Selective solvent conditions influence sequence development and supramolecular assembly in step-growth copolymerization
Selective solvent conditions influence sequence development and supramolecular assembly in step-growth copolymerization
复制标题
选择性溶剂条件影响逐步生长共聚中的序列开发和超分子组装
DOI：
10.1039/d1sm01571k
复制
发表时间：
2022
期刊：
影响因子：
3.4
通讯作者：
DuBay, Kateri H.
中科院分区：
文献类型：
--
作者：
Hamblin, Ryan L.;Nguyen, Nhu Q.;DuBay, Kateri H.
由于序列对材料性能和自组织的影响，合成共聚物中的序列控制仍然是聚合物科学中一个诱人的目标。更好地理解整个聚合过程中的序列发展将有助于设计简单的，可推广的方法来控制序列和调整超分子组装。在以前的模拟溶液为基础的逐步增长的共聚，我们已经表明，弱，非键合的吸引力相同类型的单体之间可以产生一个微相分离之间的延长新生低聚物，从而改变序列。这项工作进一步探讨了这一现象，研究如何有效的吸引力的相互作用，介导的溶剂选择性的反应物种之一，影响发展的序列和超分子组装在一个简单的A-B共聚。我们发现，作为单体之间的有效吸引力的增加，一个紧急的自组织的反应物导致反应动力学和序列发展的转变。当溶剂介导的相互作用具有足够的选择性时，A和B单体的简单混合物低聚并自组装成两亲共聚物的特征结构。这些结构的组成和形态以及它们的链的序列对共聚单体种类之间的亲和力的相对平衡是敏感的。我们的研究结果表明，不同的A-B单体-溶剂的亲和力对序列开发的溶液为基础的共聚的影响，并因此知情的设计的合成方法的序列控制的两亲性共聚物及其聚集体。
Sequence control in synthetic copolymers remains a tantalizing objective in polymer science due to the influence of sequence on material properties and self-organization. A greater understanding of sequence development throughout the polymerization process will aid the design of simple, generalizable methods to control sequence and tune supramolecular assembly. In previous simulations of solution-based step-growth copolymerizations, we have shown that weak, non-bonding attractions between monomers of the same type can produce a microphase separation among the lengthening nascent oligomers and thereby alter sequence. This work explores the phenomenon further, examining how effective attractive interactions, mediated by a solvent selective for one of the reacting species, impact the development of sequence and the supramolecular assembly in a simple A–B copolymerization. We find that as the effective attractions between monomers increase, an emergent self-organization of the reactants causes a shift in reaction kinetics and sequence development. When the solvent-mediated interactions are selective enough, the simple mixture of A and B monomers oligomerize and self-assemble into structures characteristic of amphiphilic copolymers. The composition and morphology of these structures and the sequences of their chains are sensitive to the relative balance of affinities between the comonomer species. Our results demonstrate the impact of differing A–B monomer–solvent affinities on sequence development in solution-based copolymerizations and are of consequence to the informed design of synthetic methods for sequence controlled amphiphilic copolymers and their aggregates.