聚（N-氰乙基丙烯酰胺），一种在水中具有 LCST 和 UCST 行为的新型热响应均聚物,Polymer Chemistry

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聚（N-氰乙基丙烯酰胺），一种在水中具有 LCST 和 UCST 行为的新型热响应均聚物
Polymer Chemistry ( IF 4.1 ) Pub Date : 2022-01-25 , DOI: 10.1039/d2py00032f
Nicolas Audureau ₁ , Fanny Coumes ₁ , Jutta Rieger ₁ , François Stoffelbach ₁

Affiliation

我们最近证明了通过可逆加成-断裂链转移（RAFT）自由基聚合合成的聚（N-氰基甲基丙烯酰胺）（PCMAm）在水中表现出典型的上临界溶解温度（UCST）型转变，冷却和冷却之间的滞后非常小。加热步骤，并且PCMAm的浊点 ( T _{CP ) 强烈依赖于摩尔质量。}在这篇研究文章中，我们通过首次研究 N 的 RAFT 聚合，扩展了对 N-氰基烷基丙烯酰胺家族的研究。-氰乙基丙烯酰胺 (CEAm)，它与 CMAm 的不同之处在于在酰胺和氰基官能团之间存在第二个亚甲基。因此，获得了在纯水中表现出较低临界溶解温度 (LCST) 或同时具有 LCST 和 UCST (LCST < UCST) 的新型 CEAm 热响应均聚物。有趣的是，这种转变是尖锐和可逆的，具有低滞后。_{对不同浓度 DP n} ∼ 200的 PCEAm 的研究提出了一个闭环相图。最后，还介绍了在聚合物链中添加共聚单体单元（CMAm 或丙烯酰胺）对溶解度窗口的影响以及它们在实现可调双热响应性中的相互作用。

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Poly(N-cyanoethylacrylamide), a new thermoresponsive homopolymer presenting both LCST and UCST behavior in water

We have recently demonstrated that poly(N-cyanomethylacrylamide) (PCMAm) synthesized by reversible addition–fragmentation chain transfer (RAFT) radical polymerization exhibits a typical upper critical solution temperature (UCST)-type transition in water with a very small hysteresis between cooling and heating steps, and that the cloud point (T_CP) of PCMAm is strongly molar mass dependent. In this research article, we have extended the study of the N-cyanoalkylacrylamide family by studying for the first time the RAFT polymerization of N-cyanoethylacrylamide (CEAm), which differs from CMAm by the presence of a second methylene group between the amide and cyano functional groups. Thereby, novel thermoresponsive homopolymers of CEAm displaying either a lower critical solution temperature (LCST) or both a LCST and an UCST (with LCST < UCST) in pure water were obtained. Interestingly, the transitions were sharp and reversible with low hysteresis. The investigation of PCEAm with a DP_n ∼ 200 at different concentrations proposed a closed-loop phase diagram. Finally, the effect of the addition of comonomer units (CMAm or acrylamide) in the polymer chains on the window of solubility and their interplay in achieving tunable double thermoresponsiveness are also presented.

更新日期：2022-01-25

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