改性聚乙烯醇膜的研究进展

doi:10.16085/j.issn.1000-6613.2020-1487

摘要/Abstract

摘要：

聚乙烯醇（PVA）因其良好的化学稳定性、耐酸碱、耐有机溶剂性以及优异的成膜性和生物安全性，成为应用最广泛的亲水性膜材料之一。但亲水性PVA膜力学性能弱和耐水性能差等缺点严重限制其实际应用。近些年，人们通过共混、纳米复合、热处理、化学交联以及协同改性等方法对PVA膜进行了大量的改性研究工作并取得了众多成果。本文总结了不同PVA膜改性方法的特点及存在的问题，重点阐述了性能优异的填料在纳米复合改进PVA膜力学性能上的研究现状，简述了共混、热处理、化学交联对改性PVA膜的作用，强调了协同改性对提高PVA膜综合性能的重要意义，为设计和制备高性能的PVA膜提供一定的参考。指出改性后的PVA膜在水处理和食品包装领域具有良好的应用前景。

关键词: 聚乙烯醇膜, 改性, 纳米复合, 力学强度, 耐水性

Abstract:

Polyvinyl alcohol (PVA) has become one of the most widely used hydrophilic membrane materials because of its good chemical stability, acid resistance, alkali resistance and organic solvent resistance, as well as excellent film-forming property and biological safety. However, the weak mechanical properties and poor water resistance of hydrophilic PVA membrane seriously limit its practical applications. In recent years, a lot of studies have been carried out to promote the properties of PVA membrane by blending, nanocomposite, heat treatment, chemical crosslinking and synergistic modifications, which have achieved great success. In this paper, the characteristics and existing problems of different PVA membrane modification methods were summarized, and the research status of excellent fillers in improving the mechanical properties of PVA membrane by nano-composite was emphasized. Also, the effects of blending, heat treatment and chemical crosslinking for the modification of PVA membrane were briefly introduced, and the significance of synergistic modification to improve the comprehensive properties of PVA membrane was stressed. This paper would provide a novel perspective for the design and preparation of high-performance PVA membrane. The modified PVA membrane had a good application prospect in the fields of water treatment and food packaging.

Key words: polyvinyl alcohol (PVA) membrane, modification, nanocomposite, mechanical strength, water resistance

中图分类号:

O632.31

刘超, 董岸杰, 张建华. 改性聚乙烯醇膜的研究进展[J]. 化工进展, 2021, 40(6): 3258-3269.

LIU Chao, DONG Anjie, ZHANG Jianhua. Research progress of modified polyvinyl alcohol membrane[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3258-3269.

图/表 6

图1 LA对PVA膜力学性能的增强机理[16]

图2 PVA和PVA/LNM复合膜水汽阻隔性能的机理[17]

图3 PVA/GO复合膜力学性能的增强机理[23]

图4 BSA对SiO2的表面改性以及PVA/SiO2@BSA纳米复合膜的制备[31]

图5 静电纺丝制备PVA/GO/ZnO纳米纤维膜示意图[52]

图6 BCNW增强与二元羧酸交联PVA的协同效应[53]

