Effect of coagulation bath composition on the structure and performance of SMA/CPVC blend ultrafiltration membrane

doi:10.16085/j.issn.1000-6613.2020-0861

Abstract

Abstract:

The styrene-maleic anhydride copolymer (SMA)/chlorinated polyvinyl chloride (CPVC) blend ultrafiltration membranes was prepared bynon-solvent induced phase separation (NIPS). The effects of different solvent (DMAc) content in coagulation bath on the degree of anhydride group segregation of membranes surface, microstructure, hydrophilicity, water flux, rejection and anti-pollution of the ultrafiltration membrane were discussed. The results showed that the increase of DMAc content in the coagulation bath inhibited the degree of segregation of anhydride on the membrane surface, resulting in the decrease of hydrophilicity. At the same time, the decrease of the diffusion rate between DMAc and water molecules in the casting solution caused delayed phase separation, which made the pore size of the membrane surface smaller and the distribution narrower. When the mass ratio of DMAc was 3%, the BSA retention rate of ultrafiltration membrane increased to 98.10% with the flux recovery rate of 96.82%, and the irreversible contamination rate decreased to 3.77%, indicating that the appropriate solvent in the coagulation bath could further improve the anti-pollution performance of the ultrafiltration membrane.

Key words: non-solvent phase separation, ultrafiltration membrane, surface segregation, anti-pollution

摘要：

通过非溶剂致相分离（NIPS）法制备了苯乙烯-马来酸酐共聚物（SMA）/氯化聚氯乙烯（CPVC）共混超滤膜，探讨了凝固浴中不同溶剂（DMAc）含量对其超滤膜表面酸酐基团偏析程度、微观结构、亲水性、水通量、截留率和抗污染的影响。结果表明：凝固浴中溶剂含量的增加抑制了酸酐基团向膜表面的偏析，导致亲水性减弱；同时，铸膜液中溶剂与水分子之间扩散速率的变小引起延迟分相，使得膜表面孔径变小和分布变窄。当溶剂质量分数为3%时，超滤膜对牛血清白蛋白（BSA）截留率提升至98.10%、通量恢复率为96.82%，且不可逆污染率降为3.77%，表明凝固浴中适量的溶剂可进一步提高超滤膜抗污染性能。

关键词: 非溶剂致相分离, 超滤膜, 表面偏析, 抗污染

CLC Number:

TQ028.8

CHEN Guijing, YANG Yuanyuan, KANG Dongdong, SHAO Huiju, QIN Shuhao. Effect of coagulation bath composition on the structure and performance of SMA/CPVC blend ultrafiltration membrane[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1284-1291.

陈贵靖, 杨园园, 康冬冬, 邵会菊, 秦舒浩. 凝固浴组成对SMA/CPVC共混超滤膜的结构与性能影响[J]. 化工进展, 2021, 40(3): 1284-1291.

