Preparation of corn stover-based lignin-cellulose acetate ultraviolet shielding film and its properties
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摘要:
为减少紫外线对人类造成的伤害和对设施的破坏，研究人员已经开发了多种聚合物复合材料结合紫外屏蔽剂的紫外线屏蔽膜。但是大部分聚合物复合材料具有生物降解性差、环境污染严重、回收率较低等缺点。醋酸纤维素具有优异的光学透明性、成膜性、电绝缘性、刚性、高热稳定性和可再生性。有机屏蔽剂具有一定的毒性，在光照下也能够被降解，无机紫外线屏蔽剂可以诱导聚合物光降解。而木质素作为一种天然聚合物具有极强的紫外线吸收性能，可以作为添加剂应用于紫外屏蔽复合材料中。本研究以过氧乙酸复合马来酸预处理(PAM)玉米秸秆得到的纤维素产物为原料，以三氟乙酸作为催化剂和溶剂通过相转化法制备具有紫外屏蔽功能的玉米秸秆基醋酸纤维素膜。随着PAM预处理温度的提高，乙酰化程度和醋酸纤维素产率分别增加到42.19%和93.97%。制得的醋酸纤维素膜(ZCA-80~120)的光学性能表征结果表明：该醋酸纤维素膜紫外线屏蔽性能良好，ZCA-110的中波紫外线(UVB)和长波紫外线(UVA)屏蔽率分别达到96.51%和73.72%。同时，揭示了ZCA-80~120在紫外光区(200~400 nm)的屏蔽率以及在660 nm处透光率(T660)与木质素含量的相关关系：Y1=1.46X+77.04 (R2=0.94)，Y2=-6.49X+115.74 (R2=0.86)。采用紫外分光光度计、接触角测试仪、XRD和FT-IR对未添加壳聚糖(ZCA-110)和添加壳聚糖(CS/ZCA-5)的醋酸纤维素膜进行比较研究，发现添加壳聚糖的膜透光率得到改善、亲水性增强、结晶度降低。本研究制备的木质纤维基醋酸纤维素膜将为生物可降解紫外屏蔽材料的研发提供新思路。 ZCA-80~120的UVA、UVB屏蔽率和T660(a)以及UV(200~400 nm)屏蔽率与木质素含量的关系(b) Abstract: In order to reduce the harm caused by ultraviolet rays to human beings and the damage to facilities, The cellulose product obtained from peracetic acid and maleic acid pretreatment (PAM) corn stover was used as raw material, and the corn stover-based cellulose acetate film with UV shielding function was prepared by phase inversion method using trifluoroacetic acid as catalyst and solvent in this study. With the increase of PAM pretreatment temperature, the degree of acetylation and the yield of cellulose acetate increase to 42.19% and 93.97%, respectively. The optical properties of the prepared cellulose acetate films (ZCA-80~120) show that the corn stover-based cellulose acetate films have good UV shielding performance, UVB and UVA shielding rates of ZCA-110 reach 96.51% and 73.72%, respectively. At the same time, the relationship between the UV (200~400 nm) shielding rate, the transmittance at 660 nm (T660) of ZCA-80~120 and lignin content was revealed, indicating that the lignin content is the key factor determining the UV shielding performance of cellulose acetate film. A comparative study of corn stover-based cellulose acetate films without chitosan (ZCA-110) and with chitosan (CS/ZCA-5) was carried out by UV spectrophotometer, contact angle tester, XRD and FT-IR, it is found that the light transmittance of the film added with chitosan is improved, the hydrophilicity is enhanced, the crystallinity is reduced. The lignocellulose-based cellulose acetate film prepared in this study will provide new ideas for the development of biodegradable UV shielding materials.-
Key words:
- corn stover /
- lignin /
- cellulose acetate film /
- UV shielding /
- light transmittance /
- chitosan
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图 1 不同过氧乙酸复合马来酸预处理(PAM)预处理温度下的玉米秸秆组成成分(a)和FT-IR光谱图(b)
Figure 1. Composition (a) and FT-IR spectrum (b) of corn stover at different peracetic acid and maleic acid pretreatment (PAM) pretreatment temperature
图 2 乙酰化程度、醋酸纤维素产率(a)和醋酸纤维素的FT-IR光谱图(b)
Figure 2. The degree of acetylation, the yield of cellulose acetate (a) and the FT-IR spectrum of cellulose acetate (b)
图 3 玉米秸秆基醋酸纤维素膜的紫外-可见光透射率曲线(a)和吸光度曲线(b)
Figure 3. UV-Vis transmittance curve (a) and absorbance curve (b) of corn stover-based cellulose acetate film
图 4 ZCA-80~120的UVA、UVB屏蔽率和T660
Figure 4. UVA, UVB shielding rates and T660 of ZCA-80~120
图 5 ZCA-80~120的UV (200~400 nm)屏蔽率(a)，T660(b)与木质素含量的关系
Figure 5. The relationship between the UV (200~400 nm) shielding rate (a), T660 (b) of ZCA-80~120 and the lignin content
图 6 ZCA-110与CS/ZCA-5~9的UVA、UVB屏蔽率和T660
Figure 6. UVA, UVB shielding rates and T660 of ZCA-110 and CS/ZCA-5~9
图 7 紫外灯照射前后的玉米秸秆基醋酸纤维素紫外屏蔽膜的接触角示意图
Figure 7. Schematic diagram of contact angle of corn stover-based cellulose acetate UV shielding film before and after UV lamp irradiation
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