参考文献 53

1	YANG E L, QIN X H, WANG S Y. Electrospun crosslinked polyvinyl alcohol membrane[J]. Mater. Lett., 2008, 62(20): 3555-3557.
2	GOHIL J M, BHATTACHARYA A, RAY P. Studies on the crosslinking of poly (vinyl alcohol)[J]. J. Polym. Res., 2006, 13(2): 161-169.
3	DONG Y Q, ZHANG L, SHEN J N, et al. Preparation of poly(vinyl alcohol)-sodium alginate hollow-fiber composite membranes and pervaporation dehydration characterization of aqueous alcohol mixtures[J]. Desalination, 2006, 193(1/2/3): 202-210.
4	ABDULLAH Z W, DONG Y, DAVIES I J, et al. PVA, PVA blends, and their nanocomposites for biodegradable packaging application[J]. Polym. Plast. Technol. Eng., 2017, 56(12): 1307-1344.
5	BONILLA J, FORTUNATI E, ATARÉS L, et al. Physical, structural and antimicrobial properties of poly vinyl alcohol-chitosan biodegradable films[J]. Food Hydrocolloids, 2014, 35: 463-470.
6	WANG C R, FAN J, XU R, et al. Quaternary ammonium chitosan/polyvinyl alcohol composites prepared by electrospinning with high antibacterial properties and filtration efficiency[J]. J. Mater. Sci., 2019, 54(19): 12522-12532.
7	YIN M L, WANG Y F, ZHANG Y, et al. Novel quaternarized N-halamine chitosan and polyvinyl alcohol nanofibrous membranes as hemostatic materials with excellent antibacterial properties[J]. Carbohydr. Polym., 2020, 232: 115823.
8	ZHENG F Y, LI R S, HU J D, et al. Chitin and waste shrimp shells liquefaction and liquefied products/polyvinyl alcohol blend membranes[J]. Carbohydr. Polym., 2019, 205: 550-558.
9	WANG Z, YAN F, PEI H C, et al. Antibacterial and environmentally friendly chitosan/polyvinyl alcohol blend membranes for air filtration[J]. Carbohydr. Polym., 2018, 198: 241-248.
10	GRISHKEWICH N, MOHAMMED N, TANG J, et al. Recent advances in the application of cellulose nanocrystals[J]. Current. Opinion. Colloid & Interface Science, 2017, 29: 32-45.
11	JAHAN Z, NIAZI M B K, GREGERSEN ϕ W. Mechanical, thermal and swelling properties of cellulose nanocrystals/PVA nanocomposites membranes[J]. J. Ind. Eng. Chem., 2018, 57: 113-124.
12	CAI J Y, CHEN J, ZHANG Q, et al. Well-aligned cellulose nanofiber-reinforced polyvinyl alcohol composite film: mechanical and optical properties[J]. Carbohydr. Polym., 2016, 140: 238-245.
13	NIAZI M B K, JAHAN Z, BERG S S, et al. Mechanical, thermal and swelling properties of phosphorylated nanocellulose fibrils/PVA nanocomposite membranes[J]. Carbohydr. Polym., 2017, 177: 258-268.
14	BEISL S, FRIEDL A, MILTNER A. Lignin from micro- to nanosize: applications[J]. Int. J. Mol. Sci., 2017, 18(11): UNSP 2367.
15	GILLET S, AGUEDO M, PETITJEAN L, et al. Lignin transformations for high value applications: towards targeted modifications using green chemistry[J]. Green Chem., 2017, 19(18): 4200-4233.
16	ZHANG X, LIU W F, YANG D, et al. Biomimetic supertough and strong biodegradable polymeric materials with improved thermal properties and excellent UV-blocking performance[J]. Adv. Funct. Mater., 2019, 29(4): 1806912.
17	ZHANG X, LIU W F, LIU W Q, et al. High performance PVA/lignin nanocomposite films with excellent water vapor barrier and UV-shielding properties[J]. Int. J. Biol. Macromol., 2020, 142: 551-558.
18	ZHAO F L, YAO D, GUO R W, et al. Composites of polymer hydrogels and nanoparticulate systems for biomedical and pharmaceutical applications[J]. Nanomaterials, 2015, 5(4): 2054-2130.
