Atom transfer radical polymerization of methyl acrylate, methyl methacrylate and styrene in the presence of trolamine as a highly effective promoter

Atom transfer radical polymerization of methyl acrylate, methyl methacrylate and styrene in the presence of trolamine as a highly effective promoter
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三乙醇胺作为高效促进剂时丙烯酸甲酯、甲基丙烯酸甲酯和苯乙烯的原子转移自由基聚合

DOI:
10.1016/j.cclet.2015.03.012
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发表时间:
2015-06
影响因子:
9.1
通讯作者:
Hua-Dong Tang
Hua-Dong Tang
中科院分区:
化学1区
文献类型:
--
作者:
Qiao Xu;Yi-Feng Zhu;Zhao Yuan;Hua-Dong Tang

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过渡金属介导的原子转移自由基聚合(ATRP)是一种“活性”/受控自由基聚合。最近,人们对降低 ATRP 中催化剂分离和聚合后纯化的高成本越来越感兴趣。在这项工作中,发现三乙醇胺显着增强了 CuBr/N,N,N',N'-四(2-吡啶甲基)乙二胺 (CuBr/TPEN) 和 CuBr/三[2-(二甲氨基)乙胺] (CuBr/Me6TREN) 的催化性能。添加相对于 CuBr 25 倍摩尔量的三乙醇胺后,CuBr/TPEN 和 CuBr/Me6TREN 的催化剂负载量分别从 1 的催化剂与引发剂的比率大幅降低至 0.01 和 0.05。在三乙醇胺存在下,丙烯酸甲酯、甲基丙烯酸甲酯和苯乙烯的聚合仍表现出一级动力学,并产生分子量接近理论值和低多分散性的聚丙烯酸甲酯、聚甲基丙烯酸甲酯和聚苯乙烯。这些结果表明三乙醇胺是一种高效且多功能的 ATRP 促进剂,具有潜在的工业应用前景。
Transition metal-mediated atom transfer radical polymerization (ATRP) is a “living”/controlled radical polymerization. Recently, there has been widely increasing interest in reducing the high costs of catalyst separation and post-polymerization purification in ATRP. In this work, trolamine was found to significantly enhance the catalytical performance of CuBr/N,N,N′,N′-tetrakis(2-pyridylmethyl) ethylenediamine (CuBr/TPEN) and CuBr/tris[2-(dimethylamino) ethylamine] (CuBr/Me6TREN). With the addition of 25-fold molar amount of trolamine relative to CuBr, the catalyst loadings of CuBr/TPEN and CuBr/Me6TREN were dramatically reduced from a catalyst-to-initiator ratio of 1 to 0.01 and 0.05, respectively. The polymerizations of methyl acrylate, methyl methacrylate and styrene still showed first-order kinetics in the presence of trolamine and produced poly(methyl acrylate), poly(methyl methacrylate) and polystyrene with molecular weights close to theoretical values and low polydispersities. These results indicate that trolamine is a highly effective and versatile promoter for ATRP and is promising for potential industrial application.
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