静电纺丝阻燃纳米纤维的研究进展

鲍艳; 赵海航; 高璐; 张文博

doi:10.13801/j.cnki.fhclxb.20231127.002

静电纺丝阻燃纳米纤维的研究进展

doi: 10.13801/j.cnki.fhclxb.20231127.002

鲍艳^1, ,,
赵海航^{1, 2},
高璐^{1, 2},
张文博¹

1.
陕西科技大学轻工科学与工程学院(柔性电子学院), 西安 710021
2.
陕西科技大学轻化工程国家级实验教学示范中心, 西安 710021

基金项目: 国家自然科学基金(22078188)；咸阳市秦创原科技创新专项(2021 ZDZX-GY-0007)资助项目

详细信息

通讯作者:
鲍艳，博士，教授，博士生导师。研究方向为有机无机纳米复合材料及功能性皮革化学品　E-mail： baoyan@sust.edu.cn

中图分类号: TB383.2；TB332
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- 文章访问数: 330
- HTML全文浏览量: 187
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2023-09-13
- 修回日期: 2023-11-10
- 录用日期: 2023-11-17
- 网络出版日期: 2023-11-28
- 刊出日期: 2024-06-15

Research progress of electrospinning flame retardant nanofiber

BAO Yan^{1
, ,},
ZHAO Haihang^{1, 2},
GAO Lu^{1, 2},
ZHANG Wenbo¹

1.
College of Bioresources Chemistry and Materials Engineering (College of Flexible Electronics), Shaanxi University of Science & Technology, Xi’an 710021, China
2.
National Demonstration Center for Experinenced Light Chemical Engineering Education, Shaanxi University of Science & Technology, Xi’an 710021, China

Funds: National Natural Science Foundation of China (22078188); Xianyang City Qin Chuangyuan Science and Technology Innovation Special Project (2021 ZDZX-GY-0007)

摘要

摘要: 静电纺丝纳米纤维具有可调控的纤维直径和分布、相互连通的孔结构、高孔隙率、高比表面积、可控纤维堆积密度等优点，成为近年来研究的热点。阻燃性是高分子材料的重要特性，阻燃纤维相较普通纤维具有使用安全性高的特点，研发具有阻燃特性的纳米纤维具有重要意义。静电纺丝技术提供了将纳米颗粒结合到聚合物溶液中并获得具有多种功能复合纤维材料的可能性。基于此，本文综述了采用静电纺丝技术制备阻燃纳米纤维的研究进展，特别是对静电纺丝阻燃纳米纤维的结构进行了分类，主要包括共混结构、核-壳结构、并列结构和多孔结构，并总结了不同结构阻燃纳米纤维的优缺点。然后对静电纺丝阻燃纳米纤维在锂离子电池隔膜、空气过滤、火灾报警传感、防护材料等领域的应用进行了归纳，最后对静电纺丝阻燃纳米纤维未来的发展方向进行了展望。
- 静电纺丝 /
- 阻燃 /
- 纳米纤维 /
- 结构 /
- 应用
Abstract: Electrospinning nanofiber exhibits several advantages, such as adjustable fiber diameter and distribution, interconnected pore structure, high porosity, high specific surface area, and controllable fiber packing density, which is a prominent research hot spot in recent years. Flame-retardant is an important characteristic of polymer materials, and flame-retardant fibers have the characteristic of higher safety in use compared to ordinary fibers. The development of nanofibers with flame-retardant properties is of great significance. Electrospinning technology refers to the jet spinning of polymer solutions or melts under strong electric fields, providing technical support for constructing nanofibers with special functions. It not only provides the possibility of combining functional fillers into polymers, but also provides the possibility of uniform dispersion of functional fillers within the polymer, which helps to more conveniently produce nanocomposites with special properties in situ. Based on this, this review introduced the development of flame-retardant nanofibers via electrospinning technology. Specially, the structure of electrospinning flame-retardant nanofibers was discussed, mainly including blend structure, core-shell structure, side-by-side structure, and porous structure. Their advantages and disadvantages were also emphasized. Moreover, the application status of flame-retardant nanofibers in lithium-ion battery separators, air filtration systems, fire alarm sensors, and protective materials were introduced. Finally, the future development directions of electrospinning flame-retardant nanofibers were foreseen.
- electrospinning /
- flame retardant /
- nanofiber /
- structure /
- application

HTML全文

图 1 静电纺丝法制备PAN/DOPO纳米纤维膜的示意图^[20]

Figure 1. Schematic diagram of PAN/DOPO nanofiber membrane prepared by electrospinning^[20]

PAN—Polyvinylidene fluoride; DOPO—9, 10-dihydro-9-oxa-10-phosphaphenanthrene

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图 2 锂离子电池用具有热触发阻燃特性的“智能”静电纺丝隔膜示意图^[29]

Figure 2. Schematic of the "smart" electrospun separator with thermal-triggered flame-retardant properties for lithium-ion batteries^[29]

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图 3 (a)并列式双组分静电纺丝设备示意图; (b)聚乳酸纳米夹层纤维的成型工艺^[34]

Figure 3. (a) Schematic diagram of parallel two-component electrospinning equipment; (b) Forming process of the polylactic acidnano-crystalline sandwich fiber^[34]

PVDF—Poly(vinylidene fluoride); PI—Polyimide; PLLA—Polylactic acid

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图 4 静电纺丝技术制备PAN/HPCTP多孔复合膜示意图^[39]

Figure 4. Schematic diagram of PAN/HPCTP mutipore composite membrane prepared by electrospinning^[39]

