Yan Xiaojin, Hou Bo, Shao Yu, Xu Yu-Chun, Li Wei-Yi, Guo Qing-Yun, He Jinlin, Ni Peihong, Zhang Wen-Bin
College of Chemistry, Chemical Engineering and Materials Science, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Soochow University, Suzhou, Jiangsu, 215123, P. R. China.
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
Macromol Rapid Commun. 2023 Jan;44(1):e2200319. doi: 10.1002/marc.202200319. Epub 2022 Jun 16.
Due to the fast phase separation kinetics and small feature size, the self-assembly of giant molecules has attracted lots of attention. However, there is not much study on multicomponent giant surfactants. In this work, through a modular synthetic strategy, different polyhedral oligomeric silsesquioxane (POSS)-based molecular nanoparticles are installed with diverse functionalities (hydrophobic octavinyl POSS (VPOSS), hydrophilic dihydroxyl-functionalized POSS (DPOSS), and omniphobic perfluoroalkyl-chain-functionalized POSS (FPOSS)) on the ends of one polystyrene (PS) chain to build up a series of triblock bola-form giant surfactants denoted as XPOSS-PS -FPOSS (X represents V or D). The target molecules are prepared by a combination of atom transfer radical polymerization (ATRP), esterification, as well as Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and thiol-ene "click" reactions. These macromolecules are thoroughly characterized by combined technologies including nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analyses. It is revealed by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) that VPOSS-PS -FPOSS adopts a two-phase separation scenario where VPOSS and POSS are segregated in one phase. DPOSS-PS -FPOSS with a third hydrophilic DPOSS shows a three-phase separation scenario, where highly ordered phase structures are difficult to develop owing to the competition of mutual phase separation processes and may be trapped in kinetically metastable states.
由于快速的相分离动力学和微小的特征尺寸，大分子的自组装引起了广泛关注。然而，关于多组分巨型表面活性剂的研究并不多。在这项工作中，通过模块化合成策略，在一条聚苯乙烯（PS）链的末端安装了具有不同功能的不同多面体低聚倍半硅氧烷（POSS）基分子纳米颗粒（疏水性八乙烯基POSS（VPOSS）、亲水性二羟基官能化POSS（DPOSS）和全疏性全氟烷基链官能化POSS（FPOSS）），以构建一系列三嵌段bola型巨型表面活性剂，记为XPOSS-PS -FPOSS（X代表V或D）。目标分子通过原子转移自由基聚合（ATRP）、酯化反应以及铜（I）催化的叠氮化物-炔烃环加成（CuAAC）和硫醇-烯“点击”反应相结合的方法制备。这些大分子通过包括核磁共振（NMR）、尺寸排阻色谱（SEC）和基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF MS）分析在内的联合技术进行了全面表征。小角X射线散射（SAXS）和透射电子显微镜（TEM）表明，VPOSS-PS -FPOSS呈现两相分离情况，其中VPOSS和POSS在一相中分离。带有第三个亲水性DPOSS的DPOSS-PS -FPOSS呈现三相分离情况，由于相互相分离过程的竞争，难以形成高度有序的相结构，并可能被困在动力学亚稳态中。
