纳米纤维素的疏水改性及应用研究进展

doi:10.3969/j.issn.1673-5854.2020.04.009

Abstract

Abstract:

As a renewable nanomaterial, nanocellulose displays excellent performances and exhibits wide application potentials. However, nanocellulose has extremely strong hydrophilicity due to its abundant hydroxyl groups. Thus, the above characteristics not only seriously affect the performance of nanocellulose in terms of hydrophobicity, but also limit its applications in the field of composite materials to a certain extent. This article summarized the research advances of hydrophobic modification of nanocellulose in three aspects:physical adsorption, surface chemical modification(silylation, alkanoylation, esterification, etc.), and polymer graft copolymerization. Current wide applications of hydrophobic nanocellulose were also summarized in fields of packaging materials, papermaking, and water purification. At the end of this paper, the future development of hydrophobically modified nanocellulose was prospected, aiming to provide reference for the research and wide application of hydrophobic nanocellulose.

Key words: nanocellulose, hydrophobic modification, packaging materials, papermaking, water purification

CLC Number:

TQ352.79

Lin SUN,Huayu LIU,Kun LIU,Xiaoyi ZHANG,Hongxiang XIE,Rui ZHANG,Haiming LI,Chuanling SI. Research Progress in Nanocellulose Hydrophobic Modification and Applications[J]. Biomass Chemical Engineering, 2020, 54(4): 57-66.

Figures/Tables 7

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Table 1

Summary of nanocellulose hydrophobic modification methods"

改性方法 modification method		改性剂 modifier	疏水效果 hydrophobic result	参考文献 references
物理吸附法 physical adsorption	吸附阳离子表面活性剂 adsorbing cationic surfactant	十六烷基三甲基溴化铵 cetyltrimethylammonium bromide	在CNC表面产生疏水结构域，疏水性增加 generating hydrophobic domains on the surface of CNC, increasing hydrophobicity	[10~14]
	吸附阳离子表面活性剂 adsorbing cationic surfactant	(1H，1H，2H，2H-十七氟癸基)三氯硅烷 (1H, 1H, 2H, 2H-heptadecafluoro decyl) trichlorosilane	接触角超过155° contact angle over 155°	^[34]
	吸附季铵盐 adsorbing quaternary ammonium salt	硬脂基三甲基氯化铵 stearyl trimethyl ammonium chloride	接触角由35.8°增大到54.6° increasing contact angle from 35.8° to 54.6°	[15]
		二烯丙基二甲基氯化铵 diallyldimethylammonium chloride	接触角由35.8°增大到48° increasing contact angle from 35.8° to 48°	[15]
		苄基三甲基氯化铵 benzyltrimethylammonium chloride	接触角由35.8°增大到46° increasing contact angle from 35.8° to 46°	[15]
		季烷基铵 quaternary alkylammonium	接触角由50°增大到100° increasing contact angle from 50° to 100°	[16]
		季铵盐水溶液 quaternary ammonium salt solution	接触角由17°增大到71° increasing contact angle from 17° to 71°	[17]
	吸附二嵌段共聚物分散剂 adsorbing diblock copolymer dispersant	聚甲基丙烯酸-2-羟乙酯 poly 2-hydroxyethyl methacrylate	接触角由48°增大到101° increasing contact angle from 48° to 101°	[19]
化学法 chemical	甲硅烷基化 silylation	三甲基氯硅烷 trimethylchlorosilane	接触角由0°增大到138° increasing contact angle from 0° to 138°	[22]
		甲基三甲氧基硅烷 methyltrimethoxysilane	接触角最高达到160° contact angle up to 160 °	[23]
		三甲基氯硅烷 trimethylchlorosilane	接触角由0°增大到117° increasing contact angle from 0° to 117°	[35]
		甲基三甲氧基硅烷 methyltrimethoxysilane	接触角最高达到157° contact angle up to 157°	[36]
	烷酰化 alkanoylation	丁酰氯 butyryl chloride	表面羟基部分被丁酰基基团取代，在低极性体系丙酮中分散性好，疏水性能提高replacing hydroxyl groups on the surface by butyryl groups, good dispersibility in low-polarity acetone and better hydrophobic properties	[24]
	烷酰化 alkanoylation	10-十一碳烯酰氯 10-undecenoyl chloride	疏水性能提高 hydrophobic properties increased	[25]
	酯化 esterification	乳酸 lactic acid	CNF的羟基与乳酸的羧基之间发生酯化反应，疏水性能提高 occuring esterification reaction between the hydroxyl group of cnf and the carboxyl group of lactic acid, better hydrophobic properties	[27~28]
	酯化 esterification	醋酸 acetic acid	接触角由23°增大到45° increasing contact angle from 23° to 45°	[29]
聚合物接枝法 polymer graft		2-(二甲基氨基)甲基丙烯酸乙酯 2-(dimethylamino) ethyl methacrylate	接触角从70°增大到140° increasing contact angle from 70° to 140°	[31]
		聚己内酯二醇 polycaprolactone diol	改性后的复合材料在水中聚集并漂浮在水面上，在疏水性氯仿中分散性好，疏水性能提高the modified composite material aggregating and floating in water, and good dispersion in hydrophobic chloroform, better hydrophobic properties	[32]
		N, N-二甲基氨基-2-甲基丙烯酸甲酯 N, N-dimethylamino-2-ethyl methacrylate	接触角最高达到130° contact angle up to 130°	[33]
		聚甲基丙烯酸甲酯 polymethylmethacrylate	接触角最高达到96° contact angle up to 96°	[37]
		聚丙烯酸甲酯 polymethyl acrylate	接枝后纳米纤维素的分散程度比接枝前纳米纤维素的好，疏水性能提高 increasing the degree of dispersion of nanocellulose after grafting, better hydrophobic properties	[38]