19	CHUNG C, KIM Y K, SHIN D, et al. Biomedical applications of graphene and graphene oxide[J]. Acc. Chem. Res., 2013, 46(10): 2211-2224.
20	GOENKA S, SANT V, SANT S. Graphene-based nanomaterials for drug delivery and tissue engineering[J]. J. Control. Release, 2014, 173: 75-88.
21	HUANG X, QI X Y, BOEY F, et al. Graphene-based composites[J]. Chem. Soc. Rev., 2012, 41(2): 666-686.
22	WANG J C, WANG X B, XU C H, et al. Preparation of graphene/poly(vinyl alcohol) nanocomposites with enhanced mechanical properties and water resistance[J]. Polym. Int., 2011, 60(5): 816-822.
23	TAO C A, ZHANG H, WANG F, et al. Mechanical properties of graphene oxide/polyvinyl alcohol composite film[J]. Polymers and Polymer Composites, 2017, 25(1): 11-16.
24	LIU Y C, WU K, LUO F B, et al. Significantly enhanced thermal conductivity in polyvinyl alcohol composites enabled by dopamine modified graphene nanoplatelets[J]. Composites Part A: Applied Science and Manufacturing, 2019, 117: 134-143.
25	ZHOU T N, CHEN F, TANG C Y, et al. The preparation of high performance and conductive poly (vinyl alcohol)/graphene nanocomposite via reducing graphite oxide with sodium hydrosulfite[J]. Compos. Sci. Technol., 2011, 71(9): 1266-1270.
26	BHATTACHARYA M. Polymer nanocomposites—A comparison between carbon nanotubes, graphene, and clay as nanofillers[J]. Materials, 2016, 9(4): 262.
27	LUAN X, YOUNSE H, HONG H, et al. Improving mechanical properties of PVA based nano composite using aligned single-wall carbon nanotubes[J]. Mater. Res. Express, 2019, 6(10): 1050a6.
28	SHIRAZI Y, TOFIGHY M A, MOHAMMADI T. Synthesis and characterization of carbon nanotubes/poly vinyl alcohol nanocomposite membranes for dehydration of isopropanol[J]. J. Membrane Sci., 2011, 378(1/2): 551-561.
29	WANG Y L, MA H M, WANG X D, et al. Novel signal amplification strategy for ultrasensitive sandwich-type electrochemical immunosensor employing Pd-Fe₃O₄-GS as the matrix and SiO₂ as the label[J]. Biosens. Bioelectron., 2015, 74: 59-65.
30	ARIF Z, SETHY N K, MISHRA P K, et al. Investigating the influence of sol gel derived PVA/SiO₂ nano composite membrane on pervaporation separation of azeotropic mixture I. Effect of operating condition[J]. J. Porous Mater., 2018, 25(4): 1203-1211.
31	MALLAKPOUR S, NAZARI H Y. The influence of bovine serum albumin-modified silica on the physicochemical properties of poly(vinyl alcohol) nanocomposites synthesized by ultrasonication technique[J]. Ultrason. Sonochem., 2018, 41: 1-10.
32	GUO R L, MA X C, HU C L, et al. Novel PVA-silica nanocomposite membrane for pervaporative dehydration of ethylene glycol aqueous solution[J]. Polymer, 2007, 48(10): 2939-2945.
33	GAIDUKOV S, DANILENKO I, GAIDUKOVA G. Characterization of strong and crystalline polyvinyl alcohol/montmorillonite films prepared by layer-by-layer deposition method[J]. Int. J. Polym. Sci., 2015, 2015: 123469.
34	JOSE T, GEORGE S C, GM M, et al. Effect of bentonite clay on the mechanical, thermal, and pervaporation performance of the poly(vinyl alcohol) nanocomposite membranes[J]. Ind. Eng. Chem. Res., 2014, 53(43): 16820-16831.
35	WANG B, WANG Q, LI L. Morphology and properties of poly(vinyl alcohol)/MMT nanocomposite prepared by solid-state shear milling (S3M)[J]. J. Macromol. Sci., 2014, 53(1): 78-92.
