超临界CO2诱导相转化法制备聚苯乙烯膜及膜体系的相图计算

doi:10.7503/cjcu20160208

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (8): 1573.doi: 10.7503/cjcu20160208

超临界CO₂诱导相转化法制备聚苯乙烯膜及膜体系的相图计算

刘学武¹(), 陈淑花²(), 詹世平²

1. 大连理工大学化工机械与安全学院, 大连 116023
2. 大连大学环境与化学工程学院, 大连 116622

收稿日期:2016-04-05 出版日期:2016-07-14 发布日期:2016-07-14
作者简介:
联系人简介: 刘学武, 男, 博士, 副教授, 主要从事超临界流体技术/气体分离净化研究. E-mail: liuxuewu@dlut.edu.cn.陈淑花, 女, 博士, 副教授, 主要从事超临界流体技术研究. E-mail: chensh1976@126.com
基金资助:
国家自然科学基金(批准号: 21106010, 21376035)资助

Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO₂-induced Phase Inversion^†

LIU Xuewu^1,^*(), CHEN Shuhua^2,^*(), ZHAN Shiping²

1. School of Chemical Machinery and Safety Engineering, Dalian University of Technology, Dalian 116023, China
2. School of Environmental and Chemical Engineering, Dalian University, Dalian 116622, China

Received:2016-04-05 Online:2016-07-14 Published:2016-07-14
Contact: LIU Xuewu,CHEN Shuhua E-mail:liuxuewu@dlut.edu.cn;chensh1976@126.com
Supported by:
Supported by the National Natural Science Foundation of China(Nos.21106010, 21376035)

摘要/Abstract

摘要：

以甲苯为溶剂, 利用超临界CO₂诱导相转化法制备了多孔非对称聚苯乙烯膜. 通过扫描电镜对膜结构进行了表征, 探讨了不同温度、压力和铸膜液中聚苯乙烯浓度对膜形态、孔径分布及膜孔隙率的影响; 同时, 基于Tompa扩展的Flory-Huggins聚合物溶液理论计算了聚苯乙烯/超临界CO₂/甲苯铸膜体系的三元相图. 研究表明, 在温度为35~65 ℃、压力为8~16 MPa及聚合物质量分数为15%~35%条件下, 制备的聚苯乙烯膜截面呈胞腔状孔结构, 孔隙率为53.54%~84.67%, 且孔隙率随温度、压力和聚苯乙烯浓度均呈现出先增大后减小的趋势. 相图计算结果表明, 温度对体系双节线位置的改变影响较小, 而压力对其影响相对较大.

关键词: 超临界CO2相转化, 聚苯乙烯, 微孔聚合物, 孔隙率, 三元相图

Abstract:

Microporous asymmetric polystyrene(PSt) membranes were prepared by supercritical CO₂-induced phase inversion. The experiments were designed and conducted to investigate the effects of different process parameters, such as temperature, CO₂ pressure and PSt concentration in casting solution, on the membrane morphologies, pore size distribution and especially on the porosity of the membranes. The ternary phase diagrams of polystyrene/supercritical CO₂/toluene system were determined based on the extended Flory-Huggins theory of polymer solutions of Tompa. The prepared PSt membrane had a cellular structure. The porosity of the products was in the range of 53.54%—84.67%; and it showed a tendency of increasing to a peak and then decreasing with the increase of each parameter(temperature, pressure or PSt concentration). The theoretical phase diagrams indicated that pressure has more influence in changing the binodal curve location than that of temperature.

Key words: Supercritical CO2 phase inversion, Polystyrene, Microporous membrane, Porosity, Ternary phase diagram(Ed.: D, Z)

中图分类号:

TrendMD:

刘学武, 陈淑花, 詹世平. 超临界CO₂诱导相转化法制备聚苯乙烯膜及膜体系的相图计算. 高等学校化学学报, 2016, 37(8): 1573.

LIU Xuewu,CHEN Shuhua,ZHAN Shiping. Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO₂-induced Phase Inversion^†. Chem. J. Chinese Universities, 2016, 37(8): 1573.

图/表 13

Fig.1 Schematic illustration of the ScCO2 setup P: Pressure gauge; TCI: temperature control indicator; 1. CO2 tank; 2,4,5. valve; 3. compressor; 6. polymer membrane;7. supporting block; 8. membranes formation vessel.

Fig.2 Effect of temperature on PSt(25%, mass fraction) membrane cross-section at 12 MPa Temperature/℃: (A) 35; (B) 55.

Fig.3 Cell size distribution of PSt(25%) membrane at 35 ℃(a) and 55 ℃(b) with 12 MPa

Fig.4 Porosity of PSt(25%) membrane at different temperature with 12 MPa

Fig.5 Effect of pressure on PSt(25%) membrane cross-section at 40 ℃ Pressure/MPa: (A) 9; (B) 16.

Fig.6 Cell size distribution of PSt(25%) membrane with 9 MPa(a) and 16 MPa(b) at 40 ℃

Fig.7 Porosity of PSt(25%) membrane with different pressure at 40 ℃

Fig.8 Effect of polymer concentration on PSt membrane cross-section at 40 ℃ and 10 MPa Mass fraction of PSt: (A) 15%; (B) 35%.

Fig.9 Cell size distribution of 15% PSt(a) and 35% PSt(b) membranes at 40 ℃ and 10 MPa

Fig.10 Porosity of PSt membrane with different mass fractions of PSt at 40 ℃ and 10 MPa

Table 1 Input parameters for calculating the ternary phase diagram of PSt/ScCO2/toluene system

Component	Hansen solubility parameter/MPa^1/2			Molar volume/(cm³·mol^-1)	Reference
Component	δ_d			δ_p	δ_h
PSt	21.28	5.75	4.30	40909	[21]
Toluene	18.00	1.40	2.00	107	[21]
ScCO₂(35 ℃, 12 MPa)	9.71	4.30	4.73	57	This paper
ScCO₂(55 ℃, 12 MPa)	5.79	3.50	3.75	86	This paper
ScCO₂(40 ℃, 9 MPa)	5.54	3.44	3.76	89	This pepar
ScCO₂(40 ℃, 16 MPa)	10.14	4.38	4.79	55	This pepar

Fig.11 Phase diagram of the PSt/ScCO2/toluene system with different temperatures

Fig.12 Phase diagram of the PSt/ScCO2/toluene system with different pressures

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超临界CO₂诱导相转化法制备聚苯乙烯膜及膜体系的相图计算

Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO₂-induced Phase Inversion^†

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