Preparation and properties of maleic acid modified lignin reinforced nanocellulose composite film
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摘要: 以小麦秸秆为原料，采用金属氯化物催化马来酸分离提取木质素纳米颗粒(LNP)。随着金属氯化物的添加，制备得到粒径小、羧基含量高(4.83 mmol/g)、分散性好、含有不同金属离子的LNP。然后将LNP作为增强剂添加到纳米纤维素(CNF)中，采用真空过滤法制备得到复合薄膜材料。对纯CNF膜和复合膜的表面形貌、光学性能、表面色度值和力学性能进行比较分析，结果表明LNP添加量为3wt%时，复合膜具有超过95%的UVA屏蔽率和超过99%的UVB屏蔽率。同时，LNP的加入显著提高了复合膜的拉伸强度(最高达到188.5 MPa)，采用AFM测得CNF和不同LNP之间的相互作用力(276~ 406 nN)均高于CNF之间的相互作用力(202 nN)，与复合膜的拉伸强度提高相一致。综上所述，本研究在CNF膜中引入含金属离子的LNP，在复合膜中构建了具有金属离子交联和氢键结合相互作用的超强网络，为木质素增强纤维素基薄膜材料的开发提供新思路。Abstract: Lignin nanoparticles (LNP) was isolated from wheat straw using metal chloride-catalyzed maleic acid pretreatment in this study. With the addition of metal chlorides, LNP with small particle size, high carboxyl content (4.83 mmol/g), good dispersion and containing different metal ions were prepared. Subsequently, LNP was added as reinforcing agents to CNF, and the composite films were successfully prepared by vacuum filtration method. The surface morphology, optical property, surface chromaticity value and mechanical property of pure CNF and composite films are compared and analyzed. The results show that the composite films could achieve more than 95% UVA shielding ratio and 99% UVB shielding ratio when LNP content is only 3wt%. Meanwhile, the addition of LNP significantly increase the tensile strength of composite film (up to 188.5 MPa). The interaction forces between CNF and different LNPs (276~ 406 nN) are all higher than those between CNFs (202 nN) as measured using AFM, which is consistent with the improvement in tensile strength of the composite films. In summary, LNP containing metal ions are introduced into CNF films to construct super-strong network with metal ion cross-linking and hydrogen bonding interactions, which provides a new idea for the development of lignin-reinforced cellulose-based film materials.
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图 1 木质素的分子量分布图 (a) 和羧基含量图 (b) 及分别对应LNP、Fe3+-LNP、Cu2+-LNP、Al3+-LNP ((c), (d), (e), (f)) 的FE-SEM图像
Figure 1. Molecular weight distribution (a), carboxyl group content (b), and FE-SEM images of LNP, Fe3+-LNP, Cu2+-LNP, Al3+-LNP ((c), (d), (e), (f))
图 2 CNF (a) 及对应5 LNP-CNF、5 Fe3+-LNP-CNF、5 Cu2+-LNP-CNF、5 Al3+-LNP-CNF ((b), (c), (d), (e))复合膜材料的FE-SEM图像
Figure 2. FE-SEM images of CNF film (a) and different composite film material including 5 LNP-CNF, 5 Fe3+-LNP-CNF, 5 Cu2+-LNP-CNF and 5 Al3+-LNP-CNF ((b), (c), (d), (e))
图 4 CNF膜及复合膜材料的UVA和UVB屏蔽率 (a) 和表面色度值 (b)
Figure 4. UVA and UVB blocking rate (a) and surface chromaticity value (b) of CNF film and composite film material
图 3 CNF膜及复合膜材料的光学照片 (a) 、660 nm波长处的透光率 (b) 和紫外-可见光谱 (c)
Figure 3. Optical photographs (a), transmittance at 660 nm (b) and UV-vis transmission spectra (c) of CNF film and composite film material
图 5 CNF膜及复合膜材料的力学性能： (a) 应力-应变曲线； (b) 拉伸应力； (c) 断裂伸长率； (d) 杨氏模量
Figure 5. Mechanical properties of CNF film and composite film material: (a) Stress-strain curve; (b) Tensile stress; (c) Elongation to break; (d) Young’s modulus
图 6 CNF膜及复合膜材料的拉伸应力及其组成成分间的相互作用力
Figure 6. Tensile stresses of pure CNF and composite film materials and interaction forces between their components
表 1 LNP的平均粒径及平均分子量
Table 1. The average particle size and average molecular weight of LNP
Sample Average particle size (nm) Mn Mw Mw/Mn LNP 457.40± 3.61 2489 6215 2.50 Fe3+-LNP 599.87± 5.03 2075 6079 2.93 Cu2+-LNP 450.10± 2.14 2464 6292 2.55 Al3+-LNP 454.03± 3.42 2510 6451 2.57 Notes: Mn- Number-average molecular weight; Mw- Weight-average molecular weight; Mw/Mn- Polydispersity index. 
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