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Design of a hydrophilic ruthenium catalyst for metal-catalyzed living radical polymerization: highly active catalysis in water

机译:金属催化活性自由基聚合的亲水性钌催化剂的设计:水中高活性催化

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A novel hydrophilic phosphine ligand for a ruthenium catalyst was synthesized towards useful living radical polymerization in water. Triethylene glycol (TEG) was introduced at the para position of triphenylphosphine and the resultant TEG-decorated ligand was combined with a Cp*-based ruthenium precursor ([Cp*Ru(μ _(3) -Cl)] _(4) ) to prepare a hydrophilic ruthenium complex. The obtained ruthenium complex induced homogeneous controlled polymerization of poly(ethylene glycol) methacrylate (PEGMA) in water: the monomer conversion reached over 90% in 20 min, and the obtained polymers showed narrow MWD ( M _(w) / M _(n) < 1.16). The ruthenium catalyst was active enough to allow a decrease in catalyst amount ([Ru] _(0) /[initiator] _(0) = 1/100) or polymerization at low temperature, 0 °C [for 2-hydroxyethyl methacrylate (HEMA)]. The catalyst also induced aqueous block copolymerization for the combination of water-soluble monomers: PEGMA/HEMA and PEGMA/2-(dimethylamino)ethyl methacrylate (MeDMA).
机译:将用于钌催化剂的新型亲水膦配体朝向有用的活性自由基聚合中的水中。在三苯基膦的PARA位置引入三甘醇(TEG),并将所得的TEG装饰配体与CP *基于钌前体组合([CP * Ru(μ_(μ_(3)-Cl)] _(4))制备亲水钌络合物。将得到的钌复合物诱导水(乙二醇)甲基丙烯酸酯(PEGMA)在水中的均相控制聚合:20分钟内的单体转化率达到90%,并且所得聚合物显示窄MWD(M _(W)/ m _(n <1.16)。钌催化剂足够活跃,以允许在低温下的催化剂量([Ru] _(0)/ [引发剂] _(0)= 1/100)或聚合在低温下的聚合,0℃[甲基丙烯酸2-羟乙基乙酯( hema)]。催化剂还诱导水溶性单体组合的含水嵌段共聚:PEGMA / hema和PEGMA / 2-(二甲基氨基)甲基丙烯酸乙酯(MEDMA)。

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