聚丙烯/聚硅氧烷-二氧化硅中空纤维膜的制备与性能分析

doi:10.16085/j.issn.1000-6613.2023-1353

摘要/Abstract

摘要：

为了提高气液分离用聚丙烯（PP）微孔膜的疏水性能，本研究将聚硅氧烷-二氧化硅纳米粒子和聚丙烯树脂熔融共混，采用熔融-拉伸法制备疏水聚丙烯中空纤维膜，进行了差示扫描量热仪、综合热分析仪、扫描电子显微镜、原子力显微镜、孔隙率、水接触角、气体/纯水通量等测试与表征，研究了不同含量的聚硅氧烷-二氧化硅对中空纤维膜结构和性能的影响。结果表明，随着聚硅氧烷-二氧化硅质量分数的增加，膜的水接触角逐渐增大，平均孔径、纯水通量和气体通量均呈现先增大后减小的趋势。当聚硅氧烷-二氧化硅质量分数为2%时，膜的水接触角从108.6°增加到127.6°，表明PP微孔膜的疏水性能得到明显改善。膜孔隙率为59.4%，气体通量为61.76L/(m²∙s)，是纯PP膜的2.16倍。同时聚硅氧烷-二氧化硅可以起到异相成核的作用，改善聚丙烯PP微孔膜的退火效果，使主片层结构变得稳定，孔结构依然由分离的片晶组成。

关键词: 聚硅氧烷, 二氧化硅, 聚丙烯微孔膜, 疏水性

Abstract:

To improve the hydrophobic performance of polypropylene (PP) microporous membranes for gas-liquid separation, the polysiloxane-silica and polypropylene resin were blended and made into hydrophobic polypropylene hollow fiber membranes by the melt-stretching method. DSC, TGA, SEM, AFM, porosity, water contact angle and gas/pure water fluxes were carried out to investigate the effect of polysiloxane-silica contents on the structure and performance of the hollow fiber membrane. The results showed that as the polysiloxane-silica content increased, the water contact angle of the membrane gradually increased, and the average pore size, pure water flux and gas flux indicated a trend of increasing and then decreasing. When the polysiloxane-silica content increased from 0 to 2%, the water contact angle of the membrane increased from 108.6° to 127.6°, indicating that the hydrophobicity of the PP microporous membrane was significantly improved. The membrane porosity was 59.4%, and the gas flux was 61.76L/(m²∙s), which was 2.16 times that of the pure PP membrane. Additionally, the polysiloxane-silica played the role of heterogeneous nucleation, improved the annealing effect, and made the structure of the main lamellae stable. The pore structure still consisted of separated lamellae crystals.

Key words: polysiloxane, silica, polypropylene microporous membrane, hydrophobicity

中图分类号:

TQ028

阳梦萍, 孙军军, 张晨曦, 薛昊龙, 肖长发. 聚丙烯/聚硅氧烷-二氧化硅中空纤维膜的制备与性能分析[J]. 化工进展, 2024, 43(9): 5106-5112.

YANG Mengping, SUN Junjun, ZHANG Chenxi, XUE Haolong, XIAO Changfa. Preparation and analysis of polypropylene/polysiloxane-silica hollow fiber membrane[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5106-5112.

图/表 10

图1 聚丙烯中空纤维膜拉伸致孔原理

图2 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜SEM图及三维形貌图

图3 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜DSC曲线

图4 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜TGA曲线

图5 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜水接触角

表1 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜平均孔径与孔隙率

样品	平均孔径/μm	孔隙率/%
M0	0.365	54.2
M0.5	0.376	54.7
M1	0.460	55.7
M2	0.501	59.4
M3	0.293	37.8

图6 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜的孔径及其分布

图7 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜的渗透性能

图8 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜的应力-应变曲线

表2 不同质量分数PP/聚硅氧烷-二氧化硅中空纤维膜力学性能

样品	断裂强度/MPa	断裂伸长率/%
M0	49.1	58.6
M0.5	54.2	47.9
M1	61.6	42.3
M2	68.3	38.2
M3	71.1	35.3

