳621010 [2]中国工程物理研究院化工材料研究所高分子物理研究室,四川绵阳621900

出　　处：《光谱学与光谱分析》2025年第3期665-671,共7页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(52103101,22275150,U2230130);四川省自然科学基金项目(2022NSFSC1228,2022JDTD0017);西南科技大学博士基金项目(21zx7102)资助。

摘　　要：三嵌段共聚物(TTPs)在稀溶液中经分级自组装形成多隔室胶束(MCMs)的过程,通常包括TTPs分子链自组装形成星形胶束、星形胶束自组装形成MCMs两个主要步骤,其中前一步骤理论上存在单级自组装或分级自组装两种未被阐明的可能途径。选择非晶态TTPs聚苯乙烯-b-聚丁二烯-b-聚甲基丙烯酸甲酯(PS-b-PB-b-PMMA,SBM)为模型分子,通过溶剂交换的方法使SBM在稀溶液中自组装,采用动态及静态光散射技术对SBM自组装形成星形胶束进一步自组装形成MCMs的过程进行实时、动态表征,并结合透射电镜(TEM)辅助测试结果进行分析。研究结果表明,SBM在稀溶液中自组装形成星形胶束的途径是直接由SBM链团/网经单级自组装途径形成星型胶束,而不是存在单链或多链胶束等过渡形态的分级自组装途径。SBM稀溶液浓度对该自组装途径无明显影响,该自组装过程在12 h内已达到动态平衡。研究结果可为多组分嵌段共聚物在稀溶液中自组装过程的热力学和动力学研究、光散射技术在高分子溶液表征中的应用提供参考。Hierarchical self-assembly of triblock terpolymers(TTPs)in dilute solution to form multicompartment micelles(MCMs)typically involves two main steps:self-assembly of TTPs chains into intermediate star-like micelles and further self-assembly of star-like micelles into MCMs.The former step,in theory,has two possible pathways:single-stage self-assembly or hierarchical self-assembly,which has not yet been fully revealed.Here,an amorphous linear A-b-C type TTP polystyrene-block-polybutadiene-block-poly(methyl methacrylate)(abbrev.PS-b-PB-b-PMMA or SBM)was used as a model molecule;solvent exchange strategy was employed to induce self-assembly of SBM in dilute solution.Dynamic light scattering(DLS),static light scattering(SLS),and auxiliary transmission electron microscope(TEM)were used for real-time and dynamic monitoring of the self-assembly process of SBM into star-like micelles and further self-assembly of star-like micelles into MCMs.The results revealed that the self-assembly pathway of SBM in dilute solution into star-like micelles was a direct single-stage self-assembly pathway from SBM chain clusters/networks to form star-like micelles,rather than a hierarchical self-assembly pathway involving intermediate states such as single-chain or multi-chain micelles.Additionally,the concentration of SBM dilute solution had no significant effect on this self-assembly pathway,and the self-assembly process reached dynamic equilibrium within 12 hours.The results provide valuable information for the thermodynamic and kinetic studies of the self-assembly process of multi-component block copolymers in dilute solution,and for applying light scattering technology to characterize polymer solutions.

关 键 词：嵌段共聚物 自组装 胶束 途径 光散射 

分 类 号：O648.1[理学—物理化学]