Hofman Anton H, Reza Mehedi, Ruokolainen Janne, Ten Brinke Gerrit, Loos Katja
Macromolecular Chemistry and New Polymeric Materials, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747, AG, Groningen, The Netherlands.
Department of Applied Physics, Aalto University, P.O. Box 11100, FI-00076, Aalto, Finland.
Macromol Rapid Commun. 2017 Sep;38(17). doi: 10.1002/marc.201700288. Epub 2017 Jul 27.
Involving supramolecular chemistry in self-assembling block copolymer systems enables design of complex macromolecular architectures that, in turn, could lead to complex phase behavior. It is an elegant route, as complicated and sensitive synthesis techniques can be avoided. Highly grafted double-comb diblock copolymers based on symmetric double hydrogen bond accepting poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers and donating 3-nonadecylphenol amphiphiles are realized and studied systematically by changing the molecular weight of the copolymer. Double perpendicular lamellae-in-lamellae are formed in all complexes, independent of the copolymer molecular weight. Temperature-resolved measurements demonstrate that the supramolecular nature and ability to crystallize are responsible for the formation of such multiblock-like structures. Because of these driving forces and severe plasticization of the complexes in the liquid crystalline state, this supramolecular approach can be useful for steering self-assembly of both low- and high-molecular-weight block copolymer systems.
将超分子化学引入自组装嵌段共聚物体系能够设计出复杂的大分子结构，进而可能导致复杂的相行为。这是一条巧妙的途径，因为可以避免复杂且敏感的合成技术。基于对称双氢键受体聚（4-乙烯基吡啶）-嵌段-聚（N-丙烯酰基哌啶）二嵌段共聚物和供体3-十九烷基苯酚两亲物的高度接枝双梳状二嵌段共聚物得以实现，并通过改变共聚物的分子量进行了系统研究。在所有复合物中均形成了双垂直片层内片层结构，与共聚物分子量无关。温度分辨测量表明，超分子性质和结晶能力是形成此类多嵌段状结构的原因。由于这些驱动力以及复合物在液晶态下的严重增塑作用，这种超分子方法对于调控低分子量和高分子量嵌段共聚物体系的自组装可能是有用的。