Figures/Tables 9

References 23

1	LIU J Z, SU Y L, PENG J M, et al. Preparation and performance of antifouling PVC/CPVC blend ultrafiltration membranes[J]. Industrial & Engineering Chemistry Research, 2012, 51(24): 8308-8314.
2	WU C R, WANG Z Y, LIU S H, et al. Simultaneous permeability, selectivity and antibacterial property improvement of PVC ultrafiltration membranes via in-situ quaternization[J]. Journal of Membrane Science, 2018, 548: 50-58.
3	刘家桢. 聚氯乙烯/氯化聚氯乙烯多孔膜的制备及改性研究[D]. 天津: 天津大学, 2013.
	LIU J Z. The research on the fabrication and modification of polyvinyl chloride/chlorinated polyvinl chloride porous membrane[D]. Tianjin: Tianjin University, 2013.
4	HESAMODDIN R, SEYED M S S, AMIR M, et al. Enhancement in permeation and antifouling properties of PVC ultrafiltration membranes with addition of hydrophilic surfactant additives: Tween-20 and Tween-80[J]. Journal of Environmental Chemical Engineering, 2016, 4(4): 4050-4061.
5	MENG X R, TANG W T, WANG L, et al. Mechanism analysis of membrane fouling behavior by humic acid using atomic force microscopy: effect of solution pH and hydrophilicity of PVDF ultrafiltration membrane interface[J]. Journal of Membrane Science, 2015, 487: 180-188.
6	DENG L, MRKSICH M, WHITESIDES G M. Self-assembled monolayers of alkanethiolates presenting tri(propylene sulfoxide) groups resist the adsorption of protein [J]. Journal of the American Chemical Society, 1996, 118(21): 5136-5137.
7	HOLMLIN R E, CHEN X, CHAPMAN R G, et al. Zwitterionic SAMs that resist nonspecific adsorption of protein from aqueous buffer [J]. Langmuir, 2001, 17(9): 2841-2850.
8	WU Z G, CUI Z Y, LI T Y, et al. Fabrication of PVDF-based blend membrane with a thin hydrophilic deposition layer and a network structure supporting layer via the thermally induced phase separation followed by non-solvent induced phase separation process[J]. Applied Surface Science, 2017, 419: 429-438.
9	RAMZMJOUA A, MANSOUR J, CHENA V. The effects of mechanical and chemical modification of TiO₂ nanoparticles on the surface chemistry, structure and fouling performance of PES ultrafiltration membranes[J]. Journal of Membrane Science, 2011, 378: 73-84.
10	FARJAMI M, VATANPOURB V, MOGHADASSI A. Fabrication of a new emulsion polyvinyl chloride(EPVC) nanocomposite ultrafiltration membranemodified by para-hydroxybenzoate alumoxane(PHBA) additive to improve permeability andantifouling performance[J]. Chemical Engineering Research and Design, 2020, 153: 8-20.
11	朱德钦, 生瑜, 兰明荣. PVC/CPVC 复合材料的力学和耐热性能研究[J]. 聚氯烯, 2005(3): 19-20.
	ZHU D Q, SHENG Y, LAN M R. Study on mechanical and thermal properties of PVC/CPVC composites[J]. Polyvinyl Chloride, 2005(3): 19-20.
12	刘倩文, 张小娟, 顾倩倩, 等. 添加剂PEG对CPVC/PVB共混膜性能的影响[J]. 化工进展, 2017, 36(4): 1388-1394.
	LIU Q W, ZHANG X J, GU Q Q, et al. Effects of additive PEG on the properties of CPVC/PVB blended membranes[J]. Chemical Industry and Engineering Progress, 2017, 36(4): 1388-1394.
13	陈云逸, 刘倩文, 吕晓宁, 等. 共混比对氯化聚氯乙烯(CPVC)/聚乙烯醇缩丁醛(PVB)共混超滤膜的影响[J]. 环境工程学报, 2017, 11(4): 2197-2204.
	CHEN Y Y, LIU Q W, LV X N, et al. Preparation and characterization of CPVC/PVB blend ultrafiltration membrane[J]. Chinese Journal of Environmental Engineering, 2017, 11(4): 2197-2204.
14	FAN X C, SU Y L, ZHAO X T, et al. Fabrication of polyvinyl chloride ultrafiltration membranes with stable antifouling property by exploring the pore formation and surface modification capabilities of polyvinyl formal[J]. Journal of Membrane Science, 2014, 464: 100-109.
15	ZHANG Y, TONG X, ZHANG B P, et al. Enhanced permeation and antifouling performance of polyvinyl chloride (PVC) blend Pluronic F127 ultrafiltration membrane by using salt coagulation bath (SCB)[J]. Journal of Membrane Science, 2018, 548: 32–41.
16	杨振生, 李金瑞, 任艳娜, 等. 凝固浴组成对PVDF高度疏水微孔膜结构和性能的影响[J]. 天津工业大学学报, 2016, 35(5): 10-15.
	YANG Z S, LI J R, REN Y N, et al. Effect of coagulation bath composition on morphology and property of microporous PVDF high hydrophobic membrane[J]. Journal of Tianjin Polytechnic University, 2016, 35(5): 10-15.
17	姜忠义, 陈文娟, 苏延磊. 抗污染膜表面构建的研究进展[J]. 膜科学与技术, 2011, 31(3): 64-68.
	JIANG Z Y, CHEN W J, SU Y L. Research progress in surface construction of antifouling membranes[J]. Membrane Science and Technology, 2011, 31(3): 64-68.
18	LIU Y, SU Y L, LI Y F, et al. Antifouling property improved of PVDF membranes by incorporating amphiphilic block-like copolymer for oil/water emulsion separation[J]. RSC Advances, 2015, 5: 21349-21359.
19	JIANG R, YAO S, CHEN Y C, et al. Effect of chain topological structure on the crystallization, rheological behavior and foamability of TPEE using supercritical CO₂ as a blowing agent[J]. The Journal of Supercritical Fluids, 2019, 147: 48-58.
20	YONG M, ZHANG Y Q, SUN S, et al. Properties of polyvinyl chloride (PVC) ultrafiltration membrane improved by lignin: hydrophilicity and antifouling[J]. Journal of Membrane Science, 2019, 575: 50-59.
21	QIU G M, ZHU B K, XU Y Y, et al. Synthesis of ultrahigh molecular weight poly(styrene-alt-malei canhydride) in supercritical carbon dioxide[J]. Macromolecules. 2006, 39: 3231-3237.
22	HOSSWIN M, FATEMEH A. An efficient nanofiltration membrane based on blending of polyethersulfone with modified (styrene/maleic anhydride) copolymer[J]. Journal of the Iranian Chemical Society, 2016, 13: 873-880.
23	王越, 袁书珊, 杨杰, 等. 凝固浴对聚芳硫醚砜分离膜结构与性能的影响[J]. 合成树脂及塑料, 2017, 34(2): 1-6.
	WANG Y, YUAN S S, YANG J, et al. Effect of coagulation bath on structure and properties of PASS membranes[J]. China Synthetic Resin and Plastics, 2017, 34(2): 1-6.

