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

doi:10.11949/0438-1157.20190508

Abstract

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

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

CLC Number:

TQ 325.3

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.

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.

Figures/Tables 1

References 30

1	邴涓林, 赵劲松, 包永忠. 聚氯乙烯树脂及其应用[M]. 北京: 化学工业出版社, 2012: 25- 137.
	Bing J L, Zhao J S, Bao Y Z. Polyvinyl Chloride Resin and Its Application[M]. Beijing: Chemical Industry Press, 2012: 25- 137.
2	Starnes W H, Wojciechowski B J, Velazquez A, et al. Molecular microstructure of the ethyl branch segments in poly (vinyl chloride) [J]. Macromolecules, 2002, 25( 14): 3638- 3641.
3	Endo K. Synthesis and structure of poly (vinyl chloride) [J]. Progress in Polymer Science, 2002, 27( 10): 2021- 2054.
4	Abreu C M R, Fonseca A C, Rocha N M P, et al. Poly(vinyl chloride): current status and future perspectives via reversible deactivation radical polymerization methods [J]. Progress in Polymer Science, 2018, ( 87): 34- 69.
5	Wannemacher T, Braun D, Pfaendner R. Novel copolymers vianitroxide mediated controlled free radical polymerization of vinyl chloride [J]. Macromolecular Symposia, 2003, 202( 1): 11- 24.
6	Abreu C M R, Mendonça P V, Serra A C, et al. Reversible addition-fragmentation chain transfer polymerization of vinyl chloride [J]. Macromolecules, 2012, 45( 5): 2200- 2208.
7	Percec V, Popov A V, Ramirezcastillo E, et al. Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride [J]. Journal of the American Chemical Society, 2002, 124( 18): 4940- 4941.
8	Percec V, Popov A V, Ramirez-Castillo E, et al. Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu ⁰/tris (2-aminoethyl) amine or polyethyleneimine in water at 25℃ proceeds by a new competing pathways mechanism [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2003, 41( 21): 3283- 3299.
9	Percec V, Popov A V, Ramirez-Castillo E, et al. Non-transition metal-catalyzed living radical polymerization of vinyl chloride initiated with iodoform in water at 25℃ [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2004, 42( 24): 6267- 6282.
10	Percec V, Popov A V, Ramirez-Castillo E, et al. Single electron transfer-degenerative chain transfer mediated living radical polymerization (SET-DTLRP) of vinyl chloride initiated with methylene iodide and catalyzed by sodium dithionite [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2005, 43( 4): 773- 778.
11	Percec V, Guliashvili T, Popov A V, et al. Ultrafast synthesis of poly (methyl methacrylate)- b-poly(vinyl chloride)- b-poly (methyl methacrylate) block copolymers by the Cu(0)/tris(2-dimethylaminoethyl) amine-catalyzed living radical block copolymerization of methyl methacrylate initiated with α, ω-di(iodo) poly(vinyl chloride) in the presence of dimethyl sulfoxide at 25℃ [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2005, 43( 8): 1660- 1669.
12	Sienkowska M J, Percec V. Synthesis of α, ω-di (iodo) PVC and of four-arm star PVC with identical active chain ends by SET-DTLRP of VC initiated with bifunctional and tetrafunctional initiators [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2009, 47( 2): 635- 652.
13	尹逊迪, 黄志辉, 包永忠. 聚氯乙烯-聚丙烯酸嵌段共聚物改性的pH响应性聚氯乙烯超滤膜[J]. 高校化学工程学报, 2017, 31( 4): 938- 944.
	Yin X D, Huang Z H, Bao Y Z. pH-responsive poly (vinyl chloride) ultrafiltration membranes modified by poly (vinyl chloride)-poly (acrylic acid) block copolymers [J]. Journal of Chemical Engineering of Chinese Universities, 2017, 31( 4): 938- 944.
14	胡合成, 潘鹏举, 包永忠. 两亲性PNIPAM -b-PVC- b-PNIPAM共聚物的合成与自组装 [J]. 高校化学工程学报, 2018, 32( 2): 401- 406.
