Synthesis of Thermal Degradable Poly(alkoxyamine) through a Novel Nitroxide Radical Coupling Step Growth Polymerization Mechanism

Synthesis of Thermal Degradable Poly(alkoxyamine) through a Novel Nitroxide Radical Coupling Step Growth Polymerization Mechanism
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通过新型硝基氧自由基偶联一步生长聚合机制合成热降解聚烷氧基胺

DOI:
10.1021/ma501613x
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发表时间:
2014-11
期刊:
影响因子:
5.5
通讯作者:
Wang, Guowei
Wang, Guowei
中科院分区:
化学1区
文献类型:
--
作者:
Wang, Xuepu;Wang, Guowei

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采用氮氧自由基偶联逐步增长聚合(NRC-SGP)反应机理合成了热降解聚烷氧基胺。首次设计并合成了含两个溴基的1,4-苯撑双(2-溴-2-甲基丙酸酯)(单体1)和1,4-苯撑双(2-溴丙酸酯)(单体1′)以及含两个氮氧自由基的1,6-二(4-(2,2,6,6-四甲基哌啶-1-氧基))-己-2,4-二炔(单体2)。通过对聚合时间、温度、溶剂、催化剂、配体、单体浓度、卤素基团连接结构等因素的优化,详细研究了NRC-SGP机理。结果表明,在NRC-SGP反应机理中,缩合反应是主要的副反应,较低的反应温度(25 °C)有利于反应的进行。各因素的合理组合可形成理想的NRC-SGP手术。最后,用TG、DSC和DSC对生成的聚烷氧基胺的热稳定性进行了研究。
The thermal degradable poly(alkoxyamine) was synthesized through a novel nitroxide radical coupling step growth polymerization (NRC-SGP) mechanism. The monomers of 1,4-phenylene bis(2-bromo-2-methylpropanoate) (monomer 1) and 1,4-phenylene bis(2-bromopropanoate) (monomer 1′) with two bromide groups and 1,6-di(4-(2,2,6,6-tetramethylpiperidine-1-oxyl))-hexa-2,4-diyne (monomer 2) with two nitroxide radicals were first designed and synthesized. Then the NRC-SGP mechanism was investigated in detail by optimizing the factors such as polymerization time, temperature, solvents, catalysts, ligand, monomer concentration, and structures connected to halogen groups. The results showed that the termination by disproportionation was the major side reaction in the NRC-SGP mechanism, and the lower temperature (25 °C) would favor an important contribution. The proper combination of all factors could lead to an ideal NRC-SGP procedure. Finally, the thermal stability of formed poly(alkoxyamine) was monitored by TG, DSC and ...
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