Effect of the solvent systems on preparation of polystyrene microspheres via foam-transfer

doi:10.16085/j.issn.1000-6613.2021-0112

Abstract

Abstract:

The effect of the solvent systems which composed of different ratios of acetone (AC)/dichloromethane (DCM) on the foam-transfer process and properties of PS microspheres were investigated, and the corresponding mechanisms were interpreted. It was found that by increasing the concentration of AC, the foaming temperature increased; while the average particle size of the polystyrene microspheres decreased with narrower particle size distribution and the structure of the PS microspheres evolved from the porous to the hollow. The change on the properties of polymer microspheres was mainly due to the migration of AC from the dispersed phase to the continuous phase, which not only decreased the surface tension but also altered the evaporation process.

Key words: porous polymer microspheres, binary solvent system, foam-transfer, phase separation

摘要：

采用二氯甲烷（DCM）和丙酮（AC）组成二元溶剂体系，考察了二元溶剂体系对制备聚苯乙烯（PS）微球时泡沫的传输和微球性能的影响，并探讨了对应的作用机理。实验结果表明，随着AC质量分数的增加，体系的出泡温度升高，PS微球的平均粒径下降且粒径分布逐渐变窄，微球的结构由多孔逐渐演变为中空。这主要是由于AC对水具有一定的亲和性，会往连续相迁移，改变连续相的表面张力，并在油水界面形成一个AC/DCM的混合液膜层，该液膜层改变了溶剂挥发的过程，最终实现对微球粒径和结构的调控。

关键词: 多孔聚合物微球, 二元溶剂体系, 泡沫传输, 相分离

CLC Number:

TQ31

YU Yang, HE Yanping, LUO Shiyu, HAN Wanqing, LI Guiying, SI Tian, ZHU Linhua, ZHU Yuanzhi. Effect of the solvent systems on preparation of polystyrene microspheres via foam-transfer[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 320-326.

余杨, 何艳萍, 罗诗钰, 韩万青, 李贵营, 司甜, 祝琳华, 朱远蹠. 二元溶剂体系对泡沫传输制备聚苯乙烯微球的影响[J]. 化工进展, 2022, 41(1): 320-326.

