一种PPS/MWCNT@GO杂化膜的制备及性能

doi:10.16085/j.issn.1000-6613.2019-2074

摘要/Abstract

摘要：

将氧化后的多壁碳纳米管（MWCNT）和氧化石墨烯（GO）亲水性纳米粒子化学交联物（MWCNT@GO）作为填充物，在使用热致相分离（TIPS）法制备聚苯硫醚（PPS）膜的过程中，通过物理共混方式引入MWCNT@GO纳米粒子，制备PPS/MWCNT@GO杂化膜，用以提升PPS膜的性能。分别通过TEM、XPS、Raman、XRD和FTIR表征MWCNT和GO的结构以及交联过程中的官能团变化；利用SEM、CSM、DSC、孔径测试仪、接触角测试仪和拉伸测试仪表征杂化膜的形貌以及特性；同时，对杂化膜的水通量以及蛋白大分子和甲基蓝染料的截留性能进行了测试。结果表明，PPS/MWCNT@GO杂化膜的孔径减小到0.06μm左右，杂化膜具备优异的热稳定性和机械性能；同时，杂化膜表现出了较高的水通量，可达130L/(m²?h)；较好的分离性能，对牛血清蛋白大分子（BSA）的截留率接近100%，对甲基蓝（MB）染料的截留率也达到了92%左右。该杂化膜有望在高温、强酸、强碱和腐蚀性水污染环境中广泛应用。

关键词: 过滤, 膜, 纳米粒子, 聚苯硫醚, 多壁碳纳米管, 氧化石墨烯

Abstract:

The chemical crosslinking substance of oxidized multi-wall carbon nanotubes (MWCNT) and graphene oxide (GO) hydrophilic nanoparticles (MWCNT@GO) was prepared which was used as fillers to improve the performance of PPS membrane. During the preparation of polyphenylene sulfide (PPS) membrane by thermally induced phase separation (TIPS) method, MWCNT@GO nanoparticles were introduced by physical blending method to prepare PPS/MWCNT@GO hybrid membrane. TEM, XPS, Raman, XRD and FTIR were used to characterize the structure of nanoparticles and the changes of surface functional groups in the crosslinking process. SEM, CSM, DSC, aperture tester, contact Angle tester and tensile tester were used to characterize the morphology and structure characteristics of hybrid membranes. At the same time, the water flux of the hybrid membrane and the interception of albumin from bovine serum (BSA) or methylene blue (MB) dyes were tested. The results indicated that the pore diameter of PPS/MWCNT@GO hybrid membrane was reduced to 0.06μm, and the hybrid membrane had the excellent thermal stability and mechanical properties. At the same time, PPS hybrid membrane showed a high water flux up to 130L/(m²?h), and better separation performance of the interception rate of BSA close to 100% and the interception rate of MB dye to 92%. This hybrid membrane was expected to be widely used in high temperature, strong acid, strong alkali and corrosive water pollution environment.

Key words: filtration, membranes, nanoparticles, polyphenylene sulfide, multi-wall carbon nanotube, graphene oxide

中图分类号:

TQ028.8

贾康, 苏坤梅, 李振环. 一种PPS/MWCNT@GO杂化膜的制备及性能[J]. 化工进展, 2020, 39(10): 4102-4110.

Kang JIA, Kunmei SU, Zhenhuan LI. Preparation and properties of PPS/MWCNT@GO hybrid membrane[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4102-4110.

