Preparation and research progress of bio-based high resistance oxygen composites
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摘要: 随着环保意识的提升以及国家“以纸代塑”政策的提出，研究者一直致力于研发更环保的材料以代替石油基材料。生物质资源由于来源广泛是有望部分替代石油资源的主要可再生资源之一。本文综述了近几年一些具有高阻氧潜力生物基复合材料(纤维素、淀粉、半纤维素、壳聚糖、胶原)的研究进展。介绍了生物基材料改性的两种常用方法(薄膜基体改性和薄膜表面改性)，简要总结了氧气分子渗透的理论与机制。最后，对目前的一些具有潜力的生物基复合材料在食品、医学、先进功能材料等领域的应用进行简要概述，对存在的问题进行简单总结，最后展望了未来生物质基材料的发展方向与趋势。Abstract: With the promotion of environmental awareness and the proposal of the national "paper instead of plastic" policy, researchers have been working to develop more environmentally friendly materials to replace petroleum-based materials. Biomass resources are one of the main renewable resources that are expected to partially replace petroleum resources because of their extensive sources. In this paper, the recent research progress of bio-based composites (cellulose, starch, hemicelluloses, chitosan, collagen) with high oxygen inhibition potential is reviewed. Two common methods of modification of biobased materials (film substrate modification and film surface modification) are introduced. The theory and mechanism of oxygen molecular infiltration are briefly summarized. Finally, the current applications of some potential bio-based composites in food, medicine, advanced functional materials and other fields are briefly summarized, and the existing problems are briefly summarized. Finally, the development direction and trend of bio-based materials in the future are prospected.
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Key words:
- biomass-based materials /
- oxygen blocking /
- obstruct /
- cellulose /
- starch /
- hemicellulose /
- chitosan
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图 2 (a)TOCNF/NRL复合膜的制备过程及复合膜的阻隔机制[17]；(b)CNF和CNF5纳米复合材料在成型过程中的取向机制示意图[18]；(c)夹层膜的OTR值[15]；(d)CNP层横截面上O2和H2O的移动途径[15]；(e)原纤维素纸和MSP-g-PHMG样品的OTR[21]；
Figure 2. (a)The preparation process of TOCNF/NRL composite film and the barrier mechanism of the composite film[17]; (b)The orientation mechanism diagram of CNF and CNF5 nanocomposites during the molding process[18]; (c)OTR value of sandwich film[15]; (d)The movement path of O2 and H2 O on the cross section of the CNP laye[15]r; (e)OTR of procellulose paper and MSP-g-PHMG samples[21];
图 3 (a) MTPS/PBAT薄膜的透氧性[29]；(b) OMMT/淀粉膜的平面图和OMMT/淀粉膜的横截面[25]；(c) 纳米复合薄膜多尺度结构变化及其对水蒸气和氧气渗透的影响示意图[28]；(d) CNF、淀粉和木质素在生物复合材料中的键合机制示意图[31]
Figure 3. (a) Oxygen permeability of MTPS/PBAT films[29];(b) OMMT/ starch film plan and cross section of OMMT/ starch film[25]; (c) Schematic diagram of multi-scale structural changes of nanocomposite films and their effects on water vapor and oxygen penetration[28]; (d) Schematic diagram of the bonding mechanism of CNF, starch and lignin in biocomposites[31]
图 4 (a)使用浇注法制备HC/CMHC薄膜的工艺图、未改性的HC、CMHC-取代度(DS0.51)[33]；(b)合成薄膜分别的氧气透过率和水蒸气透过率[34]；(c) CS/hBNNS薄膜透氧率[41]；(d) PLA/CS和 PLA/SiOx/CS横截面的SEM图像[43]；(e)CS/CNC/TPP生物复合涂层的制备工艺及其在水果保鲜中的应用[39]
Figure 4. (a) Process diagram of HC/CMHC film prepared by casting method, unmodified HC, CMHC- degree of substitution (DS0.51)[33]; (b) Oxygen and water vapor transmissibility of the synthesized film respectively[34]; (c) Oxygen permeability of CS/hBNNS films[41]; (d) SEM images of PLA/CS and PLA/SiOx/CS cross sections[43]; (e) Preparation process of CS/CNC/TPP biocomposite coating and its application in fruit preservation[39]
图 5 (a)用ECG4-P30-4 PL纳米膜包装的猪肉，在储存过程中其颜色[49]；(b)草莓和灰芽孢杆菌引起的腐烂症状的图像，无包衣草莓(CK)、.用壳聚糖薄膜(CS)包衣、涂有含有 5% 姜黄提取物(CTU5)的壳聚糖薄膜、涂有含有 5% 绿茶提取物(CGT5)的壳聚糖薄膜和涂有含有 5% 姜黄提取物和 5% 绿茶提取物(CTU5 GT5)的壳聚糖薄膜[52]；(c)稻壳纤维与玉米淀粉复合膜示意图[53]；(d)接骨木果提取物的明胶-酪蛋白酸钠高氧阻隔膜对猪肉的抗氧化能力[55]；(e) 高阻隔SFF95-GB5与传统包装塑料(HDPE：高密度聚乙烯、PLA：聚乳酸，PET：聚对苯二甲酸乙二醇酯，PVA：聚乙烯醇)在50%RH下的透氧性[56]
Figure 5. (a) Pork packaged with ECG4-P30-4 PL nanomembrane, its color during storage[49]; (b) Image of strawberry and rot symptoms caused by Bacillus griseus, uncoated strawberry (CK). Coated with a chitosan film (CS), coated with a chitosan film containing 5% turmeric extract (CTU5), coated with a chitosan film containing 5% green tea extract (CGT5) and coated with a chitosan film containing 5% turmeric extract and 5% green tea extract (CTU5 GT5)[52]; (c) Schematic diagram of rice husk fiber and corn starch composite membrane[53]; (d) Antioxidant capacity of elderberry extract's gelatin-sodium caseinate hyperoxic barrier film on pork[55]; (e) Oxygen permeability of high barrier SFF95-GB5 and traditional packaging plastics (HDPE: high-density polyethylene, PLA: polylactic acid, PET: polyethylene terephthalate, PVA: polyvinyl alcohol) at 50%RH[56]
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