Preparation and Properties of Superhydrophilic Polyvinylidene Fluoride Hollow Fiber Membrane †

doi:10.7503/cjcu20190374

Abstract

Abstract:

PVDF-g-GMA membrane was prepared by grafting glycidyl methacrylate(GMA) onto the surface of polyvinylidene fluoride(PVDF) membrane by ultrasonic assisted graft polymerization. A modified membrane with zwitterionic structure surface(PVDF-g-GMA-Thr) was prepared by grafting threonine(Thr) onto the surface of the PVDF membrane through the ring opening reaction of epoxy groups induced by amino group. The chemical composition, wettability, surface morphology and antifouling performance of PVDF membrane before and after modification were systematically studied by Attenuated total reflection Fourier infrared spectroscopy(ATR-FTIR), X-ray photoelectron spectroscopy(XPS), contact angle analyzer, scanning electron microscopy(SEM) and bovine serum albumin(BSA) filtration experiments. The results show that with the increase of PVDF-g-GMA grafted threonine reaction time, the hydrophilicity of the prepared modified membrane with zwitterionic structure surface is obviously improved, and the contact angle is reduced from 90° to 0°, showing the superhydrophilicity. At the same time, the water flux of the modified membrane is obviously improved, when the threonine induces the ring opening reaction for 12 h, the modified membrane has the highest water flux as high as 686 L/(m ²·h), it increased by 204.5%. In addition, in the filtration test of BSA, the modified membrane exhibited good anti-fouling performance and retention performance. BSA rejection ratio is increased from 42% to 84% for the modified membranes. Moreover, compared with PVDF original membrane, the water flux recovery rate of the modified membrane increased from 53% to 87% and the irreversible fouling decreased from 47% to 12%, which indicated that the membrane fouling can be effectively reduced by grafting threonine to construct zwitterionic structure surface on the PVDF membrane.

Key words: Polyvinylidene fluoride membrane, Superhydrophilic, Threonine, Anti-fouling performance

CLC Number:

O631

TrendMD:

CHENG Jifeng,JIANG Tuanhui,ZHAN Xiaomei,QI Yating,YANG Yuanyuan,KANG Xun,QIN Shuhao. Preparation and Properties of Superhydrophilic Polyvinylidene Fluoride Hollow Fiber Membrane ^†[J]. Chem. J. Chinese Universities, 2020, 41(2): 358.

Figures/Tables 7

Scheme 1 Preparation process and chemical structure of superhydrophilic PVDF hollow fiber membrane

Fig.1 ATR-FTIR spectra(A) and XPS survey spectra(B) of pristine and modified membranes a. Pristine PVDF; b. M-1; c. M-6; d. M-12; e. M-18; f. M-24.

Sample	C(%)	F(%)	O(%)	N(%)	Zwitteironization degree(%)
Pristine PVDF	63.46	26.49	10.04	0	0
M-1	64.32	16.47	19.22	0	0
M-6	61.23	17.29	18.35	3.14	2.48
M-12	61.02	16.15	19.44	3.69	3.23
M-18	62.18	8.44	25.14	4.24	4.14
M-24	62.54	13.63	18.98	4.75	5.73

Fig.2 C1s core-level XPS spectra of pristine PVDF membrane(A), M-1(B) and M-6(C)

Fig.3 SEM images of surface morphology of pristine and modified membranes (A) Pristine PVDF; (B) M-1; (C) M-6; (D) M-12; (E) M-18; (F) M-24.

Fig.4 Water contact angle(A), water flux and BSA rejection(B) of the pure and modified membranes a. Pristine PVDF; b. M-1; c. M-6; d. M-12; e. M-18; f. M-24.

Fig.5 Time dependent flux(A) and the fouling parameters(B) of the pristine and modified membranes a. Pristine PVDF; b. M-1; c. M-6; d. M-12; e. M-18; f. M-24.

