氯乙烯SET-DT悬浮聚合动力学和成粒过程的相互关系

doi:10.11949/0438-1157.20190508

摘要/Abstract

摘要：

以碘仿为引发剂、连二亚硫酸钠/碳酸氢钠为催化体系、聚乙烯醇(PVA)和/或纤维素衍生物(MC)为分散体系，进行氯乙烯单电子转移-蜕化链转移(SET-DT)活性自由基悬浮聚合，采用在线示踪气相色谱法和激光粒度分析系统研究分散剂种类和浓度、搅拌转速等对聚合动力学和单体液滴/聚合物颗粒粒径分布的影响。发现在相同搅拌转速下，以MC为分散剂的氯乙烯聚合速率最大，以PVA为分散剂时反应速率最小；分散剂种类固定时，聚合速率随分散剂浓度增大而增大。SET-DT悬浮聚合过程中，水相连二亚硫酸钠分解产生的自由基向单体液滴的扩散速率与液滴粒径分布和皮膜结构有关，因此聚合成粒过程影响聚合动力学。尽管不同条件下的聚合均经历液-液分散、液滴黏并、树脂颗粒稳定(转化率>30%)等成粒阶段，但各阶段的液滴/颗粒平均尺寸随分散体系和搅拌转速的变化而变化，引起聚合速率变化；采用MC为分散剂得到的PVC树脂皮膜少，有利于水相产生的自由基向单体相的扩散，聚合速率大。

关键词: 聚合, 动力学, 粒子形成, 氯乙烯, 悬浮聚合, 活性自由基聚合

Abstract:

Single electron transfer-degenerative chain transfer (SET-DT) living radical suspension polymerizations of vinyl chloride (VC) were conducted using CHI ₃ as an initiator, NaS ₂O ₄/NaHCO ₃ as catalysts, polyvinyl alcohol (PVA) and/or methylcellulose (MC) as dispersant(s). Effects of dispersant type and concentration, agitation rate on VC polymerization rate and droplet/particle size distribution were investigated by using online gas chromatography and laser particle size analyzer. It was found that the polymerization rate of VC was greatest when MC was used as the dispersant, while the polymerization rate was lowest when PVA was used as the dispersant at a same agitation rate. The polymerization rate was increased with the increase of dispersant concentration when the dispersant type was fixed. In VC SET-DT suspension polymerization, the diffusion of free-radicals formed by decomposition of Na ₂S ₂O ₄in the water phase into monomer droplets was related to the droplet size distribution and membrane structure of PVC particles. Thus, the polymerization kinetics was influenced by the particle formation process. Although all polymerizations conducted at different conditions exhibited the liquid-liquid dispersion, droplet coalescence and particle identification stages, the average sizes of droplets or particles corresponding to different stages were varied as dispersant and agitation rate varied. The use of MC as a dispersant results in fewer PVC resin films, which is conducive to the diffusion of free radicals generated in the water phase to the monomer phase and a large polymerization rate.

Key words: polymerization, kinetics, particle formation, vinyl chloride, suspension polymerization, living radical polymerization

中图分类号:

TQ 325.3

韩剑鹏,包永忠. 氯乙烯SET-DT悬浮聚合动力学和成粒过程的相互关系[J]. 化工学报, 2020, 71(2): 854-863.

Jianpeng HAN,Yongzhong BAO. Connection between kinetics and particle formation process of vinyl chloride SET-DT suspension polymerizations[J]. CIESC Journal, 2020, 71(2): 854-863.

图/表 1

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