序号	化学组成及其质量分数/%			平均孔径 /nm
序号	C	Cl	O	平均孔径 /nm
M0	57.73	38.12	4.15	31.5
M1	59.85	36.14	4.01	29.7
M2	60.46	35.78	3.76	25.6
M3	60.77	35.58	3.65	21.4
M4	61.20	35.46	3.34	19.7
M5	61.32	35.59	3.09	16.3

序号	化学组成及其质量分数/%			平均孔径 /nm
序号	C	Cl	O	平均孔径 /nm
M0	57.73	38.12	4.15	31.5
M1	59.85	36.14	4.01	29.7
M2	60.46	35.78	3.76	25.6
M3	60.77	35.58	3.65	21.4
M4	61.20	35.46	3.34	19.7
M5	61.32	35.59	3.09	16.3

[1]	SUN Luqin, LU Huixia, WANG Jianyou. Separation of lysozyme from egg white by electrodialysis with ultrafiltration membrane(EDUF) process [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2262-2271.
[2]	YANG Junling, LI Ao, CHEN Yue, ZHU Guangcan, LI Shuping, LU Yongze. Infrared spectroscopy-multivariate curve resolution analysis of aluminum-based coagulants to mitigate membrane fouling [J]. Chemical Industry and Engineering Progress, 2022, 41(9): 5132-5141.
[3]	Zhiying WANG,Chengzhi HAN,Susu NING,Zhensheng YANG,Chunli LI. Preparation and properties of interface enhanced PVDF/PET membrane [J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1461-1467.
[4]	ZHU Zipei, TANG Xu, HE Qi, DONG Hao, ZHU Liang, XIAO Kaijun. Preparation of Al₂O₃/PVDF hybrid membrane from surface-modified silane coupling agent [J]. Chemical Industry and Engineering Progree, 2017, 36(02): 652-657.
[5]	ZHANG Chunfang，LIU Jian，BAI Yunxiang，GU Jin，SUN Yuping. Effect of Dean vortex efficiency on emulsification of diesel prepared by ultrafiltration membrane [J]. Chemical Industry and Engineering Progree, 2011, 30(10): 2141-.
[6]	TAN Lingyan，LIU Jindun，ZHANG Haoqing，LIANG Qihui. Study on sulfonated polyethersulfone(SPES)/polysulfone(PSF) blend ultrafiltration membrane [J]. Chemical Industry and Engineering Progree, 2007, 26(6): 864-.
[7]	GU Lei，LIU Youzhi，SHEN Hongyan，ZHANG Hongyu. Cleaning of ceramic membranes in filtration of emulsified suspension [J]. Chemical Industry and Engineering Progree, 2007, 26(2): 226-.