参考文献 23

1	GEDE WENTEN I, FRIATNASARY Dwi L, KHOIRUDDIN K, et al. Extractive membrane bioreactor (EMBR): Recent advances and applications[J]. Bioresource Technology, 2020, 297: 122424.
2	LUO Dajun, XIANG Li, SUN Xin, et al. Phase-change smart lines based on paraffin-expanded graphite/polypropylene hollow fiber membrane composite phase change materials for heat storage[J]. Energy, 2020, 197: 117252.
3	郑细鸣, 范荣玉. 微孔聚丙烯膜表面壳聚糖季铵盐的共价修饰及其抗菌性能[J]. 化工进展, 2021, 40(1): 332-338.
	ZHENG Ximing, FAN Rongyu. Covalent modification of chitosan quaternary ammonium salt on microporous polypropylene membrane and its antibacterial properties[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 332-338.
4	肖俊丽, 贺高红, 代岩, 等. PEGDME强化PVDF/PP复合膜的CO₂分离性能[J]. 化工进展, 2014, 33(11): 3031-3036.
	XIAO Junli, HE Gaohong, DAI Yan, et al. Improving CO₂ separation performance of PEGDME-PVDF/PP composite membrane[J]. Chemical Industry and Engineering Progress, 2014, 33(11): 3031-3036.
5	DAI Zhongde, DENG Jing, ANSALONI Luca, et al. Thin-film-composite hollow fiber membranes containing amino acid salts as mobile carriers for CO₂ separation[J]. Journal of Membrane Science, 2019, 578: 61-68.
6	黄柳青, 王雯冉, 张浴曈, 等. 地表水中全氟及多氟烷基化合物(PFASs)的污染现状研究进展[J]. 环境化学, 2024(3): 6-23.
	HUANG Liuqing, WANG Wenran, ZHANG Yutong, et al. Research progress on the pollution status of per-and polyfluoroalkyl substances (PFASs) in surface water: A review[J]. Environmental Chemistry, 2024(3): 6-23.
7	3M宣布将于2025年停产停用“永久化学品”PFAS[J]. 印染, 2023, 49(2): 82.
	3 M announced that it will stop production and stop using PFAS, a “permanent chemical”, in 2025[J]. China Dyeing & Finishing, 2023, 49(2): 82.
8	何强, 颜正, 智悦, 等. 植物对PFAS的富集机制研究进展[J]. 中国环境科学, 2022, 42(11): 5395-5407.
	HE Qiang, YAN Zheng, ZHI Yue, et al. Research progress on bioaccumulation of per- and polyfluoroalkyl compounds by plants[J]. China Environmental Science, 2022, 42(11): 5395-5407.
9	王佩, 黄欣怡, 曹致纬, 等. 新污染物共排放对生态环境监测和管理的挑战[J]. 环境科学, 2022, 43(11): 4801-4809.
	WANG Pei, HUANG Xinyi, CAO Zhiwei, et al. The challenge of co-emission of new pollutants to ecological environment monitoring and management[J]. Environmental Science, 2022, 43(11): 4801-4809.
10	CHANG Guocang, LIU Zhen, GUO Xiaojie, et al. Construction of superhydrophobic micro/nano-structure surface on polypropylene hollow fiber membrane and its application in membrane distillation[J]. Journal of Materials Science, 2022, 57(9): 5658-5678.
11	崔崑, 黄晋, 赵巧玲, 等. 高熔体强度聚丙烯中长支链结构的分析与表征方法新进展[J]. 化工进展, 2022, 41(10): 5425-5440.
	CUI Kun, HUANG Jin, ZHAO Qiaoling, et al. New progress in analysis and characterization of long-chain structure in high melt strength polypropylene[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5425-5440.
12	SAFFAR Amir, JALALI DIL Ebrahim, CARREAU Pierre J, et al. Phase behavior of binary blends of PP/PP-g-AA: Limitations of the conventional characterization techniques[J]. Polymer International, 2016, 65(5): 508-515.
13	XU Shuangshuang, WANG Qing, WANG Ning. Chemical fabrication strategies for achieving bioinspired superhydrophobic surfaces with micro and nanostructures: A review[J]. Advanced Engineering Materials, 2021, 23(3): 1-20.
14	王志英, 韩承志, 于泳波, 等. 超疏水聚偏氟乙烯复合微孔膜的制备及性能[J]. 化工进展, 2018, 37(2): 673-680.
	WANG Zhiying, HAN Chengzhi, YU Yongbo, et al. Preparation and properties of superhydrophobic PVDF microporous composite membrane[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 673-680.
15	WANG Yingqi, HE Gaohong, SHAO Yushan, et al. Enhanced performance of superhydrophobic polypropylene membrane with modified antifouling surface for high salinity water treatment[J]. Separation and Purification Technology, 2019, 214: 11-20.
16	JU Weilong, LI Shaofan, SU Yunlan, et al. Controllable synthesis of a well-defined polypropylene grafted silica nanoparticles and its effect on crystallization behavior of polypropylene[J]. Chinese Journal of Polymer Science, 2022, 40(11): 1411-1421.
17	DING Qian, FU Hao, HUA Chaoran, et al. Crystallization of post-consumer polypropylene in the presence of β-nucleating agent[J]. Journal of Thermal Analysis and Calorimetry, 2019, 138(1): 379-385.
18	刘晶如, 胡方明, 俞强. 聚丙烯接枝马来酸酐改性纳米ZnO/聚丙烯复合材料的成核结晶行为及力学性能[J]. 复合材料学报, 2017, 34(7): 1526-1532.
	LIU Jingru, HU Fangming, YU Qiang. Nucleation and crystallization and mechanical properties of nano-ZnO/polypropylene composites modified by maleic anhydride grafted polypropylene[J]. Acta Materiae Compositae Sinica, 2017, 34(7): 1526-1532.
19	GRASSIE N, SCOTT G. Polymer degradation and stabilization[M]. Cambridge University Press, 1985.
20	FINA A, TABUANI D, CARNIATO F, et al. Polyhedral oligomeric silsesquioxanes (POSS) thermal degradation[J]. Thermochimica Acta, 2006, 440(1): 36-42.
21	WENZEL Robert N. Resistance of solid surfaces to wetting by water[J]. Industrial & Engineering Chemistry, 1936, 28(8): 988-994.
22	CASSIE A B D, BAXTER S. Wettability of porous surfaces[J]. Transactions of the Faraday Society, 1944, 40(0): 546-551.
23	田苗苗, 李雪梅, 殷勇, 等. 超疏水膜的制备及其在膜蒸馏过程中的应用[J]. 化学进展, 2015, 27(8): 1033-1041.
	TIAN Miaomiao, LI Xuemei, YIN Yong, et al. Preparation of superhydrophobic membranes and their application in membrane distillation[J]. Progress in Chemistry, 2015, 27(8): 1033-1041.

