高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

新型烷氧基胺的合成及其对MMA的调控聚合研究

罗菊香1,2，赵  磊2，肖旺钏1，程德书1,3   

  1. 1. 三明学院资源与化工学院
    2. 福州大学化工学院
    3. 东华大学材料科学与工程学院纤维材料改性国家重点实验室
  • 收稿日期:2024-12-11 修回日期:2025-03-11 出版日期:2025-03-24 发布日期:2025-03-24
  • 通讯作者: 程德书 E-mail:dscheng@mail.dhu.edu.cn
  • 基金资助:
    三明学院科学研究项目(批准号：KD23028P)，福建省自然科学基金项目(批准号：2022J011174)和福建区域发展项目(批准号：2022Y3003)资助

Synthesis of Novel Alkoxyamine and its controlled polymerization of MMA

LUO Juxiang1,2, ZHAO Lei2, XIAO Wangchuan1, CHENG Deshu1,3   

  1. 1. School of Resourses and Chemical Engineering, Sanming University 2. College of Chemical Engineering, Fuzhou University 3. College of Materials Science and Engineering, State Key Laboratory of Advanced Fiber Materials, Donghua University, 

  • Received:2024-12-11 Revised:2025-03-11 Online:2025-03-24 Published:2025-03-24
  • Contact: De-Shu cheng E-mail:dscheng@mail.dhu.edu.cn
  • Supported by:
    Supported by the Scientific Research Project of Sanming University, China(No.KD23028P), the Natural Science Foundation Project of Fujian Province, China(No.2022J011174) and the Regional Deveiopment Project of Fujian Province, China(No.2022Y3003)

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摘要： 单分子烷氧基胺调控的可逆失活自由基聚合工艺简单、制备的聚合物颜色浅、气味小，不含金属离子杂质，但设计合成可调控聚合甲基丙烯酸酯类单体的烷氧基胺是一项有挑战性的工作. 本文通过席夫碱还原、过硫酸氢钾复合盐(Oxone)氧化和自由基偶联三步反应合成了一种新型的烷氧基胺{3-[(2-氰基丙烷-2-基)氧基](异丙基)氨基}-2,2-二甲基-3-苯基丙腈(CPDMN)，研究了其对甲基丙烯酸甲酯(MMA)的调控聚合行为. 研究结果表明，单体转化率随聚合时间线性增加；聚合物分子量随着时间的延长而增大，凝胶色谱流出曲线峰型对称，没有明显的拖尾现象；聚合反应具有可控/“活性”自由基聚合的特点. 聚甲基丙烯酸甲酯(PMMA-ONR)大分子引发剂对MMA、苯乙烯(St)和甲基丙烯酸乙酯(EMA)的再引发实验进一步证明聚合物末端的烷氧基胺保留率良好. 考察了在有氧条件下CPDMN对MMA的调控性能，单体转化率达91.2%，PMMA分子量分布小于1.5，表明CPDMN可以在有氧条件下调控MMA的聚合. 该烷氧基胺拓展了氮氧自由基聚合调控单体的范围，在功能聚合物材料的合成方面具有良好的应用前景.

关键词: 氮氧稳定自由基聚合, 甲基丙烯酸甲酯, 可逆失活自由基聚合, 有氧自由基聚合

Abstract: Reversible-deactivation radical polymerization(RDRP) regulated by single-molecule alkoxyamine features a simple process, produces polymers with light color and minimal odor, and is free of metal ion impurities. However, the design and synthesis of alkoxyamines capable of regulating the polymerization of methacrylate monomers remains a challenging task. In this paper, an innovative type of alkoxyamine{3-[(2-cyanopropan-2-yl)oxy] (isopropyl)amino}-2,2-dimethyl-3-phenylpropanenitrile (CPDMN) was synthesized via Schiff base reduction, potassium persulfate complex oxidation and radical coupling, and then the controlled polymerization behavior of methyl methacrylate (MMA) mediated by CPDMN was investigated. The experimental results demonstrate that the monomer conversion rate increases linearly with polymerization time, while the polymer molecular weight grows with prolonged reaction duration. Gel permeation chromatography traces exhibit symmetrical peaks without significant tailing, indicating characteristic features of controlled/living radical polymerization. Subsequent re-initiation experiments using poly(methyl methacrylate) macroinitiator (PMMA-ONR) with MMA, styrene (St), and ethyl methacrylate (EMA) further confirm the effective retention of alkoxyamine end-groups in the resulting polymers. Finally, the regulation performance of CPDMN on MMA in the presence of oxygen was investigated, achieving a monomer conversion rate of 91.2% and a PMMA molecular weight distribution of less than 1.5, which demonstrates that CPDMN can control the polymerization of MMA with oxygen tolerance. The as-synthesized CPDMN extends the range of monomers applicable to nitroxide-mediated polymerization (NMP), demonstrating promising potential for the synthesis of functional polymeric materials.

Key words: Nitroxide-mediated radical polymerization; Methyl methacrylate, Reversible deactivation radical polymerization, Oxygen-tolerant radical polymerization

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