Table 1

References 49

1	XIE H X , ZOU Z F , DU H S , et al. Preparation of thermally stable and surface-functionalized cellulose nanocrystals via mixed H₂SO₄/oxalic acid hydrolysis[J]. Carbohydrate Polymers, 2019, 223, 115116.
2	DU H S , LIU W , ZHANG M M , et al. Cellulose nanocrystals and cellulose nanofibrils based hydrogels for biomedical applications[J]. Carbohydrate Polymers, 2019, 209, 130- 144.
3	刘慰, 司传领, 杜海顺, 等. 纳米纤维素基水凝胶的制备及其在生物医学领域的应用进展[J]. 林业工程学报, 2019, 4 (5): 11- 19.
4	YANG X H , XIE H X , DU H S , et al. Facile extraction of thermally stable and dispersible cellulose nanocrystals with high yield via a green and recyclable FeCl₃-catalyzed deep eutectic solvent system[J]. ACS Sustainable Chemistry & Engineering, 2019, 7 (7): 7200- 7208.
5	NASCIMENTOD M , NUNESY L , FIGUEIRDOMC B , et al. Nanocellulose nanocomposite hydrogels:Technological and environmental issues[J]. Green Chemistry, 2018, 20 (11): 2428- 2448.
6	LIN W S , HU X Y , YOU X Q , et al. Hydrophobic modification of nanocellulose via a two-step silanation method[J]. Polymers, 2018, 10 (9): 1035.
7	巩筱.纳米纤维素纤丝的改性及其应用研究[D].无锡:江南大学, 2018.
8	KARGARZADEH H , MARIANO M , GOPAKUMARD D , et al. Advances in cellulose nanomaterials[J]. Cellulose, 2018, 25 (4): 2151- 2189.
9	LIM C , MEI C T , XU X W , et al. Cationic surface modification of cellulose nanocrystals:Toward tailoring dispersion and interface in carboxymethyl cellulose films[J]. Carbohydrate Polymer, 2016, 107, 200- 210.
10	SYVERUD K , XHANARI K , CHINGA-CARRASCO G , et al. Films made of cellulose nanofibrils:Surface modification by adsorption of a cationic surfactant and characterization by computer-assisted electron microscopy[J]. Journal of Nanoparticle Research, 2011, 13 (2): 773- 782.
11	WEI X Q , YONG W , YOU Y W , et al. The modified nanocrystalline cellulose for hydrophobic drug delivery[J]. Applied Surface Science, 2016, 366, 404- 409.
12	李缓, 陈奎, 王园, 等. 丁二酸酐接枝纳米纤维素负载木犀草素及其苷(英文)[J]. 化学研究, 2017, 28 (4): 493- 500.
13	RAGESH P , RAJIV T , GIL G , et al. Modulating the zeta potential of cellulose nanocrystals using salts and surfactants[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2016, 509, 11- 18.
14	PAN Y F , XIAO H N , CAI P X , et al. Cellulose fibers modified with nano-sized antimicrobial polymer latex for pathogen deactivation[J]. Carbohydrate Polymers, 2016, 135, 94- 100.
15	YIN Y Y , HONG Z Z , TIAN X Z , et al. Cellulose nanocrystals modified with quaternary ammonium salts and its reinforcement of polystyrene[J]. Polymer Bulletin, 2018, 75 (5): 2151- 2166.
16	SHIMIZU M , SAITO T , FUKUZUMI H , et al. Hydrophobic, ductile, and transparent nanocellulose films with quaternary alkylammonium carboxylates on nanofibril surfaces[J]. Biomacromolecules, 2014, 15 (11): 4320- 4325.
17	SALAJKOVÁ M , BERGLUND L A , ZHOU Q . Hydrophobic cellulose nanocrystals modified with quaternary ammonium salts[J]. Journal of Materials Chemistry, 2012, 22 (37): 19798- 19805.
18	TAHANI K , ANDREA T , LARS A B . Molecular engineering of the cellulose poly(caprolactone) bio-nanocomposite interface by reactive amphiphilic copolymer nanoparticles[J]. ACS Nano, 2019, 13, 6409- 6420.
19	SAKAKIBARA K , YANO H , TSUJII Y . Surface engineering of cellulose nanofiber by adsorption of diblock copolymer dispersant for green nanocomposite materials[J]. ACS Applied Materials & Interfaces, 2016, 8 (37): 24893- 24900.
20	IFTIKHAR K , MARIA A , RUBA B , et al. Paclitaxel-loaded micro or nano transfersome formulation into novel tablets for pulmonary drug delivery via nebulization[J]. International Journal of Pharmaceutics, 2020, 575, 118919.
21	杨伟胜, 焦亮, 愈智怀, 等. 纳米纤维素膜疏水化改性研究进展[J]. 纤维素科学与技术, 2017, 25 (3): 60- 68.
22	周丽洁, 周欢, 李佳佳, 等. 纳米纤维素基吸油气凝胶的制备及性能[J]. 林业工程学报, 2019, 4 (1): 67- 73.