Figures/Tables 7

References 34

1	侯雅琦, 沈敬尧, 易达, 等. 异丙基丙烯酰胺水凝胶纳米微球粒径的控制及其对多肽吸附的影响[J]. 化工学报, 2020, 71(S2): 267-272.
	HOU Yaqi, SHEN Jingyao, YI Da, et al. Influences on diameter of isopropylacrylamide hydrogel nanoparticles and its effect on peptide affinity[J]. CIESC Journal, 2020, 71(S2): 267-272.
2	ANDERSON J M, SHIVE M S. Biodegradation and biocompatibility of PLA and PLGA microspheres[J]. Advanced Drug Delivery Reviews, 2012, 64(S1): 72-82.
3	PARK H, HA D H, HA E S, et al. Effect of stabilizers on encapsulation efficiency and release behavior of exenatide-loaded PLGA microsphere prepared by the W/O/W solvent evaporation method[J]. Pharmaceutics, 2019, 11(12): 627.
4	温霜, 巨晓洁, 谢锐, 等. 肠靶向海藻酸钙基微胶囊的制备及控释性能研究[J]. 化工学报, 2020, 71(8): 3797-3806.
	WEN Shuang, JU Xaiojie, XIE Rui, et al. Fabrication and controlled-release properties of intestinal-targeted Ca-alginate-based capsules[J]. CIESC Journal, 2020, 71(8): 3797-3806.
5	SHIM H, SAH H. Qualification of non-halogenated organic solvents applied to microsphere manufacturing process[J]. Pharmaceutics, 2020, 12(5): 425.
6	JUNG Y H, LIM C H, KIM D K. Graphene-supported Na₃V₂(PO₄)₃ as a high rate cathode material for sodium-ion batteries[J]. Journal of Materials Chemistry A, 2013, 1(37): 11350-11354.
7	YUE X Y, WANG J J, XIE Z K, et al. Coral reef-like MoS₂ microspheres with 1T/2H phase as high-performance anode material for sodium ion batteries[J]. Journal of Materials Science, 2020, 55(29): 14389-14400.
8	ZHOU L, YAO J G, REN Z X, et al. Development of magnetic multi-shelled hollow catalyst for biodiesel production[J]. Energies, 2020, 13(11): 2754.
9	张开莲, 杨凯, 李笑笑, 等. 一步水热合成In₂S₃/CdIn₂S₄异质结微球及其光催化性能[J]. 化工学报, 2020, 71(8): 3602-3613.
	ZHANG Kailian, YANG Kai, LI Xiaoxiao, et al. One-step hydrothermal synthesis of In₂S₃/CdIn₂S₄ heterojunction microsphere and its photocatalytic performance[J]. CIESC Journal, 2020, 71(8): 3602-3613.
10	KIM Y J, KIM J W, LEE J E, et al. Synthesis and adsorption properties of gold nanoparticles within pores of surface-functional porous polymer microspheres[J]. Journal of Polymer Science A： Polymer Chemistry, 2004, 42(22): 5627-5635.
11	王伟浩, 杨鑫, 李飞, 等. 载酶海藻酸钙复合微球稳定水包油型Pickering乳液及其强化界面酶催化反应[J]. 化工学报, 2019, 70(12): 4777-4786.
	WANG Weihao, YANG Xin, LI Fei, et al. E@Alg@s-TiO₂ microsphere stabilized O/W Pickering emulsion and the enhancement of interfacial enzymatic catalysis[J]. CIESC Journal, 2020, 71(8): 3602-3613.
12	ANCESCHI A, BINELLO A, CALDERA F, et al. Preparation of microspheres and monolithic microporous carbons from the pyrolysis of template-free hyper-crosslinked oligosaccharides polymer[J]. Molecules, 2020, 25(13): 3034.
13	HAO L, CHEN I C, OH J K, et al. Solid-shelled microspheres loaded with solvent as diluents for extracting blockages by heavy-oil and asphaltene precipitates[J]. Fuel, 2018, 234(15): 656-663.
14	WANG L L, LING C, LI B S, et al. Highly efficient removal of Cu(Ⅱ) by novel dendritic polyamine—Pyridine-grafted chitosan beads from complicated salty and acidic wastewaters[J]. RSC Advances, 2020, 10(34): 10943-19951.
15	LIU H J, CHEN M, ZHANG H, et al. One-step synthesis of hierarchical flower-like SnO₂/BiOCOOH microspheres with enhanced light response for the removal of pollutants[J]. Langmuir, 2020, 36(30): 9005-9013.
16	赵红永, 曹金城, 丁晓莉, 等. PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO₂渗透分离性能[J]. 化工学报, 2020, 71(S2): 210-215.
	ZHAO Hongyong, CAO Jincheng, DING Xiaoli, et al. Synthesis of PEO/hollow polypyrrole nanoparticle mixed matrix membranes for CO₂ separation[J]. CIESC Journal, 2020, 71(S2): 210-215.
17	WANG J M, WANG X Y, LI Y, et al. Preparation and properties of magnetic polymer microspheres[J]. Polymer, 2020, 199(11): 122569.
18	ZHAO S J, MA J T, LIN X P, et al. Preparation of tetragonal zirconia microspheres as surrogate precursor for uranium nitride microspheres[J]. Nuclear Engineering and Design, 2020, 362: 110542.
19	MILOH T, NAGLER J. Electrorotation of leaky-dielectric and conducting microspheres in asymmetric electrolytes and angular velocity reversal[J]. Electrophoresis, 2020, 41(15): 1296-1307.
20	LI J B, NIU L W, WU W X, et al. The reservoir adaptability and oil displacement mechanism of polymer microspheres[J]. Polymers, 2020, 12(4): 885.
21	GAO J F, LI W, WONG J S P, et al. Controllable morphology and wettability of polymer microspheres prepared by nonsolvent assisted electrospraying[J]. Polymer, 2014, 55(12): 2913-2920.
22	KANG D E, BYEON S J, HEO M S, et al. Fabrication of ordered honeycomb structures and microspheres using polystyrene-block-poly(tert-butyl acrylate) star polymers[J]. Journal of Polymer Research, 2014, 21(6): 382.
23	HE Y P, GUO W F, SHAN M X, et al. Technical improvement for producing porous polymer microspheres in foam phase[J]. Materials Letters, 2017, 8(15): 54-57.
24	HE Y P, LI X, ZHU T C, et al. Controlling the internal structures of polymeric microspheres via the introduction of a water-soluble organic solvent[J]. Polymers, 2018, 10(7): 789.
25	姚顺治, 单梦醒, 朱天赐, 等. 泡沫分离法制备聚苯乙烯多孔微球[J]. 化工进展, 2018, 37(7): 2753-2758.
	YAO Shunzhi, SHAN Mengxing, ZHU Tianci, et al. Preparation of porous polystyrene micropheres by using foam phase seperation[J]. Chemical Industry and Engineering Progress, 2018, 37(7): 2753-2758.
26	KARAKASHEV S I, GROZDANOVA M V. Foams and antifoams[J]. Advance in Colloid and Interface Science, 2012, 176/177(8/9): 1-17.
27	HILL C, EASTOE J. Foams: from nature to industry[J]. Advance in Colloid and Interface Science, 2017, 247(9): 496-513.
28	GOKMEN M T, DU PREZ F E. Porous polymer particles—A comprehensive guide to synthesis characterization, functionalization and applications[J]. Progress in Polymer Science, 2012, 37(3): 365-405.
29	WU D C, XU F, SUN B, et al. Design and preparation of porous polymers[J]. Chemical Reviews, 2012, 112(7): 3959-4015.
30	GILCHRIST S E, BITTERFIELD D, LETCHFORD K, et al. Phase separation behavior of fusidic acid and rifampicin in PLGA microspheres[J]. Molecular Pharmaceutics, 2012, 9(5): 1489-1501.
31	HE X H, JI Y, XIE J N, et al. Emulsion solvent evaporation induced self-assembly of polyarylene ether nitrile block copolymers into functional metal coordination polymeric microspheres[J]. Polymer, 2020, 186(9): 122024.
32	IM H Y, KIM J, SAH H K. Another paradigm in solvent extraction-based microencapsulation technologies[J]. Biomacromolecules, 2010, 11(3): 776-786.
33	PIACENTINI E, LAKSHMI D S, FIGOLI A. Polymeric microspheres preparation by membrane emulsification-phase separation induced process[J]. Journal of Membrane Science, 2013, 448(15): 190-197.
34	TORYANIK A I, POREBNYAK V G. Surface tension of aqueous solutions of acetone[J]. Journal of Structural Chemistry, 1977, 17(3): 464-465.

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