Research progress on the application of lignin-based functional materials in barrier packaging paper
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摘要: 随着石油资源的逐渐枯竭，生物质基阻隔包装材料作为传统石油基塑料包装的绿色替代品受到越来越多重视。木质素作为自然界中第二丰富的天然高分子聚合物，也是唯一富含重复苯环结构单元的可再生资源，具有生物可降解性、生物相容性和出色的加工性等优势。现阶段，大部分木质素仍作为工业副产物被焚烧处理，其高值化利用程度较低。虽然木质素独特的化学结构和耐水、耐溶剂、抗老化、抗紫外等功能特性，使其在制备生物基阻隔材料方面具有巨大潜力。但木质素的结构、木质素基阻隔材料的多重阻隔性能、构效关系及应用场景仍需深入思考。鉴于此，本文对木质素基功能材料在阻隔包装纸中的应用研究进展进行了系统总结和全面评述。首先，简述了木质素的结构和来源。其次，详细概括了木质素基功能材料在阻隔包装纸上的应用现状，重点介绍了木质素基功能材料在包装纸阻隔水、气体、油脂、紫外线以及阻燃方面的应用进展。最后，探讨了木质素基功能材料在阻隔包装纸应用中面临的主要挑战和未来的发展方向。本文将为木质素基功能材料在制备具有单一或多重阻隔性能包装纸的应用研究领域提供理论参考，对工业化生产木质素基高附加值产品具有实际意义。Abstract: With the gradual depletion of petroleum resources, bio-based barrier packaging materials have garnered growing attention as an eco-friendly alternative to conventional petroleum-based plastic packaging. Lignin, the second most abundant natural polymer and the only renewable resource rich in repetitive benzene ring structural units, possesses biodegradability, biocompatibility and excellent processability. Currently, the majority of lignin is still disposed of through incineration as industrial by-products, resulting in limited utilization and low added value. Due to its unique chemical structure, water resistance, solvent resistance, aging resistance, and UV resistance, lignin exhibits significant potential in the development of bio-based barrier materials. However, further consideration is required regarding the structural characteristics of lignin, its multifaceted barrier properties in material applications, the establishment of structure-property relationships, and exploration of diverse application scenarios. Therefore, the present review provides a systematic and comprehensive review of the application of lignin-based functional materials in barrier packaging paper. Firstly, the structure and origin of lignin are briefly elucidated. A comprehensive overview of the current status of the application of lignin-based functional materials in barrier packaging papers is then provided, with particular emphasis on the advances in the use of lignin-based functional materials for water, gas, oil, ultraviolet radiation and flame retardancy properties in packaging paper. Finally, the primary challenges and future prospects for the development of lignin-based functional materials in barrier packaging paper applications are discussed. This review will provide a theoretical foundation for the utilization of lignin-based functional materials in the production of paper with single or multiple barrier properties, thereby providing practical significance for the industrial-scale manufacturing of value-added products derived from lignin.
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Key words:
- Lignin /
- Barrier packaging materials /
- Functional paper /
- High value utilization /
- Biomass
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图 1 (a) 木质素在植物中的分布，(b) 木质素的三种基本单体，(c) 不同规模制备木质纤维素生物质衍生的木质素
Figure 1. (a) Distribution of lignin in plants, (b) Three basic monomers of lignin, (c) Preparation of lignocellulosic biomass-derived lignin at different scales.
图 2 木质素基功能材料在阻隔包装纸中的应用
Figure 2. Application of lignin-based functional materials in barrier packaging paper
图 3 (a) 木质素的长效紫外线阻隔机制，SQ自由基生成、转化和稳定结构[43]。(b) 紫外-可见透射光谱、说明性数码照片和透射率雾度值[44]。(c) LCNP的制备示意图[45]。(d). LPANPs制备方案、光学雾度和紫外阻隔示意图[46]
Figure 3. (a) Long-lasting UV-blocking mechanism of lignin, SQ radical generation, transformation and stabilization of structures [43]. (b) UV-Vis transmission spectra, illustrative digital photographs and transmittance haze values. [44]. (c) Schematic diagram of LCNP preparation [45]. (d) Schematic of LPANPs preparation scheme, optical haze and UV blocking [46].
图 5 (a) 植物性纤维素-木质素增强复合材料示意图，纤维素-木质素复合吸管的照片[54]。(b) 木质素-纤维素复合材料的制造示意图[55]。(c) 麦草中木质素的提取和含木质素的纤维素涂布纸制备流程示意图[56]
Figure 5. (a) Schematic diagram of plant-based cellulose-lignin reinforced composites, photos of cellulose-lignin composite straws [54]. (b) Schematic diagram of the fabrication of lignin-cellulose composites [55]. (c) Schematic diagram of the process of extraction of lignin from wheatgrass and preparation of lignin-containing cellulose-coated paper [56]
图 6 (a) 改性微纤化纤维素及木质素沉积纸制备过程示意图[6]。(b) 涂布纸张制备示意图及纸张渗水期间信号强度的变化曲线[58]
Figure 6. (a) Schematic diagram of the preparation process of modified microfibrinated cellulose and lignin-deposited paper [6]. (b) Schematic diagram of coated paper preparation, variation curve of signal intensity during paper bleeding [58].
图 7 (a) LCNF涂层纸折叠形成碗状，纸碗五个月后容纳植物油数码照片[60]。(b1) 未改性的对照滤器、(b2) 2.44 g·m−2湿滤器、(b3) 8.34 g·m−2湿滤器和(b4) 8.22 g·m−2干滤器过滤前(i)和过滤后(ii)油水乳液的数码照片和显微镜成像[63]
Figure 7. (a) LCNF coating paper folding form bowl, paper bowl after five months for vegetable oil digital photos [60]. (b) Digital photographs and microscopic imaging of oil-water emulsions before (i) and after (ii) filtration through (b1) unmodified control filter, (b2) 2.44 g·m−2 wet filter, (b3) 8.34 g·m−2 wet filter and (b4) 8.22 g·m−2 dry filter [63].
图 8 (a) GnP/CNT/木质素涂层纸的制造和火焰测试示意图[67]。(b) 热处理(在225℃、20和60 min，在1和75 v/v%的水蒸气气氛中)与UB、OD和FB纸浆片的初始ISO亮度之间的关系曲线图，及对于UB、OD和FB纸浆片材，经过热处理(在225℃，20和60 min，在1和75 v/v%的水蒸气气氛中)与初始光吸收系数k之间的关系曲线图[68]
Figure 8. (a) Schematic of manufacturing and flame testing of GnP/CNT/lignin coated paper [67]. (b) Plot of the relationship between heat treatment (at 225℃, 20 and 60 min, in a water vapor atmosphere of 1 and 75 v/v%) and the initial ISO brightness of UB, OD and FB pulp sheets, and for UB, OD and FB pulp sheets, after heat treatment (at 225℃, 20 and 60 min, P < 0.05). Between 1 and 75 v/v) % of water vapor atmosphere and the relationship between the initial light absorption coefficient k graph [68]
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