23	朱兆栋, 郑学梅, 付时雨, 等. 纤维素微纳颗粒的硅烷化改性对制备超疏水材料的影响[J]. 中国造纸, 2018, 37 (12): 14- 20.
24	周静, 沈葵忠, 房桂干, 等. 漂白竹浆疏水改性纳米纤丝化纤维素的制备和表征[J]. 林业工程学报, 2017, 2 (2): 101- 106.
25	LI W , WANG S F , WANG W , et al. Facile preparation of reactive hydrophobic cellulose nanofibril film for reducing water vapor permeability(WVP)in packaging applications[J]. Cellulose, 2019, 26 (5): 3271- 3284.
26	何孝清. 纳米纤维素的制备及其在造纸领域的应用[J]. 中国造纸, 2019, 38 (10): 68- 74.
27	JATIN S , MUHAMMAD F , SUNANDA S , et al. Water resistant nanopapers prepared by lactic acid modified cellulose nanofibers[J]. Cellulose, 2018, 25 (1): 259- 268.
28	SPINELLA S, RE G L, LIU B, et al.Modification of cellulose nanocrystals with lactic acid for direct melt blending with PLA[C/OL]//AIP Conference Proceedings, 2015.http://dx.doi.org/10.1063/1.4918454.
29	刘星, 王文俊, 邵自强, 等. 纳米纤维素/聚乳酸全绿色纳米复合材料的制备及性能[J]. 高等学校化学学报, 2018, 39 (2): 373- 381.
30	SYVERUD K , XHANARI K , CHINGA-CARRASCO G , et al. Films made of cellulose nanofibrils:Surface modification by adsorption of a cationic surfactant and characterization by computer-assisted electron microscopy[J]. Journal of Nanoparticle Research, 2011, 13 (2): 773- 782.
31	LI M , LIU X H , LIU N , et al. Effect of surface wettability on the antibacterial activity of nanocellulose-based material with quaternary ammonium groups[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2018, 554, 122- 128.
32	ZHOU L , HE H , LI M C , et al. Grafting polycaprolactone diol onto cellulose nanocrystals via click chemistry:Enhancing thermal stability and hydrophobic property[J]. Carbohydrate Polymers, 2018, 189, 331- 341.
33	LI Y Z , ZHU L Q , GRISHKEWICH N , et al. CO₂-responsive cellulose nanofibers aerogels for switchable oil-water separation[J]. ACS Applied Materials & Interfaces, 2019, 11, 9367- 9373.
34	HU D , ZHANG Z , LIU M , et al. Multifunctional UV-shielding nanocellulose films modified with halloysite nanotubes-zinc oxide nanohybrid[J]. Cellulose, 2019, 27, 401- 413.
35	XU Z , ZHOU H , JIANG X , et al. Facile synthesis of reduced graphene oxide/trimethyl chlorosilane-coated cellulose nanofibres aerogel for oil absorption[J]. IET Nanobiotechnology, 2017, 11 (8): 929- 934.
36	尚倩倩, 胡云, 刘承果, 等. 超疏水纤维素复合气凝胶的制备及其油水分离[J]. 林业工程学报, 2019, 4 (3): 86- 92.
37	FARNOOSH S , TAYEBEH B , MOHAMMAD S E . Facile strategy for improvement properties of whey protein isolate/walnut oil bio-packaging films:Using modified cellulose nanofibers[J]. International Journal of Biological Macromolecules, 2019, 139, 858- 866.
38	胡雪娇.聚丙烯酸甲酯接枝纳米纤维素的改性研究[D].哈尔滨:哈尔滨理工大学, 2015.
39	谭温珍.再生纤维素基复合薄膜的制备及阻隔性研究[D].西安:西安理工大学, 2019.
40	刘雨雨. ZnO-乙基纤维素/明胶复合纳米纤维膜的制备及性质探究[D].杭州:浙江大学, 2019.
41	SONG Z P , XIAO H N , ZHAO Y . Hydrophobic-modified nano-cellulose fiber/PLA biodegradable composites for lowering water vapor transmission rate(WVTR) of paper[J]. Carbohydrate Polymers, 2014, 111, 442- 448.
42	陈启杰, 康美存, 郑学铭, 等. 纳米纤维素在纸基功能材料中的应用进展[J]. 林产化学与工业, 2018, 38 (4): 1- 8.
43	李静.纳米纤维素的疏水改性及其在制浆造纸中的应用[D].济南:齐鲁工业大学, 2014.
44	THOMPSON L , AZADMANJIRI J , NIKZAD M , et al. Cellulose nanocrystals:Production, functionalization and advanced applications[J]. Reviews on Advanced Materials Science, 2019, 58 (1): 1- 16.
45	张碟, 蔡杰, 徐威, 等. 纤维素纳米纤维水凝胶的构筑与吸附性能研究[J]. 林业工程学报, 2019, 4 (2): 92- 98.
46	尚倩倩, 陈健强, 杨晓慧, 等. 超疏水磁性纤维素气凝胶的制备及其吸油性能[J]. 林业工程学报, 2019, 4 (6): 105- 111.
47	王爱婷.聚合环氧大豆油改性纤维素吸油材料的制备与性能研究[D].青岛:青岛科技大学, 2016.
48	JEDDI M K , LAITINEN O , LIIMATAINEN H . Magnetic superabsorbents based on nanocellulose aerobeads for selective removal of oils and organic solvents[J]. Materials & Design, 2019, 183, 108115.
49	HUANG J D , WANG S Q , LYU S Y , et al. Preparation of a robust cellulose nanocrystal superhydrophobic coating for self-cleaning and oil-water separation only by spraying[J]. Industrial Crops and Products, 2018, 122, 438- 447.