References 34

[1]	Chen G., Sun Y., Xu Z. L., Yang H., Huang H. H., Liu Y. J., Korean J., Chem. Eng., 2015,32(12), 2492— 2500
[2]	Gumus H ., J. Mol. Struct., 2018,1174, 122— 126 doi: 10.1016/j.molstruc.2018.04.088 URL
[3]	Luo D. J., Shao H. J., Jin J. B., Xie G. Y., Cui Z. Y., Yu J., Qin S. H., Chem. J. Chinese Universities, 2018,39(8), 1838— 1845
	( 罗大军, 邵会菊, 靳进波, 谢高艺, 崔振宇, 于杰, 秦舒浩 . 高等学校化学学报, 2018,39(8), 1838— 1845)
[4]	Zhang M. G., Nguyen Q. T., Ping Z. H., J. Membr. Sci., 2009,327(1/2), 78— 86 doi: 10.1016/j.memsci.2008.11.020 URL
[5]	Luo D. J., Wei F. J., Shao H. J., Xiang L.., Cui Z. Y., Qin S. H., Yu J., Sep. Purif. Technol., 2019,213, 328— 338 doi: 10.1016/j.seppur.2018.12.052 URL
[6]	Liu F., Hashim N. A., Liu Y. T., Abed M. R. M., Li K., J. Membr. Sci., 2011,375(1/2), 1— 27 doi: 10.1016/j.memsci.2011.03.014 URL
[7]	Pieracci J., Wood D. W., Crivello J. V., Belfort G., Chem. Mater., 2000,12(8), 2123— 2133
[8]	Wavhal D. S., Fisher E. R., Langmuir, 2003,19(1), 79— 85 doi: 10.1021/la020653o URL
[9]	Qiu J. H., Zhang Y. W., Shen Y. B., Zhang Y. T., Zhang H. Q., Liu J. D., Appl. Surf. Sci., 2010,256(10), 3274— 3280 doi: 10.1016/j.apsusc.2009.12.018 URL
[10]	Wang C., Feng R., Yang F ., J. Colloid Interf. Sci., 2011,357(2), 273— 279 doi: 10.1016/j.jcis.2011.01.094 URL
[11]	Yasui K., Tuziuti T., Lee J., Kozuka T., Towata A., Iida Y ., J. Chem. Phys., 2008,128(18), 184705— 184712 doi: 10.1063/1.2919119 URL
[12]	Xiao R., He Z. Q., Diaz-Rivera D., Pee G. Y., Weavers L. K., Ultrason. Sonochem., 2014,21(1), 428— 435 doi: 10.1016/j.ultsonch.2013.06.012 URL
[13]	Sancheti S. V., Gogate P. R., Ultrason. Sonochem., 2017,36, 527— 543 doi: 10.1016/j.ultsonch.2016.08.009 URL
[14]	Shao H. J., Wei F. J., Luo D. J., Zhang K. Z., Liang S. M., Tian Q., Qin S. H., Yu J., Polym. Eng. Sci., 2019,59(S1), 51— 58
[15]	Qi Y. T., Shao H. J., Luo D. J., Xiang L., Luo J. Y., Tian Q., Qin S. H., Polym. Eng. Sci., 2019, 446— 454
[16]	Alswieleh A. M., Cheng N., Canton I., Ustbas B., Xue X., Ladmiral V., Xia S. J., Ducker R. E., Zubir O. E., Cartron M. L., Hunter C. N., Leggett G. J., Armes S. P., J. Am. Chem. Soc., 2014,136(26), 9404— 9413 doi: 10.1021/ja503400r URL
[17]	Zhu Y. Z., Zhang F., Wang D., Pei X. F., Zhang W. B., Jin J., J. Mater. Chem. A, 2013,1(18), 5758— 5765 doi: 10.1039/c3ta01598j URL
[18]	He M., Gao K., Zhou L. J., Jiao Z. W., Wu M. Y., Cao J. L., You X. D., Cai Z. Y., Su Y. L., Jiang Z. Y., Acta Biomater., 2016,40, 142— 152 doi: 10.1016/j.actbio.2016.03.038 URL
[19]	Yang Y. F., Li Y., Li Q. L., Wan L. S., Xu Z. K., J. Membrane Sci., 2010,362(1/2), 255— 264 doi: 10.1016/j.memsci.2010.06.048 URL
[20]	Zhu Y. Z., Zhang F., Wang D., Pei X. F., Zhang W. B., Jin J., J. Mater. Chem. A, 2013,1(18), 5758— 5765 doi: 10.1039/c3ta01598j URL
[21]	Li Q., Bi Q. Y., Zhou B., Wang X. L., Appl. Surf. Sci., 2012,258(10), 4707— 4717 doi: 10.1016/j.apsusc.2012.01.064 URL
[22]	Chiang Y. C., Chang Y., Higuchi A., Chen W. Y., Ruaan R. C., J. Membrane Sci., 2009,339(1), 151— 159 doi: 10.1016/j.memsci.2009.04.044 URL
[23]	Li M. Z., Li J. H., Shao X. S., Miao J., Wang J. B., Zhang Q. Q., Xu X. P., J. Membrane Sci., 2012,405/406, 141— 148 doi: 10.1016/j.memsci.2012.02.062 URL
[24]	Liu Q., Singh A., Liu L ., Biomacromolecules, 2013,14(1), 226— 231 doi: 10.1021/bm301646y URL
[25]	Peter L., Ling D., Chii W. L., Frank G., Langmuir, 2014,30(22), 6497— 6507 doi: 10.1021/la500243s URL
[26]	Shi Q., Su Y., Chen W., Peng J., Nie L., Zhang L., Jiang Z ., J. Membrane Sci., 2011,366(1/2), 398— 404 doi: 10.1016/j.memsci.2010.10.032 URL
[27]	An Z. H., Dai F. Y., Wei C. J., Zhao Y. P., Chen L., J. Biomed. Mater. Res. Part B, 2018,106
[28]	Xu C., Liu X. J., Xie B. B., Yao C., Hu W. H., Li Y., Li X. S., Appl. Surf. Sci., 2016,385(16), 130— 138 doi: 10.1016/j.apsusc.2016.05.084 URL
[29]	Wang C. A., Zhao S., Wei Y. M., Chinese J. Chem., 2012,30(10), 2473— 2482 doi: 10.1002/cjoc.201200443 URL
[30]	Li Q., Bi Q. Y., Zhou B., Wang X. L., Appl. Surf. Sci., 2012,258(10), 4707— 4717 doi: 10.1016/j.apsusc.2012.01.064 URL
[31]	Liu Z. M., Xu Z. K., Wan L. S., Wu J., Ulbricht M., J. Membr. Sci., 2005,249, 21— 31 doi: 10.1016/j.memsci.2004.10.001 URL
[32]	Mi Y. F., Zhao F. Y., Guo Y. S., Weng X. D., Ye C. C., An Q. F., J. Membr. Sci., 2017,541, 29— 38 doi: 10.1016/j.memsci.2017.06.091 URL
[33]	Chen G. E., Sun W. G., Kong Y. F., Wu Q., Sun L., Yu J., Xu Z. L., Polym. Plast. Technol. Eng., 2017,57(2), 108— 117 doi: 10.1080/03602559.2017.1315640 URL
[34]	Liu D. P., Zhu J., Qiu M., He C. J., Sep. Purif. Technol., 2016,171, 1— 10 doi: 10.1016/j.seppur.2016.07.006 URL