苯乙烯与丙烯酸可逆加成-断裂链转移（RAFT）共聚反应中单体相对反应活性的控制
Control over the relative reactivities of monomers in RAFT copolymerization of styrene and acrylic acid.
作者信息
Chernikova E V, Zaitsev S D, Plutalova A V, Mineeva K O, Zotova O S, Vishnevetsky D V
机构信息
Polymer Department, Faculty of Chemistry, Lomonosov Moscow State University Lenin Hills, 1, bld.3 Moscow 119991 Russian Federation
Nizhni Novgorod State University pr. Gagarina, 23 Nizhni Novgorod 603950 Russian Federation
出版信息
RSC Adv. 2018 Apr 18;8(26):14300-14310. doi: 10.1039/c8ra00048d. eCollection 2018 Apr 17.
The relative monomer reactivities in the reversible addition-fragmentation chain transfer (RAFT) radical copolymerization of styrene (S) and acrylic acid (AA) in a solution of the polar solvent ,-dimethylformamide are found to be dependent on the chemical nature of the RAFT agent. Polymeric RAFT agents based on polyacrylic acid enhance the difference in monomer reactivities (dithiobenzoate - = 0.09 ± 0.02, = 3.5 ± 1.2, trithiocarbonate - = 0.08 ± 0.04, = 3.03 ± 1.78) compared to low molecular weight RAFT agents (dibenzyl dithiobenzoate - = 0.14 ± 0.01, = 1.00 ± 0.01, dibenzyl trithiocarbonate - = 0.08 ± 0.01, = 0.85 ± 0.03). The opposite effect on the relative reactivity of acrylic acid is observed when polymeric RAFT agents based on polystyrene are used (dithiobenzoate - = 3.3 ± 0.4, = 0.72 ± 0.05, trithiocarbonate - = 0.11 ± 0.01, = 0.54 ± 0.03). In all the investigated systems the copolymers formed are characterized by narrow MWD due to the high efficiency of the chosen RAFT agents.
在极性溶剂N，N-二甲基甲酰胺溶液中，苯乙烯（S）与丙烯酸（AA）的可逆加成-断裂链转移（RAFT）自由基共聚反应中，发现相对单体反应活性取决于RAFT试剂的化学性质。与低分子量RAFT试剂（二苄基二硫代苯甲酸酯 - r = 0.14±0.01，Q = 1.00±0.01，二苄基三硫代碳酸酯 - r = 0.08±0.01，Q = 0.85±0.03）相比，基于聚丙烯酸的聚合物RAFT试剂增强了单体反应活性的差异（二硫代苯甲酸酯 - r = 0.09±0.02，Q = 3.5±1.2，三硫代碳酸酯 - r = 0.08±0.04，Q = 3.03±1.78）。当使用基于聚苯乙烯的聚合物RAFT试剂时，观察到对丙烯酸相对反应活性的相反影响（二硫代苯甲酸酯 - r = 3.3±0.4，Q = 0.72±0.05，三硫代碳酸酯 - r = 0.11±0.01，Q = 0.54±0.03）。在所有研究的体系中，由于所选RAFT试剂的高效率，形成的共聚物具有窄的分子量分布。
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