Exploration of highly active bidentate ligands for iron (III)-catalyzed ATRP
Exploration of highly active bidentate ligands for iron (III)-catalyzed ATRP
复制标题
DOI：
10.1016/j.polymer.2016.03.027
复制
发表时间：
2016-05
期刊：
影响因子：
4.6
通讯作者：
M. Y. Khan;Jun Zhou;Xiangxiong Chen;Abuzar Khan;Hasan Mudassir;Zhigang Xue;Seung Woo Lee;S. Noh
中科院分区：
文献类型：
--
作者：
M. Y. Khan;Jun Zhou;Xiangxiong Chen;Abuzar Khan;Hasan Mudassir;Zhigang Xue;Seung Woo Lee;S. Noh
新型高效取代P-N配体对甲基丙烯酸甲酯（MMA）和甲基丙烯酸丁酯（BMA）的原子转移自由基聚合（ATRP）具有显著的促进作用。采用高氧化态金属（FeX3）偶联2-溴异丁酸乙酯（EBriB）作为ATRP引发剂催化反应。通过逐渐加入fex3来检测MMA聚合，观察到不受控制的ATRP （PDI ~ 1.59）完全转化为受控的聚合体系（PDI ~ 1.13）。聚合反应得到很好的控制，平均分子量（Mn）线性增加，单体转化率高达90%，无并发症。DTBP配体的实验分子量与理论值吻合较好，与其他配体相比，pdi更窄（<1.2）。此外，潜在活性催化剂（FeBr3/DTBP）在50 ppm的催化剂负载下成功用于MMA的聚合。并确定了不加外源添加剂的fex3的可能机理。
Novel highly active substituted P-N ligands were found to be remarkably efficient for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) and butyl methacrylate (BMA). The reaction was catalyzed by a high oxidation state metal (FeX3) coupled with ethyl-2-bromoisobutyrate (EBriB) as an ATRP initiator. MMA polymerization was examined by the gradual addition of FeX3and the complete transformation of uncontrolled ATRP (PDI∼1.59) to a controlled polymerization system (PDI∼1.13) was observed. The polymerizations were well controlled with a linear increase in the mean molecular weight (Mn) and monomer conversion reached up to 90% without complications. In the case of the DTBP ligand, the experimental molecular weights matched the theoretical values well and the PDIs were narrower (<1.2) compared to the other ligands. Furthermore, the potentially active catalyst (FeBr3/DTBP) was used successfully for the polymerization of MMA at a 50-ppm catalyst loading. The probable mechanism using FeX3without an external additive was also determined.