Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization of Methyl Methacrylate and Styrene with N-Heterocyclic Carbene as Ligands for Fe-Based Catalysts.
Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization of Methyl Methacrylate and Styrene with N-Heterocyclic Carbene as Ligands for Fe-Based Catalysts.
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DOI：
10.1021/mz500539j
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发表时间：
2014-09
影响因子：
5.8
通讯作者：
S. Okada;Sangwoo Park;K. Matyjaszewski
中科院分区：
文献类型：
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作者：
S. Okada;Sangwoo Park;K. Matyjaszewski
研究了铁基氮杂环卡宾（FeX 3（NHC））配合物作为连续活化剂再生原子转移自由基聚合（ICAR ATRP）的引发剂。用FeX_3（IDipp）（IDipp = 1，3-双（2，6-二异丙基苯基）咪唑烷-2-亚基，X = Cl（I-Cl）或Br（I-Br））和FeX_3（HIDipp = 1，3-双（2，6-二异丙基苯基）咪唑烷-2-亚基，X = Cl（H-Cl）或Br（H-Br））对甲基丙烯酸甲酯（MMA）和苯乙烯（St）进行了一系列ICAR ATRP。聚合显示出良好的活性，导致聚合物具有可控的分子量和窄的分子量分布（MWD）与低负载的催化剂（50 ppm）。特别地，I-Br和H-Br产生具有较窄MWD的聚合物。例如，MMA与50 ppm催化剂（H-Br）的ICAR ATRP在T = 60 °C下在50% v/v苯甲醚中在24小时后在65%单体转化率下产生Mw/Mn = 1.20的PMMA。72小时后St的ICAR ATRP导致在53%单体转化率下Mw/Mn = 1.15的PSt。
Iron-based N-heterocyclic carbene (FeX3(NHC)) complexes were used in initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP). A series of ICAR ATRPs of methyl methacrylate (MMA) and styrene (St) were carried out using FeX3(IDipp) where IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene with X = Cl (I-Cl) or Br (I-Br) and FeX3(HIDipp) (HIDipp =1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene) with X = Cl (H-Cl) or Br (H-Br). The polymerizations showed good activity, resulting in polymers with controlled molecular weights and narrow molecular weight distribution (MWD) with low loading of catalysts (50 ppm). In particular, I-Br and H-Br generated polymers with narrower MWD. For example, ICAR ATRP of MMA with 50 ppm catalysts (H-Br) after 24 h at T = 60 °C in 50% v/v anisole resulted in PMMA with Mw/Mn = 1.20 at 65% monomer conversion. ICAR ATRP of St after 72 h resulted in PSt with Mw/Mn = 1.15 at 53% monomer conversion.