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浙江大学学报(工学版)
化学工程与生物工程     
发泡剂存在下的偏氯乙烯悬浮共聚合成粒过程
谢贵明, 王稚阳, 包永忠
1.浙江大学 化学工程国家重点实验室,化学工程与生物工程学院,杭州,310027
2.贵州大学 化学与化工学院,贵阳 550025
Particle formation process of vinylidene chloride suspension copolymerizations in presence of blowing agent
XIE Gui ming, WANG Zhi yang, BAO Yong zhong
1. State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University.Hangzhou 310027, China; 
2. School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China
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摘要:

为了探究悬浮聚合体系中加入发泡剂对聚合成粒过程的影响,在不同沸点烷烃发泡剂存在下进行偏氯乙烯-甲基丙烯酸甲酯(VDC-MMA)悬浮共聚,采用在线激光粒度分析仪和光学显微镜跟踪聚合过程中液滴和聚合物颗粒粒径和形貌的演变,并根据液滴和聚合物颗粒形貌、聚合物/油相溶胀特性和聚合物玻璃化温度随聚合过程的变化,分析核-壳结构VDC-MMA共聚物/烷烃粒子的形成机理.结果表明,当不加发泡剂时,VDC-MMA(质量比为70/30)悬浮共聚得到的颗粒形貌规整、内部密实,粒径变化与珠状悬浮聚合成粒相符.当添加发泡剂后,成粒的准稳态和增长阶段持续时间缩短,恒定阶段粒子收缩不明显,得到的粒子为表面褶皱、核-壳结构较完善的微胶囊粒子.

Abstract:
In order to investigate effects of blowing agent on the particle formation process in suspension polymerization, vinylidene chloride-methyl methacrylate (VDC-MMA) suspension copolymerizations were carried out in the presence of paraffin blowing agents with different boiling points,and evolutions of mean size and morphology of droplets/polymer particles during polymerization process were monitored by using an on-line laser particle size analyzer and optical microscope, respectively. The formation mechanism of the core-shell structure VDC-MMA copolymer/paraffin microspheres was discussed based on the evolutions of droplet/particle size, the swelling behavior of oil phase in the formed copolymer and the glass temperature of swollen copolymers with conversions.Results show that the spherical particles with regular shape andcompact internal structures are obtained when the VDC-MMA (mass ratio is 70/30) suspension copolymerization is conducted in absence of blowing agent, and variation of particle size is in consistent with the typical particle formation features of bead suspension polymerization. As blowing agent added, the quasi-steady state and growth stages are significantly shortened, and the shrinkage of particles in identification stages is not obvious. The copolymer microspheres with wrinkled surface and core-shell structure can be prepared.
出版日期: 2017-03-06
CLC:  TQ 325  
基金资助:

国家自然科学基金资助项目(21176209)

通讯作者: 包永忠,男,教授.ORCID: 0000-0002-8144-015X     E-mail: yongzhongbao@zju.edu.cn
作者简介: 谢贵明(1984—),男,博士生,从事悬浮聚合等研究.ORCID∶0000-0001-5151-3584. E-mail: xieguiming@zju.edu.cn
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谢贵明, 王稚阳, 包永忠. 发泡剂存在下的偏氯乙烯悬浮共聚合成粒过程[J]. 浙江大学学报(工学版), 10.3785/j.issn.1008-973X.2017.02.021.

XIE Gui ming, WANG Zhi yang, BAO Yong zhong. Particle formation process of vinylidene chloride suspension copolymerizations in presence of blowing agent. JOURNAL OF ZHEJIANG UNIVERSITY (ENGINEERING SCIENCE), 10.3785/j.issn.1008-973X.2017.02.021.

