基于从头算的动力学建模来理解 RAFT 交换：以 2-氰基-2-丙基十二烷基三硫代碳酸酯和苯乙烯为例。
Ab-Initio-Based Kinetic Modeling to Understand RAFT Exchange: The Case of 2-Cyano-2-Propyl Dodecyl Trithiocarbonate and Styrene.
机构信息
Laboratory for Chemical Technology, Department of Materials, Textiles and Chemical Engineering, Ghent University, Technologiepark 914, Ghent, 9052, Belgium.
出版信息
Macromol Rapid Commun. 2018 Jan;39(2). doi: 10.1002/marc.201700403. Epub 2017 Oct 27.
Ab-initio-calculated rate coefficients for addition and fragmentation in reversible-addition fragmentation chain transfer (RAFT) polymerization of styrene with 2-cyano-2-propyl dodecyl trithiocarbonate initiated by azobisisobutyronitrile allow the reliable simulation of the experimentally observed conversion, number average chain length, and dispersity. The rate coefficient for addition of a macroradical R to the macroRAFT agent R X at 333 K (6.8 10 L mol s ) is significantly lower than to the initial RAFT agent R X (3.2 10 L mol s ), mainly due to a difference in activation energy (15.4 vs 3.0 kJ mol ), which causes the dispersity to spike in the beginning of the polymerization.
用偶氮二异丁腈引发的 2-氰基-2-丙基十二烷基三硫代碳酸酯的可逆加成-断裂链转移（RAFT）聚合苯乙烯的从头算计算得到的加成和断裂的速率系数，可可靠地模拟实验观察到的转化率、数均链长和分散度。在 333 K 下，大分子自由基 R 与大分子 RAFT 试剂 R X 的加成速率系数（6.8×10 L mol s ）明显低于与初始 RAFT 试剂 R X 的加成速率系数（3.2×10 L mol s ），主要是由于活化能的差异（15.4 与 3.0 kJ mol ），这导致在聚合开始时分散度突然增加。
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