[1]	Weijiao SHANG,Lu WANG. Status and Analysis of Nanocellulose Technology Based on Patents [J]. Biomass Chemical Engineering, 2020, 54(4): 49-56.
[2]	Linna LU,Qilin LU. Preparation of Nanocellulose by Cellulase Hydrolysis Under Sonication-assisted [J]. Biomass Chemical Engineering, 2020, 54(1): 55-59.
[3]	Heng ZHANG,Hongkun GAO,Zhe WANG,Xiaolong ZHU,Dongyang LIU. Progress in Preparation and Application of Hydrophobized Modified Nanocellulose [J]. Biomass Chemical Engineering, 2019, 53(1): 61-66.
[4]	YANG Xuan, TANG Lirong, LIN Fengcai, LU Qilin, HUANG Biao. Preparation and Properties of Nanocellulose/Chitosan/Gelatin Composite Films [J]. bce, 2018, 52(1): 17-22.
[5]	LIU Xin-xin, LIU Zhi-ming. Preparation and Characterization of Hydrophobic Cellulose/SiO₂ Composite Aerogel [J]. bce, 2016, 50(2): 39-44.
[6]	ZHANG Kai-tao, SUN Pei-pei, SHANG Shi-bin, LIU He, WANG Dan, LI Jing-jing. Preparation of Nanocellulose and Its Aerogel from Bagasse Pulp [J]. bce, 2015, 49(5): 7-10.
[7]	WU Qiao-mei, CHEN Yan-dan, HUANG Biao, CHEN Xue-rong. Advances in Inorganic-nanocellulose Hybrid Nanomaterials [J]. bce, 2014, 48(1): 28-36.
[8]	REN Jun-li;SUN Run-cang;LIU Chuan-fu. Progress of Application of Hemicellulose and Its Derivatives as Additives in Papermaking [J]. , 2006, 40(1): 35-39.

Research Progress in Nanocellulose Hydrophobic Modification and Applications

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