Catalytic effect of DMSO in metal‐catalyzed radical polymerization mediated by disproportionation facilitates living and immortal radical polymerizations
Catalytic effect of DMSO in metal‐catalyzed radical polymerization mediated by disproportionation facilitates living and immortal radical polymerizations
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DOI：
10.1002/pol.20220632
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发表时间：
2023-02
影响因子：
3.4
通讯作者：
Devendra S. Maurya;Jasper Adamson;Nabil Bensabeh;Gerard Lligadas;V. Percec
中科院分区：
文献类型：
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作者：
Devendra S. Maurya;Jasper Adamson;Nabil Bensabeh;Gerard Lligadas;V. Percec
DMSO是一种用于铜催化的活性自由基聚合（LRP）的有趣溶剂，其通过反硝化作用介导，没有表现出Cu（I）X到Cu（0）和Cu（II）X2的最大反硝化作用。在合适的条件下，DMSO可提供100%的转化率和无终止，通过活性和不朽聚合促进复杂结构方法的发展。目前正在研究产生这种精确度的机制。在这里，我们比较了在八种反硝化溶剂的存在下，由反硝化配体三（2-二甲基氨基乙基）胺、Me6-TREN、三（2-氨基乙基）胺、TREN和Me6-TREN/TREN = 1/1介导的丙烯酸甲酯的Cu（0）-线催化的LRP，其中一些在反硝化中比DMSO更有效。出乎意料的是，我们观察到当单体浓度降低时，所有溶剂都增加了聚合速率。这种与常规LRP相反的趋势证明了溶剂的催化作用。在一定浓度以上，观察到经典的浓度-速率依赖性。表观增长速率常数的外部反应顺序，kpappon溶剂浓度证明了最高的反应顺序为最少的纯化DMSO。在研究的所有溶剂中，DMSO具有最高的稳定Cu（0）纳米颗粒的能力，因此产生最高活性的Cu（0）纳米颗粒，而不是它们的最大浓度。讨论了溶剂在该反应及其它反应中的催化作用。
DMSO, an interesting solvent for copper‐catalyzed living radical polymerization (LRP) mediated by disproportionation, does not exhibit the greatest disproportionation of Cu(I)X into Cu(0) and Cu(II)X2. Under suitable conditions, DMSO provides 100% conversion and absence of termination, facilitating the development of complex‐architecture methodologies by living and immortal polymerizations. The mechanism yielding this level of precision is being investigated. Here we compare Cu(0)‐wire‐catalyzed LRP of methyl acrylate mediated by disproportionating ligands tris(2‐dimethylaminoethyl)amine, Me6‐TREN, tris(2‐aminoethyl)amine, TREN, and Me6‐TREN/TREN = 1/1 in presence of eight disproportionating solvents, some more efficient than DMSO in disproportionation. Unexpectedly, we observed that all solvents increased the rate of polymerization when monomer concentration decreased. This reversed trend from that of conventional LRPs demonstrates catalytic effect for disproportionating solvents. Above a certain concentration, the classic concentration‐rate dependence was observed. The external order of reaction of the apparent rate constant of propagation,kpappon solvent concentration demonstrated the highest order of reaction for the least disproportionating DMSO. Of all solvents investigated, DMSO has the highest ability to stabilize Cu(0) nanoparticles and therefore, yields the highest activity of Cu(0) nanoparticles rather than their greatest concentration. The implications of the catalytic effect of solvent in this and other reactions were discussed.