含硅改性磷氮阻燃Lyocell纤维的制备及其性能

doi:10.13475/j.fzxb.20250201001

摘要/Abstract

摘要： 为提高Lyocell纤维的阻燃性能,采用正硅酸乙酯对1,2-二(2-氧-5,5-二甲基-1,3,2-二氧磷环己基-2-亚氨基)乙烷(DDPON)进行改性,制备了含硅改性磷氮阻燃剂(Si-DDPON),通过原液共混工艺将其应用于Lyocell纤维中,制备了含硅改性磷氮阻燃Lyocell纤维。借助红外光谱仪、扫描电镜、热重分析仪、氧指数测试仪及纤维强伸度仪研究了Si-DDPON对Lyocell纤维的微观形貌、热稳定性、阻燃性能及力学性能的影响,并利用热重-红外光谱联用仪及拉曼光谱仪分析了阻燃Lyocell纤维热解气体和残炭形貌,提出了Si-DDPON对Lyocell纤维的阻燃机制。结果表明:添加质量分数为35%的Si-DDPON,Lyocell纤维的最大热降解温度从357.4 ℃降低到316.0 ℃,在800 ℃时残炭量提升2.2倍,LOI值由18.0%提高到28.5%,阻燃效果显著改善;在燃烧过程中Si-DDPON通过降低Lyocell纤维燃烧时可燃气体的释放量,以及释放不可燃气体起到气相阻燃作用,同时通过提高炭渣的石墨化程度和致密度,促进形成致密连续的含硅膨胀炭层起到凝聚相阻燃作用,二者共同作用提升了Lyocell纤维的阻燃性能。

关键词: Lyocell纤维, 磷氮阻燃剂, 阻燃性能, 力学性能, 阻燃机制

Abstract:

Objective Lyocell fiber is a green and environmentally regenerable cellulose fiber, but has high flammability and high flame propagation. With wide application of Lyocell fibers in the fields of textile materials, nonwoven materials and high-performance filler materials, the potential danger of fire is increasing, which is a serious threat to the safety of people's lives and properties. Therefore, it is necessary to prepare flame retardant Lyocell fibers to slow down their thermal decomposition process and reduce their flammability.

Method Silicon-containing modified phosphorus-nitrogen flame retardant Si-DDPON was prepared by modifying 1,2-bis(2-oxo-5,5-dimethyl-1,3,2-dioxyphosphacyclohexy-2-imino)ethane(DDPON)with tetraethylorthosilicate (TEOS), and then Si-DDPON was used to prepare flame retardant Lyocell fibers by physical blending process. The effects of Si-DDPON on the micro morphology, thermal properties, flame retardant properties and mechanical properties of Lyocell fibers were characterized and analyzed by using scanning electron microscope, thermogravimetric analyzer, limiting oxygen index and mechanical properties tests. The pyrolysis gas and the char morphology of the Lyocell fibers were analyzed by the thermogravimetric-infrared spectroscopy and Raman spectroscopy, and the retardant mechanism was explored.

