聚合条件下原子转移自由基聚合（ATRP）平衡常数的测定
Determination of ATRP Equilibrium Constants under Polymerization Conditions.
作者信息
Wang Yu, Kwak Yungwan, Buback Johannes, Buback Michael, Matyjaszewski Krzysztof
机构信息
Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
Institute for Physical Chemistry, University of Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany.
出版信息
ACS Macro Lett. 2012 Dec 18;1(12):1367-1370. doi: 10.1021/mz3005378. Epub 2012 Nov 13.
Atom transfer radical polymerization (ATRP) equilibrium constants () were measured during polymerization of methyl acrylate (MA) with CuBr/CuBr in either dimethyl sulfoxide (DMSO) or acetonitrile (MeCN) in the presence of either tris(2-pyridylmethyl)amine (TPMA) or tris[2-(dimethylamino)ethyl]amine (MeTREN) as the ligand and with ethyl 2-bromopropionate as the initiator. The ln() values changed linearly with the volume fraction of solvents in the reaction medium, allowing extrapolation of the values for to bulk conditions, which were 2 × 10 and 3 × 10 for TPMA and MeTREN ligands at 25 °C, respectively. The temperature effect on values was studied in MA/MeCN = 1/1 (v/v) with TPMA as the ligand in the temperature range from 0 to 60 °C. The values increased with temperature providing Δ = 36 kJ mol in MeCN.
在以2-溴丙酸乙酯为引发剂、三（2-吡啶甲基）胺（TPMA）或三[2-（二甲氨基）乙基]胺（MeTREN）为配体的条件下，于二甲基亚砜（DMSO）或乙腈（MeCN）中，用CuBr/CuBr引发丙烯酸甲酯（MA）聚合，测定了原子转移自由基聚合（ATRP）平衡常数（）。ln（）值随反应介质中溶剂的体积分数呈线性变化，从而可以外推到本体条件下的值，在25℃时，TPMA和MeTREN配体的的值分别为2×10和3×10。在0至60℃的温度范围内，以TPMA为配体，研究了MA/MeCN = 1/1（v/v）体系中温度对值的影响。值随温度升高而增加，在MeCN中的Δ = 36 kJ mol。
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