TY - JOUR

T1 - Can Flory-Stockmayer theory be applied to predict conventional free radical polymerization of multivinyl monomers

T2 - a study via Monte Carlo simulations

AU - Lyu, Jing

AU - Gao, Yongsheng

AU - Greiser, Udo

AU - Zhang, Zidang

AU - Tai, Hongyun

AU - Wang, Wenxin

PY - 2018/3/1

Y1 - 2018/3/1

N2 - The conventional free radical polymerization (FRP) of multivinyl monomers (MVMs) inevitably leads to gelation even at low monomer conversion resulting in difficulties to control and monitor the reaction process. Flory and Stockmayer (F-S theory) studied it based on two fundamental assumptions: (1) independent and equivalent vinyl groups, (2) no intramolecular cyclization. However, until now its applicability to FRP of MVMs (especially regarding the extent of intramolecular cyclization) is still controversial. In this paper, Monte Carlo simulations are used to study FRP of divinyl monomers by two kinetic models: with/without cyclization models. The results of the simulations are compared with the calculated gel points based on F-S theory and the experimental data. It is found that the intramolecular cyclization has a negligible impact on the polymerization process and the gel point before gelation, which are in agreement with the prediction by F-S theory, but the effect becomes significant above the gel points

AB - The conventional free radical polymerization (FRP) of multivinyl monomers (MVMs) inevitably leads to gelation even at low monomer conversion resulting in difficulties to control and monitor the reaction process. Flory and Stockmayer (F-S theory) studied it based on two fundamental assumptions: (1) independent and equivalent vinyl groups, (2) no intramolecular cyclization. However, until now its applicability to FRP of MVMs (especially regarding the extent of intramolecular cyclization) is still controversial. In this paper, Monte Carlo simulations are used to study FRP of divinyl monomers by two kinetic models: with/without cyclization models. The results of the simulations are compared with the calculated gel points based on F-S theory and the experimental data. It is found that the intramolecular cyclization has a negligible impact on the polymerization process and the gel point before gelation, which are in agreement with the prediction by F-S theory, but the effect becomes significant above the gel points

M3 - Article

VL - 61

SP - 319

EP - 327

JO - Science China Chemistry

JF - Science China Chemistry

SN - 1674-7291

IS - 3

ER -