Results After modified by TEOS, the water contact angle of DDPON was increased from (44.5°±0.9°) to (128°±2.7°), and the water solubility was reduced from 0.86 g/(100 gH₂O) to 0.001 9 g/(100 gH₂O) at 98 ℃, showing excellent hydrophobicity and water resistance. Scanning electron microscopy and X-ray photoelectron spectroscopy results showed that a small amount of flame retardant particles were attached to the surface of Lyocell fibers after the addition of Si-DDPON. Scanning electron microscopy and energy dispersive spectrometer results showed that the fiber cross-section was uniformly distributed by Si-DDPON. Thermogravimetric experiments demonstrated that the maximum thermal degradation temperature of Lyocell fiber was reduced from 357.4 ℃ to 316.0 ℃, and the amount of residual carbon was increased from 6.1% to 19.6% at 800 ℃ when Si-DDPON with a mass fraction of 35% was added, indicating that the thermal stability of the Lyocell fibers had been greatly improved. Limiting oxygen index(LOI) results indicated that the LOI value of Lyocell fibers increased from 18.0% to 28.5% when the mass fraction of Si-DDPON was 35%, and the LOI value of the fibers remained at 28% after 20 washing cycles, which showed a good performance of water washing resistance. The results of mechanical property tests showed that the mechanical properties of Lyocell fibers were reduced by the addition of Si-DDPON. However, the dry breaking strengths and wet breaking strengths of 35%Si-DDPON-Lyocell fibers were 2.87 cN/dtex and 2.46 cN/dtex, respectively, which retained 75.5% and 75.7% of the pure Lyocell fibers. The analysis of flame retardant mechanism demonstrated that Si-DDPON can improve the flame retardancy of Lyocell fibers by acting on both gas phase and condensed phase. In the gas phase, Si-DDPON inhibited the generation of flammable gas products and promoted the release of non-flammable gas during the combustion process of Lyocell fibers, whereas in the condensed phase, Si-DDPON promoted the formation of a stable expanded char layer and increased the degree of graphitization of the carbon layer, which improved the flame retardant performance of Lyocell fibers.

Conclusion Compared with pure Lyocell fibers, the thermal stability and flame retardant effects of Si-DDPON-Lyocell fibers were significantly improved. When the total amount of Si-DDPON was 35%, the maximum thermal degradation temperature of Lyocell fibers decreased from 357.4 ℃ to 316.0 ℃, the char residue increased by 2.2 times at 800 ℃, and the LOI value of Lyocell fibers rose from 18.0% to 28.5%. Moreover, the LOI value of Si-DDPON-Lyocell fibers remaind at 28.0% after 20 washing cycles, demonstrating excellent wash durability. During the combustion process of Si-DDPON-Lyocell fibers, Si-DDPON acts as a gas-phase flame retardant by reducing the amount of combustible gases and releasing non-combustible gases. Meanwhile, Si-DDPON promots the formation of dense, continuous silicon-containing expanded carbon layer in the condensed phase, both of which work together to enhance the flame retardancy of Lyocell fibers.

Key words: Lyocell fiber, phosphorus nitrogen flame retardant, flame retardant property, mechanical property, flame retardant mechanism

中图分类号:

TS102.5

高敏, 程春祖, 徐中凯, 赵庆波, 张东, 代欣欣. 含硅改性磷氮阻燃Lyocell纤维的制备及其性能[J]. 纺织学报, 2025, 46(10): 19-29.

GAO Min, CHENG Chunzu, XU Zhongkai, ZHAO Qingbo, ZHANG Dong, DAI Xinxin. Preparation and properties of Lyocell fiber with silicon-containing modified phosphorus-nitrogen flame retardant[J]. Journal of Textile Research, 2025, 46(10): 19-29.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20250201001

