A combined computer simulation and experimental study on coassembly of poly(2-(dimethylamino)ethyl methacrylate)-block-polystyrene (PDMAEMA-b-PS) block copolymers and PS brushes on silica particles was performed. PS brushes on silica particles at two different grafting densities were prepared by the “grafting to” approach, and PDMAEMA-b-PS block copolymers with different molecular weights and compositions were synthesized by reversible addition–fragmentation chain transfer polymerization. In THF/methanol mixtures, block copolymer chains and PS brushes coassemble into surface micelles (s-micelles), with collapsed PS cores and PDMAEMA coronae. Meanwhile, block copolymer chains are able to self-assemble into block copolymer micelles (b-micelles). Computer simulation results and experimental results indicate that block copolymer concentration, PS and PDMAEMA block lengths, and PS grafting density exert significant influences on the coassembly process. In low BCP concentration regime, the average size of s-micelles increases with BCP concentration and keeps unchanged at high concentration. The PS block length has a significant influence on the size of s-micelles. The average size increases with an increase in PS block length. For a BCP with long solvophilic PDMAEMA block, it is energy favorable to self-assemble into b-micelles, but to coassemble into s-micelles. With an increase in PDMAEMA block length, the morphology of the s-micelles changes from wormlike/spherical structures to spherical structures and to smaller spherical structures. The average size of the s-micelles coassembled by PS brushes at a lower grafting density is smaller than those coassembled by PS brushes at a higher grafting density.

中文翻译：

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线性二嵌段共聚物链和均聚物刷在二氧化硅颗粒上的组装：计算机模拟和实验研究的组合

进行了计算机模拟和实验研究相结合的实验，研究了聚（2-（二甲基氨基）甲基丙烯酸乙酯）-嵌段-聚苯乙烯（PDMAEMA- b- PS）嵌段共聚物和PS刷在二氧化硅颗粒上的共组装。通过“接枝到”方法制备了两种不同接枝密度的硅胶颗粒上的PS刷，PDMAEMA- b通过可逆加成-断裂链转移聚合反应合成了具有不同分子量和组成的-PS嵌段共聚物。在THF /甲醇混合物中，嵌段共聚物链和PS刷共组装成表面胶束（s-胶束），其中PS核和PDMAEMA日冕塌陷。同时，嵌段共聚物链能够自组装成嵌段共聚物胶束（b-胶束）。计算机仿真结果和实验结果表明，嵌段共聚物的浓度，PS和PDMAEMA的嵌段长度以及PS的接枝密度对共组装过程有重要影响。在低BCP浓度下，s-胶束的平均大小随BCP浓度的增加而增加，在高浓度下保持不变。PS块的长度对s胶束的大小有重要影响。平均大小随PS块长度的增加而增加。对于具有长的亲溶剂性PDMAEMA嵌段的BCP，自组装成b胶束但共组装成s胶束是有利的能量。随着PDMAEMA嵌段长度的增加，s-胶束的形态从蠕虫状/球形结构变为球形结构，并变为较小的球形结构。PS刷在较低的接枝密度下共同组装的s-胶束的平均尺寸小于PS刷在较高的接枝密度下共同组装的s-胶束的平均尺寸。s-胶束的形态从蠕虫状/球形结构变为球形结构，再到较小的球形结构。PS刷在较低的接枝密度下共同组装的s-胶束的平均尺寸小于PS刷在较高的接枝密度下共同组装的s-胶束的平均尺寸。s-胶束的形态从蠕虫状/球形结构变为球形结构，再到较小的球形结构。PS刷在较低的接枝密度下共同组装的s-胶束的平均尺寸小于PS刷在较高的接枝密度下共同组装的s-胶束的平均尺寸。