氯化胆碱低共熔溶剂在蚕丝绵片脱胶和辅助漂白中的应用

doi:10.13475/j.fzxb.20240602301

纺织学报 ›› 2025, Vol. 46 ›› Issue (04): 103-108.doi: 10.13475/j.fzxb.20240602301

氯化胆碱低共熔溶剂在蚕丝绵片脱胶和辅助漂白中的应用

张蕙¹, 杨海伟¹, 金鲜花², 杨超², 王宗乾¹()

1.安徽工程大学安徽省生态纺织印染创新中心, 安徽芜湖 241000
2.传化智联股份有限公司, 浙江杭州 311215

收稿日期:2024-06-12 修回日期:2024-11-27 出版日期:2025-04-15 发布日期:2025-06-11
通讯作者: 王宗乾(1982—),男,教授,博士。主要研究方向为功能化结构纤维调控与成形技术。E-mail :wzqian@ahpu.edu.cn。
作者简介:张蕙(2000—),女,硕士生。主要研究方向为先进纤维及纺织印染加工技术。
基金资助:
安徽省重点研究与开发计划项目(202423i08050057);安徽省重点研究与开发计划项目(2023t07020001);安徽省自然科学基金项目(2308085ME144);安徽省高校协同创新项目(GXXT-2023-035);安徽省高校协同创新项目(GXXT-2022-027);国家先进印染技术创新中心科研基金项目(2022G-CJJ13)

Application of choline chloride deep eutectic solvent in degumming and auxiliary bleaching of silk sheets

ZHANG Hui¹, YANG Haiwei¹, JIN Xianhua², YANG Chao², WANG Zongqian¹()

1. Anhui Provincial Ecological Textile Printing and Dyeing Innovation Center, Anhui Polytechnic University,Wuhu, Anhui 241000, China
2. Transfar Zhilian Co., Ltd., Hangzhou, Zhejiang 311215, China

Received:2024-06-12 Revised:2024-11-27 Published:2025-04-15 Online:2025-06-11

摘要/Abstract

摘要： 为提高蚕丝绵片的脱胶效率和脱胶质量,将预先制备的4种不同组分氯化胆碱低共熔溶剂用于对蚕丝绵片的脱胶,并与碳酸钠、尿素脱胶蚕丝进行比较。采用超景深显微系统、傅里叶变换红外光谱仪、X射线衍射仪测试了脱胶蚕丝的形貌结构、化学及聚集态结构。结果表明:氯化胆碱/草酸二水合物低共熔溶剂用于蚕丝绵片的脱胶效果最佳,脱胶率为24.5%,该脱胶工艺中蚕丝纤维直径平均膨胀至原来的1.17倍;与非碱体系的尿素脱胶对比,蚕丝的脱胶率提升,脱胶时间缩短;与碳酸钠脱胶对比,蚕丝强力受损降低;红外光谱与X射线衍射曲线表明低共熔溶剂脱胶不影响蚕丝素聚集态结构;同时添加低共熔溶剂还有助于提升双氧水对蚕丝绵片的漂白白度。剖析脱胶机制认为,一方面缘于低共熔溶剂对蚕丝纤维具有优异的膨润作用,促进了丝胶组分的溶解去除,另一方面低共熔溶剂呈现酸性,对蚕丝素组分损伤弱,降低脱胶蚕丝纤维的强力损伤。

关键词: 低共熔溶剂, 蚕丝, 脱胶工艺, 漂白, 脱胶机制, 氯化胆碱

Abstract:

Objective Silk is an extremely important natural protein fiber, and degumming is an essential step in silk processing. The conventional degumming method has problems such as long degumming time and high pollution caused by degumming. It is hence necessary to develop a new degumming process so as to improve the degumming efficiency. In this study, the degumming mechanism of silk was analyzed based on the application of choline chloride/oxalic acid dihydrate deep eutectic solvent in the degumming and auxiliary bleaching of silk sheets.

Method Silk sheets were accurately weighed, and were immerged into choline chloride deep eutectic solvents with different concentrations, followed by magnetical stirring at 90 ℃ for 80 min and washing with deionized water and drying to a constant weight. The performance of the degummed silk was tested by the LB-48B fluorescence whiteness meter and the Datacolor 650 color matching instrument, and the best deep eutectic solvent degumming process was screened. The morphology and aggregate structure of the degummed silk were measured by the VHX-970F ultra-depth-of-field microscope system and the D8 ADVANCE X-ray diffractometer. On the other hand, the mechanical properties of sodium carbonate and deep eutectic solvent degummed silk sheets were compared. In order to improve the whiteness of degummed silk with deep eutectic solvent, a mass concentration of 5 g/L hydrogen peroxide was further used to bleach the degummed silk, and the properties of the bleached silk were analyzed.

