Connection between kinetics and particle formation process of vinyl chloride SET-DT suspension polymerizations

HAN Jianpeng; BAO Yongzhong

doi:10.11949/0438-1157.20190508

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Connection between kinetics and particle formation process of vinyl chloride SET-DT suspension polymerizations

Material science and engineering\, nanotechnology | 更新时间：2026-07-24

- Connection between kinetics and particle formation process of vinyl chloride SET-DT suspension polymerizations
- CIESC Journal Vol. 71, Issue 2, Pages: 854-863(2020)
- 作者机构：
  
  1. 化学工程联合国家重点实验室，浙江大学化学工程与生物工程学院，浙江杭州 310027
  2. 浙江大学衢州研究院，浙江衢州 324000
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20190508
  CLC： TQ 325.3
- Received：15 May 2019，
  
  Revised：2019-08-13，
  
  Online First：14 August 2020，
  
  Published：05 February 2020
- 稿件说明：
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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

HAN Jianpeng, BAO Yongzhong. Connection between kinetics and particle formation of vinyl chloride SET-DT suspension polymerizations[J]. CIESC Journal, 2020, 71(2): 854-863
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 DOI： 10.11949/0438-1157.20190508.

HAN Jianpeng, BAO Yongzhong. Connection between kinetics and particle formation of vinyl chloride SET-DT suspension polymerizations[J]. CIESC Journal, 2020, 71(2): 854-863 DOI： 10.11949/0438-1157.20190508.

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。

Abstract

Single electron transfer-degenerative chain transfer (SET-DT) living radical suspension polymerizations of vinyl chloride (VC) were conducted using CHI

as an initiator

NaS

/NaHCO

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 dispers

ant type was fixed. In VC SET-DT suspension polymerization

the diffusion of free-radicals formed by decomposition of Na

in 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.

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references

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