HPCTP—Hexaphenoxycyclotriphosphazene

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图 5 (a)氢键交联纤维素/羧基化PI纳米纤维复合隔膜的制备工艺；(b) PP、PI和纤维素/羧基化PI隔膜的阻燃性能^[15]

Figure 5. (a) Preparation process of hydrogen-bonded cellulose/PI-COOH composite separator; (b) Flame retardancy of PP, PI andcellulose/PI-COOH separator ^[15]

BPDA—4, 4′-biphthalic anhydride; ODA—4, 4′-diiminodiphenylether; DMF—N, N-dimethylformamide; PAA—Poly(amic acid); PP—Polypropylene

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图 6 (a) OPBI合成工艺和静电纺丝制备示意图；(b) PP和OPBI隔板的阻燃性测试^[48]

Figure 6. (a) Schematic diagram of OPBI synthesis process and electrospinning preparation; (b) Flame retardancy test ofPP and OPBI separator^[48]

DAB—3, 3′-diaminobenzidine; OBBA—4, 4′-oxybisbenzonic acid; OPBI—Poly(aryl ether benzimidazole)

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图 7 PAN/PVP/SnO₂纳米纤维膜的制备过程示意图(a)及原始PAN (b)和纳米纤维膜(c)的阻燃性能^[57]

Figure 7. Schematic of preparation of PAN/PVP/SnO₂ nanofiber membrane (a) and flame retardancy of original PAN (b) and nanofiber membrane^[57] (c)

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图 8 三轴静电纺丝示意图(a)和纯PAN与PAN/CNTs/APP纤维过滤膜的垂直燃烧测试(b)及火灾报警性能^[61] (c)

Figure 8. Schematic diagram of triaxial electrostatic spinning (a), vertical combustion test of pure PAN (b) and PAN/CNTs/APP fiber filter and fire alarm performance^[61] (c)

CNTs—Carbon nanotubes; APP—Ammonium polyphosphate

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表 1 静电纺丝技术构建阻燃纳米纤维的结构及性能

Table 1. Structure and properties of flame-retardant nanofiber builted by electrospinning technology

Structure	Name of nanomaterial	Self-extinguish- ment	T_max/℃	Char residue/wt%	Advantage	Disadvantage	ref
Blend	PEN-PCDA	-	506	42	Optimize flame retardant performance through synergistic regulation among components	The compatibility between flame retardants and polymers is generally poor	[40]
	PEEK-PI	Yes	414	64			[41]
	PVDF-PVP	-	400	26			[42]
	PAN/PU	Yes	275	-			[43]
Core-shell	PI/PVDF-HFP	Yes	450	42	There is no need to consider the compatibility of the spinning solution, and the introduction of flame retardants is greater	The miscibility of the solution greatly affects the electrospinning process	[28]
	TPP@PVDF-HFP	Yes	420	-			[29]
	Bi@C	-	400	18			[44]
	Gelatin-gum arabic	-	250	10			[45]
	CA/Gel-Eg	-	310	22			[46]
Side-by-side	PI/PVDF-HFP	Yes	460	50	Composite fibers can fully utilize the advantages of both components and achieve synergistic flame retardant effects	Difficulty in practical operation	[33]
Side-by-side	PVDF/PI	-	230	-		Difficulty in practical operation	[32]
Porous	NiO/CB/PLA	Yes	340	8	It can significantly improve the reflection effect of thermal radiation, reduce convective heat transfer, and enhance the flame retardant performance of the material	May cause shrinkage and fracture of nanofibers	[38]
	SiO₂-TiO₂	Yes	-	-			[37]
	HPCTP-PAN	Yes	230	-			[39]

Notes：PEN—Polyarylene ether nitriles; PCDA—10, 12-pentacosadiynoic acid; PEEK—Poly(ether-ether-ketone); PVP—Polyvinylpyrrolidone; PU—Polyurethane; PVDF-HFP—Poly(vinylidene fluoride)-co-hexafluoropropylene; TPP—Triphenyl phosphate; CA—Acetate; Gel—Gelatin; Eg—Eugenol; CB—Carbon black; PLA—Polylactic acid

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表 2 静电纺丝阻燃纳米纤维的应用

Table 2. Application of flame retardant nanofiber builted by electrostatic spinning technology

Application area	Material	LOI	Char residue/ wt%	ref
Separator forlithium-ion battery material	Cellulose/PI-COOH	33.6%	59	[15]
	PI/PVDF-HFP	27.7%	42	[28]
	PI/PVDF-HFP	-	50	[33]
	PI/PS/PAA	-	10	[22]
	PAN/DOPO	-	35	[20]
	PCM-TEP@SiO₂/PP	-	56.2	[70]
Air filter material	OPAN/PVP/SnO₂/SnCl₂	-	22	[57]
Air filter material	BaTiO₃@PU/PSA	-	30	[55]
Phase change material	IL/AlN/CoPA	-	10.5	[68]
Fire alarm material	PAN/APP/A-CNTs	30.9%	68.7	[61]
	CA/CNFs	-	43.1	[60]
	SMPU/MXene	-	70.79	[62]
Flame retardant material	PMIA	-	40	[71]
Notes：PS—Polystyrene; PAA—Poly(amic acid); PCM-Phase change materials; TEP—Triethyl phosphate; OPAN—Oxidized polyacrylonitrile; PU—Polyurethane; PSA—Polysulfonamidefibre; IL—Ionic liquid; CoPA—Copolyamides; A-CNTs—Amino-functionalizedcarbon nanotube; SMPU—Shape memory thermoplastic polyurethane; PMIA—Poly(m-phenylene isophtalamide)

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