	Hu H C, Pan P J, Bao Y Z. Synthesis and self-assembly of amphiphilic PNIPAM- b-PVC- b-PNIPAM block copolymers [J]. Journal of Chemical Engineering of Chinese Universities, 2018, 32( 2): 401- 406.
15	Percec V, Popov A V, Ramirezcastillo E, et al. Phase transfer catalyzed single electron transfer-degenerative chain transfer mediated living radical polymerization (PTC-SET-DTLRP) of vinyl chloride catalyzed by sodium dithionite and initiated with iodoform in water at 43℃[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2010, 43( 4): 779- 788.
16	徐锦超. 单电子转移—蜕化链转移活性自由基细乳液聚合制备聚丙烯酸酯及其嵌段共聚物[D]. 杭州: 浙江大学, 2018.
	Xu J C. Preparation of polyacrylates and their block copolymers by single electron transfer-degenerative chain transfer living radical miniemulsion polymerizations [D]. Hangzhou: Zhejiang University, 2018.
17	Smallwood P V. The formation of grains of suspension poly (vinyl chloride) [J]. Polymer, 1986, 27( 10): 1609- 1618.
18	Smallwood P V. Vinyl chloride suspension polymerization and the control of polymer properties [J]. Makromolekulare Chemie Macromolecular Symposia, 1989, 29( 1): 1- 19.
19	Zerfa M, Brooks B W. Prediction of vinyl chloride drop sizes in stabilized liquid-liquid agitated dispersion[J]. Chemical Engineering Science, 1996, 51( 12): 3223- 3233.
20	Zerfa M, Brooks B W. Experimental investigation of vinyl chloride drop behavior during suspension polymerization [J]. Journal of Applied Polymer Science, 1997, 65( 1): 127- 134.
21	Boscher V, Helleboid R, Lasuye T, et al. On-line acoustic attenuation spectroscopy of emulsions stabilized by vinyl alcohol-vinyl acetate copolymers: a model system for the suspension polymerization of vinyl chloride[J]. Polymer International, 2010, 58( 10): 1209- 1216.
22	Xie T Y, Hamielec A E, Wood P E, et al. Experimental investigation of vinyl chloride polymerization at high conversion—conversion and tracer response relationships[J]. Journal of Applied Polymer Science, 1990, 41( 9/10): 2327- 2347.
23	Bao Y Z, Brooks B W. Phase-equilibrium behavior of vinyl chloride/ n-butane and its application in determination of vinyl chloride heterogeneous polymerization kinetics [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2001, 39( 13): 2179- 2188.
24	Bao Y Z, Brooks B W. Particle features of poly (vinyl chloride) resins prepared by a new heterogeneous polymerization process [J]. Journal of Applied Polymer Science, 2003, 90( 4): 954- 958.
25	吴招俊. 基于GC的氯乙烯聚合动力学参数实时检测系统研究[D]. 杭州: 浙江大学, 2010.
	Wu Z J. Study on real-time measurement system for kinetic parameters of vinyl chloride polymerization based on GC [D]. Hangzhou: Zhejiang University, 2010.
26	Davidson J A, Witenhafer D E. Particle structure of suspension poly (vinyl chloride) and its origin in the polymerization process [J]. Journal of Polymer Science Polymer Physics Edition, 1980, 18( 1): 51- 69.
27	Bertil T, Uustalu J. Formation of primary particles in vinyl chloride polymerization [J]. Journal of Applied Polymer Science, 1988, 35( 1): 63- 74.
28	潘祖仁. 悬浮法聚氯乙烯颗粒结构和成粒过程[J]. 聚氯乙烯, 1988, ( 3): 41- 46.
	Pan Z R. Particle structure and granulation process of PVC by suspension method [J]. Polyvinyl Chloride, 1988, ( 3): 41- 46.
29	Kotoulas C, Kiparissides C. A generalized population balance model for the prediction of particle size distribution in suspension polymerization reactors [J]. Chemical Engineering Science, 2006, 61( 2): 332- 346.
30	Zhao J S, Wang X Q, Fan C G. Formation of grains in a suspension of poly (vinyl chloride)[J]. Polymer, 1991, 32( 14): 2674- 2679.

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