乙二醇二缩水甘油醚原位交联纤维素-磷虾蛋白复合纤维的结构与性能

马跃; 郭静; 赵秒; 宫玉梅

doi:10.13801/j.cnki.fhclxb.20190923.002

乙二醇二缩水甘油醚原位交联纤维素-磷虾蛋白复合纤维的结构与性能

doi: 10.13801/j.cnki.fhclxb.20190923.002

马跃¹,
郭静^{1, 2, ,},
赵秒^{1, 2},
宫玉梅^{1, 2}

1.
大连工业大学　纺织与材料工程学院，大连 116034
2.
辽宁省功能纤维及复合材料工程技术中心，大连 116034

基金项目: 国家自然科学基金(51373027；51773024)

详细信息

通讯作者:
郭静，博士，教授，博士生导师，研究方向为高分子材料改性和纤维材料加工成型　E-mail：guojing8161@163.com

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2019-06-10
- 录用日期: 2019-09-10
- 网络出版日期: 2019-09-23
- 刊出日期: 2020-05-15

Structure and properties of cellulose-krill protein composite fibers in situ crosslinked with ethylene glycol diglycidyl ether

MA Yue¹,
GUO Jing^{1, 2
, ,},
ZHAO Miao^{1, 2},
GONG Yumei^{1, 2}

1.
College of Textile and Materials Engineering, Dalian University of Technology, Dalian 116034, China
2.
Liaoning Functional Fiber and Composite Engineering Technology Center, Dalian 116034, China

摘要

摘要: 以纤维素(Cell)和南极磷虾蛋白(AKP)为原料，以乙二醇二缩水甘油醚（EGDE）为潜在交联剂，NaOH和尿素水溶液作溶剂，在低温下溶解Cell和AKP后，加入EGDE制备Cell-AKP-EGDE复合纺丝原液，将纺丝原液挤入H₂SO₄-Na₂SO₄-H₂O构成的凝固浴中，经热拉伸定型获得EGDE原位交联的Cell-AKP复合纤维。利用FTIR研究了交联剂EGDE的含量对Cell-AKP复合体系分子间相互作用的影响，采用SEM、XRD、TG等考察了交联剂EGDE的含量与Cell-AKP复合体系的表面形态、结晶性、热稳定性和力学性能的相关性。结果表明：交联剂EGDE含量的不同对Cell-AKP复合纤维的表观黏度、力学性能、结晶性及表面形态等均有影响，且交联剂EGDE含量为3wt%时，Cell-AKP复合纤维的综合性能较好。
- 纤维素 /
- 南极磷虾蛋白 /
- 交联剂含量 /
- 复合纤维 /
- 原位交联
Abstract: Taking cellulose (Cell) and antarctic krill protein (AKP) as the raw materials, ethylene glycol diglycidyl ether (EGDE) as the latent crosslinker, NaOH and urea aqueous solution as the solvents, Cell-AKP-EGDE composite spinning solution was prepared after dissolving Cell and AKP at low temperature. Then the spinning solution was squeezed into a coagulation bath composed of H₂SO₄-Na₂SO₄-H₂O, and the Cell-AKP composite fibers crosslinked in situ by EGDE were obtained by hot stretching. The effect of the content of EGDE on the intermolecular interaction of Cell-AKP composite system was studied by FTIR. The correlation between cross-linking agent content and the surface morphology, crystallinity, thermal stability and mechanical properties of Cell-AKP composites was investigated by SEM, XRD and TG. The results show that the apparent viscosity, mechanical properties, crystallinity and surface morphology of the Cell-AKP composite fibers are affected by the content of EGDE crosslinking agent, and the comprehensive properties of the Cell-AKP composite fibers are the best when the content of EGDE crosslinking agent is 3wt%.
- cellulose /
- antarctic krill protein /
- cross-linking agent content /
- composite fibers /
- in situ crosslink

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图 1 不同剪切速率下Cell-AKP-EGDE复合溶液的黏度

Figure 1. Viscosity of Cell-AKP-EGDE composite solution with different shear rates

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图 2 Cell-AKP-EGDE复合溶液的黏度随温度变化曲线

Figure 2. Variation curves of viscosity of Cell-AKP-EGDE composite solution with temperature