[1] YUAN H G, KALFAS G, RAY W H. Suspension polymerization processes [J]. Journal of Macromolecular Science, Part C: Polymer Reviews, 1991, 31(2/3):215-299.
[2] BROOKS B W. Suspension polymerization processes [J]. Chemical Engineering & Technology, 2010, 33(11): 1737-1744.
[3] SMALLWOOD P V. The formation of grains of suspension poly(vinyl chloride) [J] Polymer, 1986, 27(10): 1609-1618.
[4] ZERFA M. Vinyl Chloride Drop behaviour in suspension polymerisation reactors [D]. Loughborough: Loughborough University, 1994.
[5] ZERFA M, BROOKS B W. Prediction of vinyl chloride drop sizes in stabilised liquid-liquid agitated dispersion [J]. Chemical Engineering Science, 1996, 51(12):3223-3233.
[6] ZERFA M, BROOKS B W. Drop coalescence processes in suspension polymerization of vinyl chloride [J]. Journal of Applied Polymer Science, 1996, 60(12):2077-2086.
[7] 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.
[8] JAHANZAD F, SAJJADI S, BROOKS B W. On the evolution of particle size average and size distribution in suspension polymerization processes [J]. Macromolecular Symposia, 2004, 206(1): 255-262.
[9] JAHANZAD F, SAJJADI S, BROOKS B W. Characteristic intervals in suspension polymerisation reactors: an experimental and modelling study [J]. Chemical Engineering Science, 2005, 60(20): 5574-5589.
[10] BERNARD E, OBI P T D B. Crystallization kinetics for semicrystalline random copolymers of vinylidene chloride (VDC) with methyl acrylate (MA), and the effects on the internal
morphology of the resin particles formed during synthesis [J]. Journal of Polymer Science: Part B: Polymer Physics, 1995, 33: 2019-2032.
[11] 谢建武,张静天,包永忠.偏氯乙烯丙烯酸甲酯悬浮共聚树脂颗粒特性[J],化工生产与技术,2009, (02): 9-12.
XIE Jian wu, ZHANG Jing tian, BAO Yong zhong. Particle features of poly(vinylidene chloride-comethyl acrylate) suspension resins [J]. Chemical Production and Technology, 2009, (02): 9-12.
[12] GONCALVES O H, STAUDT T, DE ARAJO P H H. Foaming of poly(methyl methacrylate) particles [J]. Materials Science and Engineering: C, 2009, 29(2): 479-484.
[13] JONSSON M, NORDIN O, MALMSTROM E. Suspension polymerization of thermally expandable core/shell particles [J]. Polymer, 2006, 47(10):3315-3324.
[14] 何思阳,齐会民,刘峰,等.丙烯腈丙烯酸甲酯共聚低温热膨胀微胶囊的制备与性能[J].塑料工业,2013(05): 96-100.
HE Si yang, QI Hui min, LIU Feng, et al. Preparation and Property of low temperature expandable microspheres with acrylonitrile and acrylates [J]. China Plastics Industry, 2013(05):
96-100.
[15] 侯昭升,张浩,纪晨旭,等.悬浮聚合法制备热膨胀聚(偏氯乙烯丙烯腈苯乙烯)微球及其性能[J].高分子材料科学与工程,2015, 31(9): 49-52.
HOU Zhao sheng, ZHANG hao, JI Chen xu, et al. Preparation and properties of thermal-expandable microspheres with P(VDC-AN-St) shell by suspension polymerization [J].
Polymer Materials Science and Engineering, 2015, 31(9): 49-52.
[16] KAMRUP I R, POKHREL B, KALITA A, et al. Synthesis of macroporous polymer particles by suspension polymerization using supercritical carbon dioxide as a pressureadjustable porogen [J]. Advances in Polymer Technology, 2011, 3(2): 154-162.
[17] WESSLING R A, GIBBS D S, HOWELL B A, et al. Vinylidene chloride polymers [M]. New York: John Wiley & Sons, 1997, 882-923.
[18] MOREHOUSE D S, TETREAULT R J. Expandable thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same: United States, 3615972[P]. 19711026.
[19] HOU Z S, XIA Y R, QU W Q, et al. Preparation and properties of thermoplastic expandable microspheres with P(VDC-AN-MMA) shell by suspension polymerization [J].
International Journal of Polymeric Materials and Polymeric Biomaterials 2015, 64(8): 427-431.
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