In Situ Monitoring of Polymerization-Induced Self-Assembly and Gelation During the Synthesis of Triblock Copolymers via Time-Resolved Small-Angle X-ray Scattering and Rheology
In Situ Monitoring of Polymerization-Induced Self-Assembly and Gelation During the Synthesis of Triblock Copolymers via Time-Resolved Small-Angle X-ray Scattering and Rheology
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DOI：
10.1021/acs.macromol.3c00444
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发表时间：
2023-05
期刊：
影响因子：
5.5
通讯作者：
Riku Yamanaka;Ayae Sugawara-Narutaki;Rintaro Takahashi
中科院分区：
文献类型：
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作者：
Riku Yamanaka;Ayae Sugawara-Narutaki;Rintaro Takahashi
从亲溶剂聚合物的两端聚合的疏溶剂单体在溶液中产生了BAB三嵌段共聚物。扩展的疏溶剂嵌段的自组装可能导致网络的形成和凝胶化。这一过程被称为三嵌段共聚物的聚合诱导自组装（PISA），是一个非常有趣的话题。然而，与PISA在二嵌段共聚物中的作用相比，其潜在机制尚不清楚。在这项研究中，我们首次使用两种独立的现场时间分辨技术──小角度x射线散射和振荡流变学──来监测三嵌段共聚物的PISA和凝胶化过程。我们发现，凝胶在诱导期后立即进行，与涉及聚合物的缩聚或交联反应的传统凝胶化过程不同。本研究揭示了三嵌段共聚物合成过程中PISA和网络形成的整个过程。
The polymerization of solvophobic monomers from both ends of solvophilic polymers produces BAB triblock copolymers in solution. The self-assembly of the extending solvophobic blocks may lead to network formation and gelation. This process, referred to as polymerization-induced self-assembly (PISA) in triblock copolymers, is a topic of significant interest. The underlying mechanism, however, has been poorly understood in comparison to that of PISA in diblock copolymers. In this study, we used two independentin situtime-resolved techniques─small-angle X-ray scattering and oscillatory rheology─to monitor the PISA and gelation process of triblock copolymers for the first time. We discovered that the gelation proceeds instantaneously after an induction period and is distinct from conventional gelation processes that involve the polycondensation or cross-linking reactions of polymers. This study sheds light on the entire process of PISA and network formation during the synthesis of triblock copolymers.