36	OUN A A, SHANKAR S, J-W RHIM. Multifunctional nanocellulose/metal and metal oxide nanoparticle hybrid nanomaterials[J]. Critical Reviews in Food Science and Nutrition, 2020, 60(3): 435-460.
37	EL-SHAMY A G, ATTIA W, EL-KADER K M ABD. The optical and mechanical properties of PVA-Ag nanocomposite films[J]. J. Alloys. Compdounds, 2014, 590: 309-312.
38	DAS R K, DAS M. Study of silver nanoparticle/polyvinyl alcohol nanocomposite[J]. Int. J. Plastics Tech., 2019, 23(1): 101-109.
39	SIROHI S, MITTAL A, NAIN R, et al. Effect of nanoparticle shape on the conductivity of Ag nanoparticle poly(vinyl alcohol) composite films[J]. Polym. Int., 2019, 68(12): 1961-1967.
40	CHEN X, MAO S S. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications[J]. ChemInform, 2007, 107(7): 2891-2959.
41	LEI P, WANG F, ZHANG S M, et al. Conjugation-grafted-TiO₂ nanohybrid for high photocatalytic efficiency under visible light[J]. ACS Appl. Mater. Interfaces, 2014, 6(4): 2370-2376.
42	YAN W W, CHEN Q R, DU M F, et al. Highly transparent poly(vinyl alcohol)(PVA)/TiO₂ nanocomposite films with remarkable photocatalytic performance and recyclability[J]. J. Nanosci. Nanotechno., 2018, 18(8): 5660-5667.
43	AHMAD J, DESHMUKH K, HABIB M, et al. Influence of TiO₂ nanoparticles on the morphological, thermal and solution properties of PVA/TiO₂ nanocomposite membranes[J]. Arabian. J. Sci. Eng., 2014, 39(10): 6805-6814.
44	AMANDA A, KULPRATHIPANJA A, TOENNESEN M, et al. Semicrystalline poly(vinyl alcohol) ultrafiltration membranes for bioseparations[J]. J. Membrane Sci., 2000, 176(1): 87-95.
45	AKSAKAL B, YARGı Ö, ŞAHINTURK U. Uniaxial tensile and structural properties of poly(vinyl alcohol) films: the influence of heating and film thickness[J]. J. Appl. Polym. Sci., 2017, 134(23): 44915.
46	HICKEY A S, PEPPAS N A. Mesh size and diffusive characteristics of semicrystalline poly(vinyl alcohol) membranes prepared by freezing/thawing techniques[J]. J. Membrane Sci., 1995, 107(3): 229-237.
47	FUKUMORI T, NAKAOKI T. High-tensile-strength polyvinyl alcohol films prepared from freeze/thaw cycled gels[J]. J. Appl. Polym. Sci., 2014, 131(15): 40578.
48	SUGANTHI S, MOHANAPRIYA S, RAJ V, et al. Tunable physicochemical and bactericidal activity of multicarboxylic-acids-crosslinked polyvinyl alcohol membrane for food packaging applications[J]. ChemistrySelect, 2018, 3(40): 11167-11176.
49	SONKER A K, WAGNER H D, BAJPAI R, et al. Effects of tungsten disulphide nanotubes and glutaric acid on the thermal and mechanical properties of polyvinyl alcohol[J]. Composites Science and Technology, 2016, 127: 47-53.
50	GOHIL J M, RAY P. Studies on oxalic acid as a crosslinker of polyvinyl alcohol[J]. Polymers and Polymer Composites, 2009, 17(7): 403-410.
51	IŞIKLAN N, ŞANLI O. Separation characteristics of acetic acid-water mixtures by pervaporation using poly(vinyl alcohol) membranes modified with malic acid[J]. Chem. Eng. Process., 2005, 44(9): 1019-1027.
52	ZHANG R, WANG Y H, MA D H, et al. Effects of ultrasonication duration and graphene oxide and nano-zinc oxide contents on the properties of polyvinyl alcohol nanocomposites[J]. Ultrason. Sonochem., 2019, 59: 104731.
53	SONKER A K, TIWARI N, NAGARALE R K, et al. Synergistic effect of cellulose nanowhiskers reinforcement and dicarboxylic acids crosslinking towards polyvinyl alcohol properties[J]. J. Polym. Sci A: Polym. Chem., 2016, 54(16): 2515-2525.

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