Progress in preparation and application of hydrophobic-oleophobic cellulose-based functional materials
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摘要: 基于中国“限塑令”到“禁塑令”的逐步实施，利用可再生可降解生物质基材料代替塑料成为研究热点。纤维素是自然界中最丰富的可再生生物质资源，利用绿色可降解纤维素基材料代替塑料是解决塑料污染的有效途径。本文介绍了纤维素基疏水疏油膜材料、纤维素基疏水疏油纸基材料和纤维素基疏水疏油凝胶材料的制备方法，分析比较了三种纤维素基双疏材料制备方法的特点，阐述了纤维素基双疏材料在水油分离、耐磨纺织材料、阻燃材料等领域的应用，阐明了疏水疏油机制，并对纤维素基双疏材料的发展方向进行了展望。Abstract: Based on the gradual implementation of China's "plastic restriction order" to "plastic ban order", the use of renewable and degradable biomass-based materials instead of plastics has become a research hotspot. Cellulose is the most abundant renewable biomass resources in nature. Replacing plastic with green degradable cellulose-based materials is an effective approach to solve plastic pollution. The preparation methods of cellulose-based hydrophobic-oleophobic film materials, cellulose-based hydrophobic-oleophobic paper materials and cellulose-based hydrophobic-oleophobic gel materials are introduced in this paper. The characteristics of different preparation methods of these three cellulose-based hydrophobic-oleophobic materials are analyzed and compared, and the application of cellulosic hydrophobic-oleophobic materials in the fields of water-oil separation, wear-resistant textile materials and flame-retardant materials are expounded. The hydrophobic-oleophobic mechanism are explained. The development direction of cellulose-based hydrophobic-oleophobic materials is also prospected.
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图 1 纤维素基双疏材料应用框架图
Figure 1. Application frame diagram of cellulosic hydrophobic and oleophobic materials
图 3 双疏复合纸基材料
纤维素基双疏纸：(a)氟碳表面活性剂(ST-110)-氟化烷基硅烷(FAS)-聚四氟乙烯(PTFE)纤维纸[27]；(b)PDMS-CNF双层涂布纸[25]；(c)植酸铵-聚甲基氢硅氧烷双疏纤维素纸[28]；(d)PTFE-ZrO2改性纤维素纸[11]
Figure 3. Hydrophobic and oleophobic composite paper based material
Cellulose-based Hydrophobic-oleophobic paper : (a) Fluorocarbon surfactant (ST-110) -fluoroalkyl silane (FAS) -polytetrafluoroethylene (PTFE) fiber paper[27]; (b) PDMS-CNF double-coated paper[25]; (c) ammonium phytate-polymethylhydrosiloxane hydrophobic oleophobic paper[28]; (d) PTFE-ZrO2 modified cellulose paper[11]
图 4 双疏复合凝胶材料
纤维素基双疏凝胶：(a)多孔和海绵状双疏硅型凝胶[32]；(b)BC/BaSO4双疏气凝胶[33]；(c)改性PIF纤维素凝胶[29]；(d)氧化NFC-聚乙烯亚胺(PEI)和乙二醇二缩水甘油醚(EGDE)气凝胶[34]
Figure 4. Hydrophobic and oleophobic composite gel material
Cellulose-based Hydrophobic-oleophobic gels : (a) porous and spongy Hydrophobic oleophobic silicones[32]; (b) BC/BaSO4 Hydrophobic oleophobic gel[33]; (c) Modified PIF cellulose gel[29]; (d) Oxidized NFC-polyethylene imide (PEI) and ethylene glycol Hydrophobic oleophobic ether (EGDE) aerogel[34]
图 9 液滴在固体表面的三相接触示意图
Figure 9. Schematic diagram of three-phase contact of droplets on a solid surface
图 10 粗糙表面的(a)Wenzel模型和(b)Cassie模型
Figure 10. (a) Wenzel model and (b) Cassie model for rough surfaces
图 11 纤维素基双疏材料的结合力及表面构筑图：(a)CTAB与NCC静电作用图[54]；(b)HDTMS与MCC之间的化学缩合反应[55]；(c)F-PEG分子与HMDI之间化学反应[56]；(d)水分子间氢键作用；(e)Stöber二氧化硅颗粒与CO微纳米粗糙结构构筑图[59]
Figure 11. Binding force and surface structure of cellulose-based hydrophobic-oleophobic materials : (a) Electrostatic interaction between CTAB and NCC[54]; (b) Chemical condensation reaction between HDTMS and MCC[55]; (c) Chemical reaction between F-PEG molecule and HMDI[56]; (d) hydrogen bonding between water molecules; (e) Stöber silica particles and CO micro-nano rough structure construction diagram[59]
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