Keane Daniel P, Kolozsvary Timea, McDonald Benjamin, Poling-Skutvik Ryan
Department of Chemical Engineering, University of Rhode Island, Kingston, Rhode Island 02881, United States.
Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
ACS Macro Lett. 2024 Oct 15;13(10):1304-1310. doi: 10.1021/acsmacrolett.4c00428. Epub 2024 Sep 16.
Telechelic polymers are effective rheological modifiers that bridge between associative constituents to form elastic networks. The performance of linear telechelic chains, however, is controlled by entropic forces and thus suffers from an upper limit on bridge formation. This work overcomes this limitation by utilizing telechelic triblock copolymers containing bottlebrush midblocks. By comparing the rheological properties of emulsions linked by telechelic bottlebrush polymers to those containing linear chains, we determined that telechelic polymers with bottlebrush midblocks form elastic networks more efficiently. These enhanced rheological properties arise from the high stiffness of the bottlebrush midblocks, which offsets the entropic stretching penalty for bridge formation, enabling them to more readily form networks. This molecular-level control over polymer conformation in complex fluids opens avenues for designing highly elastic networks with minimal polymeric additives.
遥爪聚合物是有效的流变改性剂,可在缔合成分之间架桥形成弹性网络。然而,线性遥爪链的性能受熵力控制,因此在桥接形成方面存在上限。这项工作通过使用含有刷状中间嵌段的遥爪三嵌段共聚物克服了这一限制。通过比较由遥爪刷状聚合物连接的乳液与含有线性链的乳液的流变性能,我们确定具有刷状中间嵌段的遥爪聚合物能更有效地形成弹性网络。这些增强的流变性能源于刷状中间嵌段的高刚性,它抵消了桥接形成时的熵拉伸惩罚,使其能够更容易地形成网络。这种对复杂流体中聚合物构象的分子水平控制为设计使用最少聚合物添加剂的高弹性网络开辟了道路。