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图 3 EGDE原位交联Cell-AKP复合纤维的机制

Figure 3. Mechanism of EGDE in situ crosslinking Cell-AKP composite fibers

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图 4 Cell、AKP、EGDE(a)和Cell-AKP-EGDE复合纤维(b)的FTIR图谱

Figure 4. FTIR spectra of Cell, AKP, EGDE (a) and Cell-AKP-EGDE composite fibers (b)

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图 5 Cell和Cell-AKP-EGDE复合纤维氢键的高斯拟合曲线

Figure 5. Gauss fitting curves of hydrogen bond of Cell and Cell-AKP-EGDE composite fibers

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图 6 Cell-AKP-EGDE复合纤维的断裂强度和断裂伸长率

Figure 6. Tensile strength and elongation at break of Cell-AKP-EGDE composite fibers

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图 7 Cell和Cell-AKP-EGDE复合纤维的TG (a)和DTG(b)曲线

Figure 7. TG (a) and DTG (b) curves of Cell and Cell-AKP-EGDE composite fibers

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图 8 原料Cell、再生Cell、AKP及Cell-AKP-EGDE复合纤维的XRD图谱

Figure 8. XRD patterns of raw Cell, regenerative Cell, AKP and Cell-AKP-EGDE composite fibers

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图 9 Cell-AKP-EGDE复合纤维表面的SEM图像

Figure 9. SEM images of surface of Cell-AKP-EGDE composite fibers

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图 10 Cell-AKP-EGDE复合纤维断面的SEM图像

Figure 10. SEM images of cross-section morphologies of Cell-AKP-EGDE composite fibers

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表 1 不同乙二醇二缩水甘油醚(EGDE)含量的纤维素-磷虾蛋白-EGDE (Cell-AKP-EGDE)复合纤维编号

Table 1. Number of cellulose-antarctic krill protein-ethylene glycol diglycidyl ether (Cell-AKP-EGDE) composite fibers with different contents of EGDE

No.	1	2	3	4	5	6
EGDE mass fraction/wt%	0	3	5	7	9	11

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表 2 不同剪切速率下AKP、Cell、AKP-EGDE、Cell-EGDE、Cell-EGDE-AKP、Cell-AKP-EGDE复合溶液的黏度η

Table 2. Viscosity η of AKP, Cell, AKP-EGDE, Cell-EGDE, Cell-EGDE-AKP and Cell-AKP-EGDE composite solutions with different shear rates

Speed/s^–1	Viscosity η/(Pa·S)
Speed/s^–1	AKP	AKP-EGDE	Cell	Cell-EGDE	Cell-EGDE-AKP	Cell-AKP	Cell-AKP-EGDE
2	0.0380	0.0540	4.061	4.567	5.876	4.785	6.214
20	0.0115	0.0164	2.918	3.259	3.663	3.338	3.981
50	0.0810	0.0115	2.434	2.634	2.831	2.682	3.106

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表 3 Cell和Cell-AKP-EGDE复合纤维的氢键拟合结果

Table 3. Hydrogen bond fitting results of Cell and Cell-AKP-EGDE composite fibers

