高通量聚苯并咪唑纳滤膜的结构调控及性能

doi:10.7503/cjcu20170618

摘要/Abstract

摘要：

聚苯并咪唑(PBI)是一种类杂环聚合物, 具有独特的耐高温性、化学稳定性和机械稳定性, 因而被广泛用作膜材料. PBI膜具有很高的选择性, 在耐溶剂纳滤领域具有较好的应用前景. 本文在PBI铸膜液中引入亲水性添加剂聚乙烯吡咯烷酮(PVP-K30), 通过调节PVP的含量来改变成膜过程中的动力学过程, 继而对PBI膜的结构进行进一步调控, 从而改善其渗透通量. 研究表明, 随着制膜液中PVP含量的增加, 通量不断升高, 对染料的截留保持稳定. 当PVP质量分数为15%时, PBI膜对亚甲基蓝的截留率达到99.18%, 表现出优异的分离性能.

关键词: 聚苯并咪唑, 聚乙烯吡咯烷酮, 耐溶剂纳滤膜, 渗透性能

Abstract:

A kind of heterocyclic polymerpolybenzimidazole(PBI) membranes are very promising for solvent resistant nanofiltration due to their excellent mechanical stability, thermal stability and chemical stability. Even though they showed high selectivity, however, the permeance is relatively low. In this study, we aim to enhance the permeance of PBI membranes while keep their selectivity. PBI membrane with different microstructures were prepared by introducing polyvinylpyrrolidone(PVP) in cast solution. The results showed that with increasing content of PVP, the flux of membrane increases, while, the rejection on dyes keeps constant. When the mass ratio of PVP is 15%, the PBI showed retention of 99.18% on methylene blue, showing very good selectivity.

Key words: Polybenzimidazole, Polyvinylpyrrolidone, Solvent resistant nanofiltration membrane, Permeance performance

中图分类号:

O635

赵彩秀, 杨溢, 刘一婷, 姜影, 袁芳, 王睿, 陈冬菊. 高通量聚苯并咪唑纳滤膜的结构调控及性能[J]. 高等学校化学学报, 2018, 39(4): 785-792.

ZHAO Caixiu, YANG Yi, LIU Yiting, JIANG Ying, YUAN Fang, WANG Rui, CHEN Dongju. High Flux Polybenzimidazole Solvent Resistant Nanofiltration Membranes: Morphology Control and Performance^†[J]. Chemical Journal of Chinese Universities, 2018, 39(4): 785-792.

图/表 14

Fig.1 Structure of PBI polymer

Table 1 Physical properties of the solvents

Solvent	Molar weight/ (g·mol^-1)	Molar volume/ (cm³·mol^-1)	Surface tension/ (mN·m^-1)	Viscosity/ (mPa·s)	Density/ (g·cm^-3)
IPA	60	76.92	21.7	1.96	0.785
Ethanol	46	58.68	22.3	1.074	0.790
THF	72	81.08	28.0	0.456	0.888
Acetone	58	73.40	23.3	0.306	0.791

Table 2 Properties of the solute

Component	Charge	Molar weight/ (g·mol^-1)	Molar volume/ (cm³·mol^-1)
Methylene blue(MB)	+	374	160
Bromothymol blue(BTB)	0	624.39	281
Rose bengal(RB)	-	1017	272.8

Fig.2 TG curve of PBI polymer

Table 3 Mechanical properties of the prepared membrane

Sample	Elasticity modulus/MPa	Elongation at break(%)	Tensile strength/MPa
15%PBI	130.54	16.00	6.74
15%PBI+10%PVP	115.87	17.17	6.52
15%PBI +20%PVP	103.06	12.11	5.75

Fig.3 Surface morphologies of PBI NF membranes(A)12%PBI; (B)12%PBI+5%PVP; (C)12%PBI+10%PVP; (D)12%PBI+15%PVP; (E)15%PBI; (F)15%PBI+5%PVP; (G)15%PBI+10%PVP; (H)15%PBI+15%PVP; (I)18%PBI; (J)18%PBI+5%PVP; (K)18%PBI+10%PVP; (L)18%PBI+15%PVP.

Fig.4 Cross-section morphologies of PBI NF membranes(A) 12%PBI; (B) 12%PBI+5%PVP; (C) 12%PBI+10%PVP; (D) 12%PBI+15%PVP;(E) 15%PBI; (F) 15%PBI+5%PVP; (G) 15%PBI+10%PVP; (H) 15%PBI+15%PVP;(I) 18%PBI; (J) 18%PBI+5%PVP; (K) 18%PBI+10%PVP; (L) 18%PBI+15%PVP.

Fig.5 FTIR spectra of PBI, PVP and PBI NF membranesa. PVP; b. 12%PBI; c. 12%PBI+5%PVP; d. 12%PBI+10%PVP; e. 12%PBI+15%PVP.

Fig.6 Permeability of different pure solvents through PBI NF membranes

Fig.7 Permeability of different pure solvents through PBI NF membranes with different compositions of casting solutions(A) a. 12%PBI; b. 12%PBI+5%PVP; c. 12%PBI+10%PVP; d. 12%PBI+15%PVP. (B) a. 15%PBI; b. 15%PBI+5%PVP; c. 15%PBI+10%PVP; d. 15%PBI+15%PVP. (C) a. 18%PBI; b. 18%PBI+5%PVP; c. 18%PBI+10%PVP; d. 18%PBI+15%PVP.

Fig.8 Separation performance of RB(A), BTB(B) and MB(C) through the PBI NF membranes(12%PBI) in IPA(a) and ethanol(b)

Fig.9 Permeability of RB(A), BTB(B) and MB(C) through the PBI NF membranes(12%PBI) in IPA(a) and ethanol(b)

Fig.10 Separation performance of RB(A), BTB(B) and MB(C) through the PBI NF membranes(15%PBI) in IPA(a) and ethanol(b)

Fig.11 Permeability of RB(A), BTB(B) and MB(C) through the PBI NF membranes(15%PBI) in IPA(a) and ethanol(b)

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