Evolution of iron catalysts for effective living radical polymerization: Design of phosphine/halogen Ligands in FeX2(PR3)(2)
Evolution of iron catalysts for effective living radical polymerization: Design of phosphine/halogen Ligands in FeX2(PR3)(2)
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DOI：
10.1021/ma071639r
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发表时间：
2007-11
期刊：
影响因子：
5.5
通讯作者：
Chihiro Uchiike;Takaya Terashima;M. Ouchi;T. Ando;M. Kamigaito;M. Sawamoto
中科院分区：
文献类型：
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作者：
Chihiro Uchiike;Takaya Terashima;M. Ouchi;T. Ando;M. Kamigaito;M. Sawamoto
本文报道了铁配合物催化甲基丙烯酸甲酯（MMA）活性自由基聚合的改进体系，通过配体的设计、引发剂/催化剂中卤素的组合以及聚合条件的优化，提高了适用催化剂的活性和聚合可控性。在传统的铁系催化剂[FeX_2（PPh_3）_2; X = Cl，Br]中引入了碱性更强的配体如PMe（Ph）_2和P-n-Bu_3来代替PPh_3，从而提高了催化剂的活性和可控性.特别地，丁基溴化膦衍生物[FeBr 2（P-n-Bu 3）2]与溴化物引发剂[（MMA）2Br]结合允许更快和更精确的聚合，其中转化率达到90%以上而没有严重的失活，并且所获得的PMMA的分子量及其分布被相当地控制（Mw/Mn = 1.2 - 1.3）。该系统的高效性已通过成功的单体聚合反应得到验证。
In this article, we report the evolved system of iron-complex-catalyzed living radical polymerization of methyl methacrylate (MMA), through design of the ligand, combination of the halogen in the initiator/catalyst, and optimization of the polymerization conditions, toward improvement of the activity and the polymerization-controllability with the applicable catalysts. Introduction of the more basic ligands such as PMe(Ph)2 and P-n-Bu3 in place of PPh3 in the conventional iron catalyst [FeX2(PPh3)2; X = Cl, Br] improved the catalytic performances such as the activity/controllability. In particular, the butylphosphine bromide derivative [FeBr2(P-n-Bu3)2] in conjunction with a bromide initiator [(MMA)2Br] allowed a faster and more precise polymerization, where the conversion reached over 90% without serious deactivation and the molecular weights and their distributions of the obtained PMMAs were fairly controlled (Mw/Mn = 1.2−1.3). The high efficiency of the system was demonstrated by the successful monomer...