Sample	Hydrogen bond type	Fitting curve	Abbreviations	Wavenumber/cm^–1	Average peak area	Relative strength/%
Cell	Free hydroxyl	Ⅰ	—OH	3 571	6.60	3.76	3.76
	Intramolecular	Ⅱ	OH...OH	3 445	103.48	59.32	60.88
	Hydrogen bond	Ⅳ	Annular polymer	3 118	2.73	1.56	–
	Hydrogen bond	Ⅲ	OH...ether O	3 274	61.70	35.36	35.36
1	Free hydroxyl	Ⅰ	—OH	3 611	2.73	4.05	4.05
	Intramolecular	Ⅲ	OH. . .OH	3 428	40.70	60.45	62.94
	Hydrogen bond	Ⅴ	Annular polymer	3 131	1.68	2.49	–
	Intermolecular	Ⅱ	OH. . .π	3 241	13.69	20.32	33.01
	Hydrogen bond	Ⅳ	OH. . .ether O	3 550	8.12	12.05	–
	–	Ⅵ	OH. . .N	3 075	0.43	0.63	–
2	Free hydroxyl	Ⅰ	—OH	3 650	0.51	0.70	0.70
	Intramolecular	Ⅲ	OH...OH	3 433	49.64	68.21	70.36
	Hydrogen bond	V	Annular polymer	3 124	1.56	2.15	–
	Intermolecular	Ⅱ	OH...π	3 238	10.40	14.30	28.94
	Hydrogen bond	Ⅳ	OH...ether O	3 577	10.36	14.25	–
	–	Ⅵ	OH...N	3 069	0.28	0.39	–
4	Free hydroxyl	I	—OH	3 625	1.72	1.91	1.91
	Intramolecular	Ⅲ	OH...OH	3 435	58.61	65.31	67.57
	Hydrogen bond	Ⅴ	Annular polymer	3 130	2.03	2.26	–
	Intermolecular	Ⅱ	OH...π	3 240	17.56	19.57	30.52
	Hydrogen bond	Ⅳ	OH...ether O	3 565	9.24	10.30	–
	–	Ⅵ	OH...N	3 075	0.58	0.65	–
6	Free hydroxyl	Ⅰ	—OH	3 629	0.81	1.27	1.27
	Intramolecular	Ⅲ	OH...OH	3 437	45.77	71.53	73.27
	Hydrogen bond	Ⅴ	Annular polymer	3 125	1.11	1.74	–
	Intermolecular	Ⅱ	OH...π	3 570	5.83	9.11	25.46
	Hydrogen bond	Ⅳ	OH...ether O	3 235	10.19	15.92	–
	–	Ⅵ	OH...N	3 074	0.28	0.43	–

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表 4 Cell-AKP-EGDE复合纤维的结晶度

Table 4. Crystallinity of Cell-AKP-EGDE composite fibers

EGDE mass fraction/wt%	0	3	5	7	9	11
Crystallinity/%	65.86	61.13	62.58	64.57	60.39	56.43

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参考文献(38)

