壳聚糖/聚乙烯醇的流变行为及其可纺性研究

doi:10.3969/j.issn.0253-2417.2023.05.004

摘要/Abstract

摘要：

采用乙酸(HAc)作为溶剂，配制壳聚糖(CS)/聚乙烯醇(PVA)纺丝液，探究纺丝液稳态流变和动态流变性能并考察其静电纺丝的可行性。研究结果表明：随着CS质量分数的增加，纺丝液的稠度系数、结构黏度指数、表观黏度、储能模量(G')、损耗模量(G″)和复合黏度(η^*)均相应增加，非牛顿指数相应减小，不利于CS/PVA纺丝液静电纺丝。随着测试温度的增加，纺丝液的稠度系数、结构黏度指数、表观黏度、G'、G″和η^*均相应减小，非牛顿指数相应增加，纺丝液流动性能加强，可纺性提升。当CS质量分数为3.0%时，纺丝液在测试温度30 ℃下的稠度系数和结构黏度指数均较小，分别为7.978 1和2.16，且非牛顿指数为0.887 7接近于1，表明该纺丝液具有良好的流动性和加工性。结合SEM和流变行为分析，在室温条件下CS质量分数为3.0%的CS/PVA纺丝液呈现优异的可纺性，可以构建连续、均匀且不带珠状连结的纳米纤维。

关键词: 壳聚糖, 稳态流变性能, 动态流变性能, 静电纺丝, 纳米纤维

Abstract:

The chitosan(CS)/polyvinyl alcohol(PVA) spinning solution was prepared using acetic acid(HAc) as solvent. The steady-state rheological and dynamic rheological properties were investigated, and the feasibility of electrospinning was examined. The results showed that with the increase of CS mass fraction, the consistency coefficient, structural viscosity index, apparent viscosity, storage modulus(G′), loss modulus(G″) and composite viscosity(η^*) of the spinning solution increased accordingly, while the non-Newtonian index decreased accordingly, which was not conducive to the electrospinning of CS/PVA spinning solution. With the increase of the test temperature, the consistency coefficient, structural viscosity index, apparent viscosity, G′, G″nd η^* of the spinning solution decreased correspondingly, whereas the non-Newtonian index increased, the flow performance of the spinning liquid was strengthened and the spinnability was improved. When the mass fraction of CS was 3.0%, the apparent viscosity, consistency coefficient and structural viscosity index of the spinning solution at the test temperature of 30 ℃ were small, which were 1.650 Pa·s, 7.978 1 and 2.16, respectively, and the non-Newtonian index was 0.887 7 close to 1, indicating that the spinning solution had good fluidity and processability. Combined with SEM and rheological behavior analysis, under room temperature the CS/PVA spinning solution with a CS mass fraction of 3.0% exhibited excellent spinnability and could construct continuous, uniform nanofibers without beaded connections.

Key words: chitosan, steady-state rheological properties, dynamic rheological properties, electrospinning, nanofiber

中图分类号:

TQ35

曾文超, 孙浩东, 张宗威, 李建国, 陈礼辉. 壳聚糖/聚乙烯醇的流变行为及其可纺性研究[J]. 林产化学与工业, 2023, 43(5): 25-31.

Wenchao ZENG, Haodong SUN, Zongwei ZHANG, Jianguo LI, Lihui CHEN. Rheological Behavior of Chitosan/Polyvinyl Alcohol and Its Spinnability[J]. Chemistry and Industry of Forest Products, 2023, 43(5): 25-31.