[1]	刘丽, 冯博, 文洋, 古启雄. 硅基介孔材料的合成、功能化及对金属的吸附研究进展[J]. 化工进展, 2024, 43(9): 5063-5078.
[2]	曹海珍, 王尚彬, 欧红香, 薛洪来, 毕海普, 王钧奇. 疏水改性纳米二氧化硅对无氟泡沫灭火剂性能影响[J]. 化工进展, 2024, 43(6): 3301-3309.
[3]	熊文婷, 罗启基, 鄢春根. 二氧化硅基气凝胶材料及其制备技术的专利分析[J]. 化工进展, 2024, 43(4): 1912-1922.
[4]	李伟杰, 康金灿, 张传明, 林丽娜, 李昌鑫, 朱红平. 锆改性Cu/SiO₂催化剂催化3-羟基丙酸甲酯选择性加氢[J]. 化工进展, 2024, 43(3): 1328-1341.
[5]	姚福春, 毕莹莹, 唐晨, 杜明辉, 李泽莹, 张耀宗, 孙晓明. 中空纤维膜臭氧接触式反应器传质机理分析[J]. 化工进展, 2024, 43(2): 1089-1097.
[6]	王尚彬, 欧红香, 薛洪来, 曹海珍, 王钧奇, 毕海普. 黄原胶和纳米二氧化硅对无氟泡沫性能的影响[J]. 化工进展, 2023, 42(9): 4856-4862.
[7]	夏慧芸, 杨浩田, 卢昌杰, 宋莉芳, 牛艳辉. 路面裂缝用聚硅氧烷密封材料研究进展[J]. 化工进展, 2023, 42(2): 814-820.
[8]	田月, 董晓涵, 苏毅. SiO₂-CTAB复合材料的制备及其对PNP的吸附性能[J]. 化工进展, 2023, 42(11): 6064-6075.
[9]	杨程瑞雪, 黄琪媛, 冉建速, 崔耘通, 王健健. 磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧[J]. 化工进展, 2023, 42(10): 5179-5190.
[10]	潘月磊, 程旭东, 闫明远, 何盼, 张和平. 二氧化硅气凝胶及其在保温隔热领域应用进展[J]. 化工进展, 2023, 42(1): 297-309.
[11]	叶玉玺, 丁晓茜, 池华睿, 朱楷伦, 刘杨, 王凌云, 郭庆杰. 疏水性低共熔溶剂氢键交互作用调控及萃取铜性能[J]. 化工进展, 2022, 41(S1): 397-406.
[12]	郭振雪, 于海斌, 张国辉, 张景成, 卢雁飞, 何艳贞, 孙彦民, 韩恩山. Si改性对NiMo/Al₂O₃催化剂加氢脱硫性能的影响[J]. 化工进展, 2022, 41(S1): 210-220.
[13]	王一茹, 宋小三, 水博阳, 王三反. 胺功能化介孔二氧化硅捕集CO₂的研究进展[J]. 化工进展, 2022, 41(S1): 536-544.
[14]	单清雯, 张娟, 王亚娟, 刘文强. 聚合离子液体的合成及其吸附脱硫性能[J]. 化工进展, 2022, 41(8): 4571-4579.
[15]	王光绪, 金晶, 张云鹏, 刘薄鉴治, 梁诗雨, 翟中媛. 硅钙摩尔比对准东煤燃烧过程中矿物演变及灰熔融特性的影响[J]. 化工进展, 2022, 41(8): 4140-4146.