[1]	SIRVIÖ J. Fabrication of regenerated cellulose nanoparticles by mechanical disintegration of cellulose after dissolution and regeneration from a deep eutectic solvent[J]. Journal of Materials Chemistry A,2019,7(2):755-763. doi: 10.1039/C8TA09959F
[2]	PUSPASARI T, AKHTAR F H, OGIEGLO W, et al. High dehumidification performance of amorphous cellulose composite membranes prepared from trimethylsilyl cellulose[J]. Journal of Materials Chemistry A,2018,6(19):9271-9279. doi: 10.1039/C8TA00350E
[3]	陈港, 胡稳, 朱朋辉, 等. 高透明羧甲基纤维素/纤维素纤维复合薄膜的制备及其力学性能[J]. 复合材料学报, 2018, 35(6):1574-1581. CHEN G, HU W, ZHU P H, et al. Preparation and mechanical properties of highly transparent CMC/cellulose composite films[J]. Acta Materiae Compositae Sinica,2018,35(6):1574-1581(in Chinese).
[4]	BABAEE M, JONOOBI M, HAMZEH Y, et al. Biodegradability and mechanical properties of reinforced starch nanocomposites using cellulose nanofibers[J]. Carbohydrate Polymers,2015,132:1-8. doi: 10.1016/j.carbpol.2015.06.043
[5]	KANNAM S K, OEHME D, DOBLIN M, et al. Hydrogen bonds and twist in cellulose microfibrils[J]. Carbohydrate Polymers,2017,175:433-439. doi: 10.1016/j.carbpol.2017.07.083
[6]	UTO T, YAMAMOTO K, KADOKAWA J I. Cellulose crystal dissolution in imidazolium-based ionic liquids: A theoretical study[J]. Journal of Physical Chemistry B,2017,122(1):258-266.
[7]	PIRAS C C, FERNÁNDEZ-PRIETO S, BORGGRAEVE W M D. Ball milling: A green technology for the preparation and functionalisation of nanocellulose derivatives[J]. Nanoscale Advances,2019,1(3):937-947. doi: 10.1039/C8NA00238J
[8]	LING Z, WANG T, MAKAREM M, et al. Effects of ball milling on the structure of cotton cellulose[J]. Cellulose,2019,26(1):305-328. doi: 10.1007/s10570-018-02230-x
[9]	GHANBARI A, TABARSA T, ASHORI A, et al. Preparation and characterization of thermoplastic starch and cellulose nanofibers as green nanocomposites: Extrusion processing[J]. International Journal of Biological Macromolecules,2018,112:442-447. doi: 10.1016/j.ijbiomac.2018.02.007
[10]	罗康佳, 郭建生, 李静怡, 等. 纤维素的溶解技术与研究现状[J]. 合成纤维, 2018, 47(1):1-5. LUO K J, GUO J S, LI J Y, et al. Dissolution technology and research status of cellulose[J]. Synthetic Fibers,2018,47(1):1-5(in Chinese).
[11]	KRYSZTOF M, OLEJNIK K, KULPINSKI P, et al. Regenerated cellulose from N-methylmorpholine N-oxide solutions as a coating agent for paper materials[J]. Cellulose,2018,25(6):3595-3607. doi: 10.1007/s10570-018-1799-y
[12]	LI W J, ZHANG F Y, WANG W K, et al. Rheological transitions and in-situ IR characterizations of cellulose/LiCl•DMAc solution as a function of temperature[J]. Cellulose,2018,25(9):4955-4968. doi: 10.1007/s10570-018-1923-z
[13]	DISSANAYAKE N, THALANGAMAARACHCHIGE V D, TROXELL S, et al. Substituent effects on cellulose dissolution in imidazolium-based ionic liquids[J]. Cellulose,2018,25(12):6887-6900. doi: 10.1007/s10570-018-2055-1
[14]	CAO J, WEI W, GOU G Y, et al. Cellulose films from the aqueous DMSO/TBAH-system[J]. Cellulose,2018,25(12):1-12.
[15]	王文聪, 杜淑宁, 王鸿博, 等. 低取代羟乙基纤维素在碱溶剂中的溶解行为及其机制[J]. 纺织学报, 2018, 39(10):18-23. WANG W C, DU S N, WANG H B, et al. Dissolution behavior and mechanisms of low substituted hydroxyethyl cellulose in alkali solvents[J]. Journal of Textiles,2018,39(10):18-23(in Chinese).
[16]	WANG S, LYU K J, SUN P, et al. Influence of cation on the cellulose dissolution investigated by MD simulation and experiments[J]. Cellulose,2017,24(11):1-11.
[17]	CHENG G, ZHU P X, LI J L, et al. All-cellulose films with excellent strength and toughness via a facile approach of dissolution-regeneration[J]. Journal of Applied Polymer Science,2019,136(2):46925-46936. doi: 10.1002/app.46925
[18]	CAI J, ZHANG L N, LIU S L, et al. Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures[J]. Macromolecules,2008,41(23):9345-9351. doi: 10.1021/ma801110g
[19]	HUANG J C, ZHONG Y, ZHANG L N, et al. Extremely strong and transparent chitin films: A high-efficiency, energy-saving, and “Green” route using an aqueous KOH/Urea solution[J]. Advanced Functional Materials,2017,27(26):1701100-1701110. doi: 10.1002/adfm.201701100