图/表 6

图1

表1

图2

图3

图4

图5

参考文献 22

1	WANG X, WANG S, LIU W, et al. Facile fabrication of cellulose composite films with excellent UV resistance and antibacterial activity[J/OL]. Carbohydrate Polymers, 2019, 225: 115213[2022-06-10]. https://doi.org/10.1016/j.carbpol.2019.115213.
2	刘维锦, 别亚琴. 湿相分离法壳聚糖膜的结构与性能研究[J]. 应用化工, 2008, (5): 530- 532. doi: 10.3969/j.issn.1671-3206.2008.05.021
	LIU W J , BIE Y Q . Study on structure and performance of chitosan film prepared by wet phase separation[J]. Applied Chemical Industry, 2008, (5): 530- 532. doi: 10.3969/j.issn.1671-3206.2008.05.021
3	张涛, 孙友谊, 刘亚青. 静电纺丝法制备壳聚糖/聚乙烯醇基复合碳纳米纤维及其电化学性能[J]. 材料导报, 2019, 33 (增刊): 516- 520.
	ZHANG T , SUN Y Y , LIU Y Q . Preparation and electrochemical performance of chitosan/polyvinyl alcohol-based composite carbon nanofibers by electrospinning[J]. Materials Reports, 2019, 33 (Suppl.): 516- 520.
4	WANG C H, CHERN J H, LIU C C, et al. Procoagulant and antimicrobial effects of chitosan in wound healing[J/OL]. International Journal of Molecular Sciences, 2021, 22(13): 7067[2022-06-10]. http://doi.org/10.3390/ijms22137067.
5	HUNLEY M T , LONG T E . Electrospinning functional nanoscale fibers: A perspective for the future[J]. Polymer International, 2008, 57 (3): 385- 389. doi: 10.1002/pi.2320
6	SOUSA A M M , SOUZA H K S , UKNALIS J , et al. Electrospinning of agar/PVA aqueous solutions and its relation with rheological properties[J]. Carbohydrate Polymers, 2015, 115, 348- 355. doi: 10.1016/j.carbpol.2014.08.074
7	MIN B M , LEE S W , LIM J N , et al. Chitin and chitosan nanofibers: Electrospinning of chitin and deacetylation of chitin nanofibers[J]. Polymer, 2004, 45 (21): 7137- 7142. doi: 10.1016/j.polymer.2004.08.048
8	徐开蒙, 王智辉, 史正军, 等. 纤维素/壳聚糖电纺纳米纤维溶剂体系研究进展[J]. 林产化学与工业, 2021, 41 (2): 119- 129.
	XU K M , WANG Z H , SHI Z J , et al. Review of solvent system for electrospinning of cellulose/chitosan nanofibers[J]. Chemistry and Industry of Forest Products, 2021, 41 (2): 119- 129.
9	杨梅, 孙润军. 静电纺壳聚糖/聚乙烯醇纳米纤维膜的制备及表征[J]. 化工新型材料, 2019, 47 (4): 120- 124.
	YANG M , SUN R J . Preparation and characterization of chitosan/PVA electrospun nanofiber membrane[J]. New Chemical Materials, 2019, 47 (4): 120- 124.
10	张慧敏, 阮弦, 胡勇有, 等. 静电纺壳聚糖/聚乙烯醇纳米纤维膜对Cu²⁺、Ni²⁺及Cd²⁺的吸附特性[J]. 环境科学学报, 2015, 35 (1): 184- 193.
	ZHANG H M , RUAN X , HU Y Y , et al. Adsorptive characteristics of Cu²⁺, Ni²⁺ and Cd²⁺ on chitosan/poly(vinylalcohol) nanofiber[J]. Acta Scientiae Circumstantiae, 2015, 35 (1): 184- 193.
11	刘永旭, 张大伟. 壳聚糖/聚乙烯醇/壳寡糖抑菌纳米纤维膜的制备和性能研究[J]. 生物质化学工程, 2020, 54 (4): 30- 36.
	LIU Y X , ZHANG D W . Preparation and properties of chitosan/PVA/chitosan oligosaccharide antibacterial nanofibrous membranes[J]. Biomass Chemical Engineering, 2020, 54 (4): 30- 36.
12	DIANA S A, JAVIER G P, ULISES P G, et al. Morphological study of chitosan/poly(vinyl alcohol) nanofibers prepared by electrospinning, collected on reticulated vitreous carbon[J/OL]. International Journal of Molecular Sciences, 2018, 19(6): 1718[2022-06-10]. https://doi.org/10.3390/ijms19061718.
13	GREINER A , WENDORFF J H . Electrospinning: A fascinating method for the preparation of ultrathin fibers[J]. Angewandte Chemie, 2010, 46 (30): 5670- 5703.
14	史铁钧, 吴德峰. 高分子流变学基础[M]. 北京: 化学工业出版社, 2009: 27- 30.
	SHI T J , WU D F . Fundamentals of Polymer Rheology[M]. Beijing: Chemical Industry Press, 2009: 27- 30.
15	SCHRAMM G. 实用流变测量学[M]. 2版. 朱怀江, 译. 北京: 石油工业出版社, 2009: 4-18.
	SCHRAMM G. Practical Rheometry[M]. 2nd ed. Translated by ZHU H J. Beijing: Petroleum Industry Press, 2009: 4-18.
16	林珊, 陈礼辉, 周永辉. 纤维素/壳聚糖/ZnCl₂·4H₂O溶液的制备及其流变性能[J]. 华中师范大学学报(自然科学版), 2012, 46 (6): 700- 704. doi: 10.3969/j.issn.1000-1190.2012.06.014
	LIN S , CHEN L H , ZHOU Y H . Preparation and rheological properties of cellulose/chitosan/ZnCl₂·4H₂O solution[J]. Journal of Huazhong Normal University(Natural Science Edition), 2012, 46 (6): 700- 704. doi: 10.3969/j.issn.1000-1190.2012.06.014
17	徐佩弦. 高聚物流变学及其应用[M]. 北京: 化学工业出版社, 2003: 49- 57.
	XU P X . Polymer Rheology and Application[M]. Beijing: Chemical Industry Press, 2003: 49- 57.
18	臧昆, 臧己. 纺丝流变学基础[M]. 北京: 中国纺织出版社, 1993: 269.
	ZANG K , ZANG J . Fundamentals of Spinning Rheology[M]. Beijing: China Textile & Apparel Press, 1993: 269.
19	余美琼, 袁红梅, 陈礼辉. 纤维素/氯化锂/N, N-二甲基乙酰胺溶液的流变性能[J]. 纺织学报, 2021, 42 (5): 23- 30.
	YU M Q , YUAN H M , CHEN L H . Rheological properties of cellulose/LiCl/N, N-dimethylacetamide solution[J]. Journal of Textile Research, 2021, 42 (5): 23- 30.
20	LI Y , LIU X , ZHUANG X , et al. Rheological behavior and spinnability of ethylamine hydroxyethyl chitosan/cellulose co-solution in N-methylmorpholine-N-oxide system[J]. Fibers and Polymers, 2016, 17 (5): 778- 788. doi: 10.1007/s12221-016-5578-9
21	袁红梅, 汪东, 吴建飞, 等. 壳聚糖对竹溶解浆溶液流变性能的影响[J]. 森林与环境学报, 2020, 40 (2): 211- 217.
	YUAN H M , WANG D , WU J F , et al. Effect of chitosan on rheological properties of bamboo dissolving pulp solution[J]. Journal of Forest and Environment, 2020, 40 (2): 211- 217.
22	张如心, 张顺花, 杨勉. 壳聚糖/聚丙烯共混熔体的剪切流变性能[J]. 现代纺织技术, 2016, 24 (5): 1- 4.
	ZHANG R X , ZHANG S H , YANG M . Shear and rheological properties of CTS/PP blends melt[J]. Advanced Textile Technology, 2016, 24 (5): 1- 4.

