Li Guoqing, Zhang Zhiyi, Xiao Wenhao, Wu Tongtong, Xu Jinbao
Jiaxing Key Laboratory of Preparation and Application of Advanced Materials for Energy Conservation and Emission Reduction, College of Advanced Materials Engineering, Jiaxing Nanhu University Jiaxing 314001 P. R. China
Jiangxi General Institute of Testing and Certification Nanchang 330052 P. R. China.
RSC Adv. 2023 Oct 3;13(41):28931-28939. doi: 10.1039/d3ra04667b. eCollection 2023 Sep 26.
The broad application of polyacrylamides (PAMs) has greatly promoted the development of new synthetic methods to prepare PAM-based functional (co)polymers regarding their traditional preparation the direct polymerization of various acrylamide monomers. Herein, we have explored the post-polymerization modification of the poly(2,2,2-trifluoroethyl acrylate) (PTFEA) homopolymer, a typical non-activated ester, and various amines using the organo-catalytic system involving 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,2,4-triazole (TA). The reaction kinetics (, the optimized reaction solvent, temperature, time, initial molar ratio of amines to esters and the molar ratio of DBU to TA) were carefully studied with the modulus substrate of iso-propylamine as the formed poly(iso-propyl acrylamide) (PNIPAM) representing the most investigated PAM. The full and partial amidation of the esters in PTFEA could be precisely regulated just by controlling the kinetic conditions to give (co)polymers with designable compositions and structures. We have demonstrated that the poly(-acryloyl pyrrolidine) obtained by the post-polymerization modification of non-activated ester and pyrrolidine exhibited a noticeable phase transition, which confirmed the robustness and versatility of the post-polymerization modification. The described method paves the way for the synthesis of various (co)polymers with amide side chains from readily available polymer precursors.
聚丙烯酰胺（PAM）的广泛应用极大地推动了新合成方法的发展，这些方法用于制备基于PAM的功能（共）聚合物，而其传统制备方法是各种丙烯酰胺单体的直接聚合。在此，我们探索了聚（丙烯酸2,2,2-三氟乙酯）（PTFEA）均聚物（一种典型的非活性酯）与各种胺在涉及1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）和1,2,4-三唑（TA）的有机催化体系下的后聚合改性。以异丙胺作为形成的聚（异丙基丙烯酰胺）（PNIPAM）（代表研究最多的PAM）作为模量底物，仔细研究了反应动力学（即优化的反应溶剂、温度、时间、胺与酯的初始摩尔比以及DBU与TA的摩尔比）。通过控制动力学条件，PTFEA中酯的完全和部分酰胺化可以精确调控，从而得到具有可设计组成和结构的（共）聚合物。我们已经证明，通过非活性酯与吡咯烷的后聚合改性得到的聚（丙烯酰基吡咯烷）表现出明显的相变，这证实了后聚合改性的稳健性和通用性。所描述的方法为从易得的聚合物前体合成各种具有酰胺侧链的（共）聚合物铺平了道路。