参考文献

1	王德禧.聚苯硫醚的特性及应用[J].塑料, 2002(2): 34-38.
1	WANG D X. Characteristics of PPS and its applied fields[J]. Plastics, 2002(2): 34-38.
2	TANTHAPANICHAKOON W, HATA M, NITTA K H, et al. Mechanical degradation of filter polymer materials: polyphenylene sulfide[J]. Polymer Degradation and Stability, 2006, 91(11): 2614-2621.
3	徐俊怡, 刘钊, 洪瑞, 等.聚苯硫醚的产业发展概况与复合改性进展[J].中国材料进展, 2015, 34(12): 883-888.
3	XU J Y, LIU Z, HONG R, et al. Progress in industry development and modification of polyphenylene sulfide[J]. Materials China, 2015, 34(12): 883-888.
4	吴忠文.特种工程塑料聚醚砜、聚醚醚酮树脂国内外研究、开发、生产现状[J].化工新型材料, 2002(6): 15-18.
4	WU Z W. Situation of research and production and development for the special engineering plastic polyether sulfone and polyether ether ketone at home and abroad[J]. New Chemical Materials, 2002(6): 15-18.
5	汪晓鹏.PPS特种工程塑料的性能和应用[J].上海塑料, 2019 (3): 8-11.
5	WANG X P. Properties and applications of PPS special engineering plastics[J]. Shanghai Plastics, 2019(3): 8-11.
6	WANG Y X, LI Y J, YANG H, et al. Super-wetting, photoactive TiO₂ coating on amino-silane modified PAN nanofiber membranes for high efficient oil-water emulsion separation application[J]. Journal of Membrane Science, 2019, 580: 40-48.
7	张佩琴,蔡邦肖.溶剂改性聚酰胺膜的研究[J].水处理技术, 2005(6): 8-11.
7	ZHANG P Q, CAI B X. Solvent modification of polyamide membrane[J]. Technology of Water Treatment, 2005(6): 8-11.
8	PAGLIERO M, BOTTINO A, COMITE A, et al. Novel hydrophobic PVDF membranes prepared by nonsolvent induced phase separation for membrane distillation[J]. Journal of Membrane Science, 2020, 596: 117575.
9	杜润红,赵家森.一种新的膜材料-聚苯硫醚[J].膜科学与技术, 2002(3): 56-59.
9	DU R H, ZHAO J S. Novel membrane material-polyphenylene sulfide[J]. Membrane Science and Technology, 2002(3): 56-59.
10	WANG X, LI Z, ZHANG M, et al. Preparation of a polyphenylene sulfide membrane from a ternary polymer/solvent/non-solvent system by thermally induced phase separation[J]. RSC Adv.， 2017, 7(17):10503-10516.
11	FAN T, LI Z, CHENG B, et al. Preparation, characterization of PPS micro-porous membranes and their excellent performance in vacuum membrane distillation[J]. Journal of Membrane Science, 2018, 556:107-117.
12	XU Z, LIU G, YE H, et al. Two-dimensional mxene incorporated chitosan mixed-matrix membranes for efficient solvent dehydration[J]. Journal of Membrane Science, 2018, 563: 625-632.
13	代俊明, 孙秀花, 高昌录. 共混改性法对有机分离膜影响进展[J].化工进展, 2019, 38(S1): 159-165.
13	DAI J M, SUN X H, GAO C L. Advances on effects of blending modification on organic separation membranes[J]. Chemical Industry and Engineering Progress, 2019, 38(S1): 159-165.
14	MARCANO D C, KOSYNKIN D V, BERLIN J M, et al. Improved synthesis of graphene oxide[J]. ACS Nano, 2010, 4(8): 4806-4814.
15	胡耀娟, 金娟, 张卉, 等.石墨烯的制备、功能化及在化学中的应用[J]. 物理化学学报， 2010, 26(8): 2073-2086.
15	HU Y J, JIN J, ZHANG H, et al. Graphene: synthesis, functionalization and applications in chemistry[J]. Acta Physico-Chimica Sinica, 2010, 26(8): 2073-2086.
16	XU Y, LI Z, SU K, et al. Mussel-inspired modification of PPS membrane to separate and remove the dyes from the wastewater[J]. Chemical Engineering Journal, 2018, 341: 371-382.
17	ZHANG Y, SU K, LI Z. Graphene oxide composite membranes cross-linked with urea for enhanced desalting properties[J]. Journal of Membrane Science, 2018, 563: 718-725.
18	GAO Y, SU K, LI Z, et al. Graphene oxide hybrid poly(p-phenylene sulfide) nanofiltration membrane intercalated by bis(triethoxysilyl) ethane[J]. Chemical Engineering Journal, 2018, 352: 10-19.
19	ZHAN W, YU S, GAO L, et al. Bioinspired assembly of carbon nanotube into graphene aerogel with “cabbagelike” hierarchical porous structure for highly efficient organic pollutants cleanup[J]. ACS Appl. Mater. Interfaces, 2018, 10(1): 1093-1103.
20	GAO L, SU K, FAN T, et al. Study on the structure and properties of PPS/PCNF hybrid membranes and their applications in wastewater treatment[J]. Polymer, 2019, 176: 274-282.
21	WU H, TANG B, WU P. Novel ultrafiltration membranes prepared from a multi-walled carbon nanotubes/polymer composite[J]. Journal of Membrane Science, 2010, 362(1/2): 374-383.
22	潘学杰, 吴礼光, 周勇, 等.碳纳米管/聚砜共混超滤膜的制备与表征[J].膜科学与技术, 2009, 29(5): 16-22.
22	PAN X J, WU L G, ZHOU Y, et al. Fabrication and characterization of blend polysulfone/modified multiwalled carbon nanotube membranes[J]. Membrane Science and Technology, 2009, 29(5): 16-22.

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