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

摘要/Abstract

摘要：

纳米纤维素作为一种性能优越的可再生纳米材料，应用前景极为广阔。然而，由于纳米纤维素结构上富含羟基，使其具有极强的亲水性，严重影响了纳米纤维素的疏水性能，并且在一定程度上限制了其在复合材料领域的应用。综述了纳米纤维素疏水改性的研究进展，从物理吸附、表面化学修饰（甲硅烷化、烷酰化、酯化等）、聚合物接枝共聚3个方面简述了目前应用较为广泛的疏水化改性方法，并对疏水纳米纤维素在包装材料、造纸、水净化等方面的应用现状进行了总结。最后对疏水改性纳米纤维素的未来发展进行了展望，旨在为疏水纳米纤维素的研究和应用提供参考。

关键词: 纳米纤维素, 疏水改性, 包装材料, 造纸, 水净化

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

中图分类号:

TQ352.79

孙琳,刘华玉,刘坤,张筱仪,解洪祥,张蕊,李海明,司传领. 纳米纤维素的疏水改性及应用研究进展[J]. 生物质化学工程, 2020, 54(4): 57-66.

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.

图/表 7

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表1

纳米纤维素疏水改性方法总结"

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]

表1

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