Results The experimental results showed that the prepared choline chloride/oxalic acid dihydrate deep eutectic solvent had the best degumming effect on silk sheets, with the degumming condition of the degumming rate 24.5% at 90 ℃, 1∶50 and 80 min. Compared with choline chloride/ethylene glycol deep eutectic solvent and choline chloride/urea deep eutectic solvent, it was neutral and weakly alkaline, which was not conducive to the dissolution and removal of sericin. The apparent viscosity of choline chloride/oxalic acid deep eutectic solvent was larger, and its degumming effect was relatively poor. Compared with the urea and sodium carbonate degumming processes, urea degumming took a long time, while sodium carbonate degumming caused silk fibroin fiber damage failing to achieve the desired degumming effect. The standard deviation of the whiteness value of the degummed silk by the choline chloride/oxalic acid dihydrate deep eutectic solvent was relatively small, indicating that the choline chloride/oxalic acid dihydrate deep eutectic solvent degumming was more uniform, and the breaking strength of sodium carbonate degummed silk was decreased significantly with the increase of tensile force. Based on the swelling and dissolution of deep eutectic solvents, the sericin on the silk surface was removed, and the fiber diameter expanded 1.17 times over the original size. X-ray diffractometer and Fourier transform infrared spectrometer analyses revealed that the intensity of the β-fold structure peak of degummed silk was enhanced, the signal of the diffraction peak of silk I. structure was weakened, and the diffraction peak of silk II structure remained unchanged. Furthermore, the reflectivity and whiteness of the degummed silk after bleaching with hydrogen peroxide were improved.

Conclusion Choline chloride/oxalate dihydrate deep eutectic solvent has strong acidity, which has the best degumming effect for silk sheets, optimizes the degumming conditions, shortens the process flow and improves efficiency compared with urea degumming, and sodium carbonate degumming is easy to cause silk damage. Compared with silk sheets, the peak strength of the β-fold structure of degummed silk was enhanced, the signal of the diffraction peak of silk I. structure was weakened, and the diffraction peak of silk II structure was not changed. Due to the excellent swelling and dissolution effect of eutectic solvent, the swelling of silk fibers is promoted and the removal of sericin components is accelerated. At the same time, the effective interaction between fiber and hydrogen peroxide is enhanced, and the whiteness of degummed silk was further improved.

Key words: deep eutectic solvent, silk, degumming process, bleaching, degumming mechanism, choline chloride

中图分类号:

TS143.3

张蕙, 杨海伟, 金鲜花, 杨超, 王宗乾. 氯化胆碱低共熔溶剂在蚕丝绵片脱胶和辅助漂白中的应用[J]. 纺织学报, 2025, 46(04): 103-108.

ZHANG Hui, YANG Haiwei, JIN Xianhua, YANG Chao, WANG Zongqian. Application of choline chloride deep eutectic solvent in degumming and auxiliary bleaching of silk sheets[J]. Journal of Textile Research, 2025, 46(04): 103-108.

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http://www.fzxb.org.cn/CN/Y2025/V46/I04/103

