Preparation and UV Resistance of Biphenyl Liquid Crystal Modified Cellulose Film
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摘要: 以1,6-二溴己烷、氰基联苯酚和N-甲基咪唑为主要原料,合成含有咪唑基团的联苯类液晶(CbP)。以离子液体1-烯丙基-3-甲基咪唑氯盐(AMIM•Cl)为溶剂,将木浆纤维素(WPC)与CbP共混得到铸膜液,再通过浸渍沉淀相转化技术将铸膜液制成纤维素液晶膜(WPC/CbP)。采用哈克流变仪对溶液性能进行表征,用傅里叶红外光谱(FT-IR)、X-射线光电子能谱(XPS)、差示扫描量热(DSC)等对膜结构和性能进行表征。结果表明,CbP的引入改变了纤维素分子内及分子间的氢键作用,提高了纤维素膜的热稳定性。当CbP在铸膜液中的质量分数为3%时,溶液黏度最低。与纯纤维素膜相比,此WPC/CbP膜的拉伸强度提高了27.56%,紫外光透光率降低了35%左右。Abstract: 4-(ω-(methylimidazole) hexyloxy)-4 ′-(cyano)-biphenyl (CbP) was synthesized using 1,6-dibromohexane, cyanobiphenol and N-methyl imidazole as main materials. The wood pulp cellulose solution was prepared by adding CbP to ionic liquid 1-allyl-3-methylimidazolium chloride(AMIM•Cl) as a cellulose solvent, and then its rheological property was tested by Haake rheometer. Wood pulp cellulose liquid crystal films (WPC/CbP) were prepared from the solution by dipping precipitation phase transformation. Fourier infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of the film and differential scanning calorimetry (DSC) was used to characterize the thermal stability of the film. The strength of the film was tested by electronic universal tensile testing machine, and the UV resistance of the film was tested by UV-visible near-infrared spectrometer. Results showed that the viscosity of WPC/CbP increased with the increase of the mass fraction of CbP, and the lowest value appeared when the mass fraction of CbP was 3%, in which a liquid crystal phenomenon was observed by polarizing microscope (POM). Compared with WPC film, the thermal stability and tensile strength of the WPC/CbP were improved because of the intramolecular and intermolecular hydrogen bonds of cellulose and CbP. The tensile strength and flexibility of the WPC/CbP were improved by 27.56% and 46.52%, respectively. However, the UV transmittance of the WPC/CbP was reduced by about 35%, indicating its potential application in the field of high strength packaging.
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Key words:
- cellulose /
- liquid crystal /
- ionic liquid /
- hydrogen bonding /
- phase inversion /
- packaging film
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表 1 CbP、WPC膜和WPC/CbP-3%膜的元素含量分布
Table 1. Element content distribution of CbP、WPC film and WPC/CbP-3% film
Sample wC /% wO /% wN /% wBr /% wSi /% CbP 81.66 6.42 8.98 2.94 — WPC film 62.91 32.18 0.79 — 3.48 WPC/CbP-3% film 70.11 25.66 2.01 — 2.22 -
[1] HEINZE T. Cellulose: Structure and properties. [J]. Adv Polym Sci,2015,271:1-52. [2] SHOGREN R, WOOD D, ORTS W, GLENN G. Plant-based materials and transitioning to a circular economy [J]. Sustainable Production and Consumption,2019,19:194-215. doi: 10.1016/j.spc.2019.04.007 [3] ZHANG J, QI Y, SHEN Y, LI H. Research progress on chemical modification and application of cellulose: A review [J]. Materials Science,2022,28(1):60-67. doi: 10.5755/j02.ms.25485 [4] HUMMEL M, MICHUD A, TANTTU M, ASAADI S, MA Y, HAURU L K J, PARVIAINEN A, KING A W T, KILPEL INEN I, SIXTA H. Ionic liquids for the production of man-made cellulosic fibers: Opportunities and challenges [J]. Adv Polym Sci,2015,271:133-168. [5] REIMER M, ZOLLFRANK C. Cellulose for light manipulation: Methods, applications, and prospects [J]. Advanced Energy Materials,2021,11(43):2003866. doi: 10.1002/aenm.202003866 [6] YADAV M, CHIU F C. Cellulose nanocrystals reinforced κ-carrageenan based UV resistant transparent bionanocomposite films for sustainable packaging applications [J]. Carbohydrate Polymers,2019,211:181-194. doi: 10.1016/j.carbpol.2019.01.114 [7] BALAKRISHNAN P, GOPI S, MS S, THOMAS S. UV resistant transparent bionanocomposite films based on potato starch/cellulose for sustainable packaging [J]. Starch-Stärke,2018,70(1-2):1700139. [8] CAZ N P, V ZQUEZ M. Improving bacterial cellulose films by ex-situ and in-situ modifications: A review [J]. Food Hydrocolloids,2021,113:106514. doi: 10.1016/j.foodhyd.2020.106514 [9] MCNAMARA J T, MORGAN J L W, ZIMMER J. A molecular description of cellulose biosynthesis [J]. Annual Review of Biochemistry,2015,84(1):895-921. doi: 10.1146/annurev-biochem-060614-033930 [10] NAGARAJAN S, SKILLEN N C, IRVINE J T S, LAWTON L A, ROBERTSON P K J. Cellulose Ⅱ as bioethanol feedstock and its advantages over native cellulose [J]. Renewable and Sustainable Energy Reviews,2017,77:182-192. doi: 10.1016/j.rser.2017.03.118 [11] ANDRADE A, HENRI´QUEZ-GALLEGOS S, ALBORNOZ-PALMA G, PEREIRA M. Effect of the chemical and structural characteristics of pulps of Eucalyptus and Pinus on the deconstruction of the cell wall during the production of cellulose nanofibrils [J]. Cellulose,2021,28(9):5387-5399. doi: 10.1007/s10570-021-03848-0 [12] 李淑芳, 石珍旭, 甘霖, 黄进. 纤维素纳米晶材料构建策略的进展 [J]. 功能高分子学报,2022,35(3):221-235.LI S F, SHI Z X, GAN L, HUANG J. Progress and prospects on construction strategies of cellulose nanocrystals-based materials [J]. Journal of Functional Polymers,2022,35(3):221-235. [13] PANG J, WU M, ZHANG Q, TAN X, XU F, ZHANG X, SUN R. Comparison of physical properties of regenerated cellulose films fabricated with different cellulose feedstocks in ionic liquid [J]. Carbohydrate Polymers,2015,121:71-78. doi: 10.1016/j.carbpol.2014.11.067 [14] CAZN P, VELAZQUEZ G, V ZQUEZ M. Characterization of mechanical and barrier properties of bacterial cellulose, glycerol and polyvinyl alcohol (PVOH) composite films with eco-friendly UV-protective properties [J]. Food Hydrocolloids,2020,99:105323. doi: 10.1016/j.foodhyd.2019.105323 [15] KOSAN B, SCHWIKAL K, MEISTER F. Solution states of cellulose in selected direct dissolution agents [J]. Cellulose,2010,17:495-506. doi: 10.1007/s10570-010-9402-1 [16] SONG J, LIU F, CHENG B, HAN Y, ZHENG Y. Phase transition and rheological behaviors of a novel cellulose solution with 4-(ω-(methylimidazole)alkyloxy)-4′-(cyano)-biphenyls as a mesogenic unit [J]. Cellulose,2017,25(2):941-951. [17] ABRAL H, IKHSAN M, RAHMADIAWAN D, HANDAYANI D, SANDRAWATI N, SUGIARTI E, MUSLIMIN A N. Anti-UV, antibacterial, strong, and high thermal resistant polyvinyl alcohol/uncaria gambir extract biocomposite film [J]. Journal of Materials Research and Technology,2022,17:2193-2202. doi: 10.1016/j.jmrt.2022.01.120 [18] NORGREN M, EDLUND H. Lignin: Recent advances and emerging applications [J]. Current Opinion in Colloid & Interface Science,2014,19(5):409-416. [19] YIN J, LUO K, CHEN X, KHUTORYANSKIY V V. Miscibility studies of the blends of chitosan with some cellulose ethers [J]. Carbohydrate Polymers,2006,63(2):238-244. doi: 10.1016/j.carbpol.2005.08.041 [20] 宋俊, 李俊男, 侯源富, 程博闻, 郝蕾, 郭雪雪. 纤维素山梨酸酯膜的制备及其抗菌性能研究 [J]. 高分子学报,2019,50(1):62-70. doi: 10.11777/j.issn1000-3304.2018.18168SONG J, LI J N, HOU Y F, CHENG B W, HAO L, GUO X X. Preparation and properties of antibacterial cellulose sorbate films [J]. Acta Plyomerica Sinica,2019,50(1):62-70. doi: 10.11777/j.issn1000-3304.2018.18168 [21] 万玉玲, 胡雨璐, 许杜鑫, 黄剑波, 许 凤, 吴玉英, 张学铭. 纤维素/木质素微球抗紫外薄膜制备与性能研究. [J]. 材料工程,2021,97(7):56-63.WAN Y L, HU Y L, XU D X, HUANG J B, XU F, WU Y Y, ZHANG X M. Fabrication and characterization of cellulose/ lignin microspheres films with UV-blocking [J]. Journal of Materials Engineering,2021,97(7):56-63. -