http://www.fzxb.org.cn/CN/Y2025/V46/I10/19

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参考文献 22

[1]	ZHAO J Y, JIANG L, ZUO C L, et al. Eco-friendly, efficient and durable flame retardant lyocell fabrics prepared via a feasible grafting of taurine[J]. Industrial Crops and Products, 2024, 218: 118925-118933. doi: 10.1016/j.indcrop.2024.118925
[2]	BAI B C, KIM E A, JEON Y P, et al. Improved flame-retardant properties of lyocell fiber achieved by phosphorus compound[J]. Materials Letters, 2014, 135: 226-228. doi: 10.1016/j.matlet.2014.07.131
[3]	ZHANG Q Y, LIU X H, REN Y L, et al. Phosphorated cellulose as a cellulose-based filler for developing continuous fire resistant lyocell fibers[J]. Journal of Cleaner Production, 2022, 368: 133242-133251. doi: 10.1016/j.jclepro.2022.133242
[4]	XU Z K, GAO M, ZHAO Q B, et al. A new method for preparing permanent flame-retardant Lyocell fibre: preparation of flame-retardant fibres by phosphorylated MTT/Lyocell blended fibres[J]. Cellulose, 2024, 31(7): 4565-4580. doi: 10.1007/s10570-024-05882-0
[5]	QI C M, WANG L S, DU J C, et al. Determination and correlation of solubilities of 1, 2-bis (2-oxo-5, 5-dimethyl-1, 3, 2-dioxyphosphacyclohexyl-2-imino) ethane in selected solvents[J]. Fluid Phase Equilibria, 2013, 360: 343-350. doi: 10.1016/j.fluid.2013.09.058
[6]	HAN F, PEI L J, XUE F F, et al. (Solid + Liquid) Phase equilibria of 1, 2-bis (2-oxo-5, 5-dimethyl-1, 3, 2-dioxyphosphacyclohexyl-2-imino) ethane in nine pure solvents[J]. Journal of Solution Chemistry, 2016, 45: 1146-1157. doi: 10.1007/s10953-016-0491-9
[7]	BOKOV D, JALI A T, Chupradit S, et al. Nanomaterial by sol-gel method: synthesis and application[J]. Advance in Materials Science and Engineering, 2021, 1: 5102014-5102034.
[8]	MA Y M, WANG Y D, MA L, et al. Fabrication of hydrophobic and flame-retardant cotton fabric via sol-gel method[J]. Cellulose, 2023, 30(18): 11829-11843. doi: 10.1007/s10570-023-05586-x
[9]	CHOWDHURY M, AIQBAL M Z, RANA M M, et al. Green synthesis of novel green ceramic-based nanoparticles prepared by sol-gel technique for diverse industrial application[J]. Results in Surfaces and Interfaces, 2024, 14: 100178-100190. doi: 10.1016/j.rsurfi.2023.100178
[10]	NACHIT W, AHSAINE H A, RAMZI Z, et al. Photocatalytic activity of anatase-brookite TiO₂ nanoparticles synthesized by sol-gel method at low temperature[J]. Optical Materials, 2022, 129: 112256-112260. doi: 10.1016/j.optmat.2022.112256
[11]	REHMAN Z U, KHAN L, HWAIN L, et al. Si-N matrix as an effective fire retardant source for cotton fabric, prepared through sol-gel process[J]. Fire, 2024, 7(3): 69-80. doi: 10.3390/fire7030069
[12]	马君志, 葛红, 王冬, 等. 溶胶-凝胶法改性阻燃粘胶纤维的制备及其性能[J]. 纺织学报, 2021, 42(1): 10-15.
	MA Junzhi, GE Hong, WANG Dong, et al. Preparation and properties of sol-gel modified flame retardant viscose fiber[J]. Journal of Textile Research, 2021, 42(1): 10-15. doi: 10.1177/004051757204200103
[13]	LIU Y, PAN Y T, WANG X, et al. Effect of phosphorus-containing inorganic-organic hybrid coating on the flammability of cotton fabrics: synthesis, characterization and flammability[J]. Chemical Engineering Journal, 2016, 294: 167-175. doi: 10.1016/j.cej.2016.02.080
[14]	高敏, 赵庆波, 王书丽, 等. 一种复配磷氮系阻燃剂、阻燃再生纤维素纤维及制备方法: 中国, 118223143A[P]. 2024-06-21.
	GAO Min, ZHAO Qingbo, WANG Shuli, et al. A compound phosphorus nitrogen flame retardant, flame retardant regenerated cellulose fiber, and its preparation method: CN 118223143A[P]. 2024-06-21.
[15]	刘晓威, 武伟红, 武翠翠, 等. 乙烯基聚硅氧烷包覆改性聚磷酸铵及其在环氧树脂中的阻燃应用[J]. 中国塑料, 2014, 28(3): 59-64.
	LIU Xiaowei, WU Weihong, WU Cuicui, et al. Vinyl polysiloxane surface-modified ammonium polyphosphate and its application in epoxy resin as flame retar-dants[J]. China Plastics, 2014, 28(3): 59-64.
[16]	ZHU B F, WANG M H, JIANG J J, et al. Spectroscopic identification and photochemistry of astrochemically relevant phosphorus-bearing mole-cules [O, C, N, P] and [2O, C, N, P][J]. The Astrophysical Journal, 2024, 964: 182-196. doi: 10.3847/1538-4357/ad2846
[17]	GUO Y B, XIAO M Y, REN Y L, et al. Synthesis of an effective halogen-free flame retardant rich in phosphorus and nitrogen for lyocell fabric[J]. Cellulose, 2021, 28(11): 7355-7372. doi: 10.1007/s10570-021-03975-8
[18]	MAKAROV I S, GOLOVA L K, KUZNETSOVA L K, et al. Composite fibers based on cellulose and tetraetoxysilane: preparation, structure and proper-ties[J]. Fibre Chemistry, 2017, 49: 101-107. doi: 10.1007/s10692-017-9851-5
[19]	YU Z R, LI S N, ZANG J, et al. Enhanced mechanical property and flame resistance of graphene oxide nanocomposite paper modified with functionalized silica nanoparticles[J]. Composites Part B: Engineering, 2019, 177: 107347-107357. doi: 10.1016/j.compositesb.2019.107347
[20]	马君志. 二硫代焦磷酸酯基阻燃粘胶纤维的协同改性、机理及其产业化研究[D]. 无锡: 江南大学, 2022: 32-33.
	MA Junzhi. Study on synergistic modification mechanism and industrialization of dithiopyrophosphate-based flame retardant viscose fiber[D]. Wuxi: Jiangnan University, 2022: 32-33.
[21]	许文迪, 陆嘉怡, 蔡博禹, 等. 含DOPO/吲哚的磺胺类化合物的合成及其阻燃环氧树脂[J]. 高分子材料科学与工程, 2024, 40(3): 56-65.
	XU Wendi, LU Jiayi, CAI Boyu, et al. Synthesis of DOPO/indole-containing sulfonamide compounds and their flame retardant epoxy resins[J]. Polymer Materials Science & Engineering, 2024, 40(3): 56-65.
[22]	李娜, 王晓, 李振宝, 等. 基于腺嘌呤核苷酸单体的光接枝生态阻燃棉织物制备及其性能[J]. 纺织学报, 2022, 43(7): 97-103.
	LI Na, WANG Xiao, LI Zhenbao, et al. Preparation and proterties of photografted flame-retardant cotton fabrics with modified adenine nucleotide[J]. Journal of Textile Research, 2022, 43(7): 97-103.

