Vo Quan V, Tram Truong Le Bich, Phuoc Hoang Loc, Hoa Nguyen Thi, Mechler Adam
The University of Danang-University of Technology and Education Danang 550000 Vietnam
Department of Science-Technology and Environment, The University of Danang Danang 550000 Vietnam
RSC Adv. 2023 Aug 4;13(34):23402-23408. doi: 10.1039/d3ra03820c.
Poly(-vinylpyrrolidone) (PVP) is a polymer with many applications in cosmetic, pharmaceutical, and biomedical formulations due to its minimal toxicity. PVP can be synthesized through radical polymerization in organic solvents; this well-known industrial process is thoroughly characterized experimentally, however, quantum chemical modeling of the process is scarce: the mechanism and kinetics have not been thoroughly investigated yet. In this work, the mechanism and kinetics of the alkoxy radical polymerization of -vinylpyrrolidone in organic solvents, namely isopropanol (IP) and toluene (TL), were successfully modeled by computational chemistry. The initiator radicals di--butyl peroxide (TBO˙) and dicumyl peroxide (CMO˙) as well as the solvents isopropanol and toluene, were shown to be capable of assisting in the initiation reactions. The rate constant was influenced by the combination of initiators and solvent and the values of the rate constant of propagation were approximately 10-10 M s. The radical polymerization of NVP with dicumyl peroxide as an initiator was comparable to that of di--butyl peroxide in all of the examined organic solvents, whereas the solvents had less of an effect.
聚乙烯吡咯烷酮（PVP）是一种聚合物，因其毒性极小而在化妆品、制药和生物医学配方中有许多应用。PVP可通过在有机溶剂中进行自由基聚合来合成；这个著名的工业过程已通过实验得到充分表征，然而，该过程的量子化学建模却很少见：其机理和动力学尚未得到充分研究。在这项工作中，通过计算化学成功地对乙烯基吡咯烷酮在有机溶剂（即异丙醇（IP）和甲苯（TL））中的烷氧基自由基聚合的机理和动力学进行了建模。引发剂自由基二叔丁基过氧化物（TBO˙）和二苯甲酰过氧化物（CMO˙）以及溶剂异丙醇和甲苯被证明能够协助引发反应。速率常数受引发剂和溶剂组合的影响，链增长速率常数的值约为10⁻¹⁰ M⁻¹ s⁻¹。在所有检测的有机溶剂中，以二苯甲酰过氧化物为引发剂的NVP自由基聚合与二叔丁基过氧化物的情况相当，而溶剂的影响较小。
