RAFT dispersion polymerization following the formulation of polymerization induced self-assembly (PISA) and micellization of pre-prepared amphiphilic block copolymers in block-selective solvents are generally used to prepare block copolymer nano-assemblies. Herein, we make a comparison between these two methods by employing two typical block copolymers of poly(acrylic acid)-block-polystyrene (PAA-b-PS) and poly(ethylene glycol)-block-polystyrene (PEG-b-PS). It is found that the block copolymer nano-assemblies prepared by these two methods are similar with each other when the solvophilic block is relatively long and the solvophobic block is relatively short. Otherwise, the block copolymer nano-assemblies by these two methods are different. The possible reasons leading to the difference between PISA and micellization are discussed, and the kinetic factors including temperature, polymer concentration and solvent are ascribed. It is thought that the present study is helpful to clarify how the kinetic factors beyond the block copolymer itself affecting block copolymer morphology.

通常将在聚合引发的自组装（PISA）和在嵌段选择溶剂中预先制备的两亲嵌段共聚物的胶束化之后的RAFT分散聚合用于制备嵌段共聚物纳米组装件。在此，我们通过使用两种典型的聚（丙烯酸）-嵌段-聚苯乙烯（PAA- b - PS ）和聚（乙二醇）-嵌段-聚苯乙烯（PEG- b）嵌段共聚物对这两种方法进行比较。-PS）。发现当亲溶剂性嵌段相对较长而疏溶剂性嵌段相对较短时，通过这两种方法制备的嵌段共聚物纳米组装体彼此相似。否则，通过这两种方法的嵌段共聚物纳米组装体是不同的。讨论了导致PISA和胶束化差异的可能原因，并归纳了动力学因素，包括温度，聚合物浓度和溶剂。认为本研究有助于阐明超出嵌段共聚物本身的动力学因素如何影响嵌段共聚物的形态。