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样品名称	T_5%/ ℃	T_max/ ℃	800 ℃时的残炭量/%
纯Lyocell纤维	289.5	357.4	6.1
25%Si-DDPPON-Lyocell纤维	288.6	341.3	11.4
35%Si-DDPPON-Lyocell纤维	286.2	316.0	19.6
45%Si-DDPPON-Lyocell纤维	284.4	304.2	27.3

样品名称	不同水洗次数下纤维的LOI值/%
样品名称	0次	5次	12次	20次
纯Lyocell纤维	18.0	-	-	-
25%Si-DDPPON-Lyocell纤维	26.6	26.3	26.0	25.7
35%Si-DDPPON-Lyocell纤维	28.5	28.2	28.2	28.0
45%Si-DDPPON-Lyocell纤维	28.9	28.5	28.5	28.2

样品名称	PHRR值/ (kW·m^-2)	THR值/ (MJ·m^-2)	T_PHRR/ s	残炭量/ %
纯Lyocell非织造布	166.7±0.3	1.98±0.01	18±1	0.6±0.1
Si-DDPON-Lyocell非织造布	117.5±0.5	1.51±0.01	20±1	4.8±0.1

样品名称	断裂强度/(cN·dtex^-1)			回潮率/%
样品名称	干态		湿态	回潮率/%
纯Lyocell纤维	3.80±0.12	3.25±0.15		10.80
25%Si-DDPPON-Lyocell纤维	3.24±0.15	2.71±0.17		7.30
35%Si-DDPPON-Lyocell纤维	2.87±0.18	2.46±0.21		7.30
45%Si-DDPPON-Lyocell纤维	2.42±0.23	2.15±0.28		7.08