[20]	CHENG D, WEI P D, ZHANG L N, et al. Surface-initiated atom transfer radical polymerization grafting from nanoporous cellulose gels to create hydrophobic nanocomposites[J]. RSC Advances,2018,8(48):27045-27053. doi: 10.1039/C8RA04163F
[21]	KAMMIOVIRTA K, JÄÄSKELÄINEN A S, KUUTTI L, et al. Keratin-reinforced cellulose filaments from ionic liquid solutions[J]. RSC Advances,2016,6(91):88797-88806. doi: 10.1039/C6RA20204G
[22]	HE M, CHEN H, ZHANG X J, et al. Construction of novel cellulose/chitosan composite hydrogels and films and their applications[J]. Cellulose,2018,25(3):1-10.
[23]	KIM J R, NETRAVALI A N. Self-healing green composites based on soy protein and microfibrillated cellulose[J]. Composites Science & Technology,2017,143:22-30.
[24]	ZHAO Y T, HE M, JIN H F, et al. Construction of highly biocompatible hydroxyethyl cellulose/soy protein isolate composite sponges for tissue engineering[J]. Chemical Engineering Journal,2018,341:402-413. doi: 10.1016/j.cej.2018.02.046
[25]	全沁果, 段伟文, 曾雪鸽, 等. 南极磷虾粉成分分析及营养学评价[J]. 食品与机械, 2018, 34(9):68-76. QUAN Q G, DUAN W W, ZENG X G, et al. Composition analysis and nutritional evaluation of antarctic krill powder[J]. Food and Machinery,2018,34(9):68-76(in Chinese).
[26]	HUANG J W, CUI C, ZHENG X J, et al. Study on defluorination technology of antarctic krill protein hydrolysate[J]. China Condiment,2018,43(1):1-8.
[27]	GUO F, WANG Z H, SHI W Z, et al. Distribution characteristics and speciation of fluorine in different parts of antarctic krill[J]. Food Science,2018,39(8):237-242.
[28]	BAX M L, AUBRY L, FERREIRA C, et al. Cooking temperature is a key determinant of in vitro meat protein digestion rate: investigation of underlying mechanisms[J]. Journal of Agricultural & Food Chemistry,2012,60(10):2569-76.
[29]	ZHANG R, GUO J, LIU Y, et al. Effects of sodium salt types on the intermolecular interaction of sodium alginate/antarctic krill protein composite fibers[J]. Carbohydrate Polymers,2018,189:72-78. doi: 10.1016/j.carbpol.2018.02.013
[30]	SONG J X, GUO J, ZHANG S, et al. Properties of cellulose/antarctic krill protein composite fibers prepared in different coagulation baths[J]. International Journal of Biological Macromolecules,2018,114:334-340. doi: 10.1016/j.ijbiomac.2018.03.118
[31]	杨利军, 郭静, 李圣林, 等. 高强度南极磷虾蛋白/海藻复合纤维的制备与表征[J]. 复合材料学报, 2016, 33(7):1524-1530. YANG L J, GUO J, LI S L, et al. Preparation and characterization of high strength antarctic krill protein/algae composite fibers[J]. Journal of Composite Materials,2016,33(7):1524-1530(in Chinese).
[32]	WU J, GUO J, YANG L J, et al. Molecular interaction and characterization of sodium alginate/antarctic krill protein/polyvinyl alcohol composite fiber[J]. Journal of Textile Research,2017,38(2):7-13.
[33]	XU S, LI R Q, ZHANG J F, et al. Ethylene glycol diglycidyl ether cross-linked with sodium alginate-carboxymethyl cellulose to immobilize lipase[J]. China Biotechnology,2017,37(12):77-83.
[34]	郭静, 李学才, 于春芳, 等. 南极磷虾蛋白的提取及其复合纤维的性能[J]. 大连工业大学学报, 2014, 33(4):270-273. GUO J, LI X C, YU C F, et al. Extraction of antarctic krill protein and properties of its composite fibers[J]. Journal of Dalian University of Technology,2014,33(4):270-273(in Chinese).
[35]	李亮, 刘淑萍, 刘让同, 等. NaOH/尿素溶液中纤维素稳态流变性的浓度依赖性[J]. 纺织科技进展, 2017(9):30-33. doi: 10.3969/j.issn.1673-0356.2017.09.008 LI L, LIU S P, LIU R T, et al. Concentration-dependent steady-state rheological properties of cellulose in NaOH/urea solution[J]. Advances in Textile Science and Technology,2017(9):30-33(in Chinese). doi: 10.3969/j.issn.1673-0356.2017.09.008
[36]	CAI J, ZHANG L N. Unique gelation behavior of cellulose in NaOH/urea aqueous solution[J]. Biomacromolecules,2006,7(1):183-189. doi: 10.1021/bm0505585
[37]	LIU J, WANG H F, ZHANG L, et al. Preparation, structure and performances of cross-linked regenerated cellulose fibers[J]. Wuhan University Journal of Natural Sciences,2019,24(1):1-7. doi: 10.1007/s11859-019-1361-2
[38]	ZHONG Z L, ZHANG X, ZHU M, et al. Effect of different pretreatments on solubility of hemp fibers in ionic liquids[J]. Journal of Donghua University (English Edition),2018,35(1):52-57.