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参考文献 17

[1]	张勇, 陆浩杰, 梁晓平, 等. 蚕丝基智能纤维及织物:潜力、现状与未来展望[J]. 物理化学学报, 2022, 38(9): 64-79.
	ZHANG Yong, LU Haojie, LIANG Xiaoping, et al. Silk materials for intelligent fibers and textiles: potential, progress and future perspective[J]. Acta Physico-Chimica Sinica, 2022, 38(9): 64-79.
[2]	WANG F, ZHANG Y Q. Effects of alkyl polyglyco-side(APG) on Bombyx mori silk degumming and the mechanical properties of silk fibroin fibre[J]. Materials Science and Engineering: C, 2017, 74: 152-158.
[3]	SCHMIDT T, PUCHALLA N, SCHENDZIELORZ M, et al. Degumming and characterization of Bombyx mori and non-mulberry silks from Saturniidae silkworms[J]. Scientific Reports, 2023. DOI:10.1038/S41598-023-46474-5.
[4]	WANG R, ZHU Y, SHI Z, et al. Degumming of raw silk via steam treatment[J]. Journal of Cleaner Production, 2018, 203: 492-497.
[5]	王宗乾, 杨海伟, 王邓峰. 脱胶对蚕丝纤维的溶解及丝素蛋白性能的影响[J]. 纺织学报, 2018, 39(4): 69-76.
	WANG Zongqian, YANG Haiwei, WANG Dengfeng. Influence of degumming on solution of silk fiber and property of fibroin[J]. Journal of Textile Research, 2018, 39(4): 69-76.
[6]	WANG Y L, LIANG Y Y, HUANG J C, et al. Proteomic analysis of silk fibroin reveals diverse biological function of different degumming processing from different origin[J]. Frontiers in Bioengineering and Biotechnology, 2022. DOI:10.3389/FBIOE.2021.777320.
[7]	王宗乾, 杨海伟, 周剑, 等. 尿素脱胶对丝素蛋白气凝胶力学性能的影响[J]. 纺织学报, 2020, 41(4): 9-14.
	WANG Zongqian, YANG Haiwei, ZHOU Jian, et al. Effect of urea degumming on mechanical properties of silk fibroin aerogels[J]. Journal of Textile Research, 2020, 41(4): 9-14.
[8]	EL-SAYED H, MOWAFI S, EL-FIKY A F, et al. Low temperature water-saving bio-degumming of natural silk using thermophilic protease[J]. Sustainable Chemistry and Pharmacy, 2022. DOI:10.1016/J.SCP.2022.100681.
[9]	CHANDRAN K, KAIT C F, WILFRED C D, et al. A review on deep eutectic solvents: physiochemical properties and its application as an absorbent for sulfur dioxide[J]. Journal of Molecular Liquids, 2021. DOI:10.1016/J.MOLLIQ.2021.117021.
[10]	YING L, ZHAO H, LI C, et al. Surface reconstruction and low-temperature dyeing performances of a poly(lactic acid) filament pretreated with a choline chlo-ride and oxalic acid deep eutectic solvent[J]. Macromolecules, 2022, 55(14): 6238-6246.
[11]	DLUGOSZ O. Natural deep eutectic solvents in the synthesis of inorganic nanoparticles[J]. Materials, 2023. DOI:10.3390/MA16020627.
[12]	王一通, 龚立, 王菲菲, 等. 蚕茧丝素纳米纤维的绿色提取及结构调控研究[J]. 蚕业科学, 2022, 48(4): 332-339.
	WANG Yitong, GONG Li, WANG Feifei, et al. Green extraction and structure regulation of silk fibroin nanofibers from silkworm cocoon[J]. Acta Sericologica Sinica, 2022, 48(4): 332-339.
[13]	HUANG H, TANG Q, LIN G, et al. Anthraquinone-assisted deep eutectic solvent degumming of ramie fibers: evaluation of fiber properties and degumming performance[J]. Industrial Crops Products, 2022. DOI:10.1016/J.INDCROP.2022.115115.
[14]	AHMED B, GWON J, THAPALIYA M, et al. Combined effects of deep eutectic solvent and microwave energy treatments on cellulose fiber extraction from hemp bast[J]. Cellulose, 2023, 30(5): 2895-2911.
[15]	ANIS P, TOPRAK T, YENER E, et al. Investigation of the effects of environmentally friendly degumming methods on silk dyeing performance[J]. Textile Research Journal, 2019, 89(7): 1286-1296.
[16]	LING S, QI Z, KNIGHT D P, et al. Synchrotron FTIR microspectroscopy of single natural silk fibers[J]. Biomacromolecules, 2011, 12(9): 3344-3349. doi: 10.1021/bm2006032 pmid: 21790142
[17]	KHAN M M R, TSUKADA M, GOTOH Y, et al. Physical properties and dyeability of silk fibers degummed with citric acid[J]. Bioresource Technology, 2010, 101(21): 8439-8445. doi: 10.1016/j.biortech.2010.05.100 pmid: 20598526

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样品编号	pH值	脱胶率/%
DES-1	6.75	11.5
DES-2	9.31	9.5
DES-3	1.25	23.0
DES-4	1.46	24.5

氯化胆碱低共熔溶剂在蚕丝绵片脱胶和辅助漂白中的应用

Application of choline chloride deep eutectic solvent in degumming and auxiliary bleaching of silk sheets

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