CS质量分数/% CS mass fraction	测试温度/℃ test temperature	Ostwald-de-waele公式Ostwald-de-waele formula			结构黏度指数(Δη) structural viscosity index
CS质量分数/% CS mass fraction	测试温度/℃ test temperature	稠度系数(K) consistency coefficient	非牛顿指数(n) non-newtonian exponent	相关系数(R²) correlation coefficient	结构黏度指数(Δη) structural viscosity index
	20	3.023 4	0.931 9	0.993 9	1.24
	30	2.111 1	0.943 7	0.990 1	1.09
2.5	40	1.290 0	0.965 2	0.991 8	0.67
	50	1.221 0	0.970 9	0.994 7	0.58
	60	0.671 3	0.981 0	0.991 3	0.45
	20	12.482 5	0.842 5	0.994 0	2.61
	30	7.978 1	0.887 7	0.995 4	2.16
3.0	40	5.442 5	0.914 3	0.994 1	1.78
	50	3.377 5	0.940 2	0.991 5	1.11
	60	2.387 8	0.962 6	0.990 6	0.95
	20	20.193 0	0.827 6	0.993 2	3.48
	30	14.252 8	0.848 0	0.998 4	2.74
3.5	40	8.509 4	0.877 1	0.995 2	2.15
	50	4.955 6	0.907 6	0.992 9	1.65
	60	3.120 3	0.926 8	0.993 7	1.21
	20	44.126 6	0.769 4	0.991 7	4.63
	30	40.049 8	0.804 8	0.997 9	3.98
4.0	40	25.609 4	0.810 1	0.993 4	3.63
	50	17.226 6	0.835 8	0.997 5	3.10
	60	9.326 1	0.887 3	0.998 4	2.12

[1]	霍薪竹, 曹梦楠, 刘守新, 陈志俊, 李坚, 李淑君. 碳点/纤维素构建多色余辉气凝胶[J]. 林产化学与工业, 2023, 43(5): 1-7.
[2]	罗丹, 苏雯皓, 舒璇, 刘秀宇, 戴红旗, 卞辉洋. 纳米纤维素基紫外屏蔽膜材料的研究进展[J]. 林产化学与工业, 2023, 43(4): 140-150.
[3]	柯珣, 杨塬兴, 赵丽红. 蔗渣全组分紫外光屏蔽膜的制备及性能研究[J]. 林产化学与工业, 2023, 43(3): 1-8.
[4]	叶结旺, 周志丹, 金贞福. 氮掺杂木质素基活性炭的制备、表征及其吸附性能研究[J]. 林产化学与工业, 2023, 43(1): 127-132.
[5]	卞辉洋, 段晟, 武瑾, 黄六莲, 姚双全, 戴红旗. 多元羧酸预处理制备木质纳米纤维素及其性能研究[J]. 林产化学与工业, 2022, 42(6): 11-16.
[6]	李翠环, 陈胜, 毛健贞, 牟佳慧, 邵自强, 许凤. 电纺纳米纤维基柔性压力传感器的制备及性能研究[J]. 林产化学与工业, 2022, 42(5): 1-7.
[7]	王硕, 王永贵, 肖泽芳, 谢延军. 生物基水凝胶制备与应用研究进展[J]. 林产化学与工业, 2022, 42(5): 122-136.
[8]	杨欣欣, 郭伟, 蔡照胜, 黄旭娟, 王婷, 丁正青. 脱氢枞酸缩水甘油酯接枝羟丙基壳聚糖制备及性能研究[J]. 林产化学与工业, 2021, 41(6): 51-56.
[9]	王颖, 马春慧, 周晋, 李梦扬, 岳金权. 纳米纤维素及其用于锂电池的研究进展[J]. 林产化学与工业, 2021, 41(6): 105-116.
[10]	卞辉洋, 扶艳荞, 陈李栋, 杨伟胜, 姚双全, 戴红旗. 疏水亲油木质纳米纤维素气凝胶的制备及表征[J]. 林产化学与工业, 2021, 41(5): 45-50.
[11]	王凌媛, 惠岚峰. 纳米纤维素疏水改性的研究进展[J]. 林产化学与工业, 2021, 41(3): 125-133.
[12]	徐开蒙, 王智辉, 史正军, 吴佳喜, 张钰禄, 杜官本. 纤维素/壳聚糖电纺纳米纤维溶剂体系研究进展[J]. 林产化学与工业, 2021, 41(2): 119-129.
[13]	王丽鑫,徐雅雯,李志森,王鸿彪,张乔会,逄锦慧. 高强度醋酸纤维素/壳聚糖复合膜的制备及其性能研究[J]. 林产化学与工业, 2020, 40(4): 107-113.
[14]	胡雨萌,侯敏杰,许苗军,李斌. 纤维素基一体化三明治结构超级电容器的制备及性能[J]. 林产化学与工业, 2020, 40(3): 23-30.
[15]	宋庭方,麦泳贤,田秀枝,邓海波,蒋学. 长链酰胺化纳米纤维素增强聚乳酸复合材料[J]. 林产化学与工业, 2020, 40(1): 31-36.