Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (07): 121-129.doi: 10.13475/j.fzxb.20230705201

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Preparation of durable and efficient P/N synergical flame retardant and its application on cotton fabrics

LI Xu1,2,3, LIU Xiangji1,2,3, JIN Xin1,2,3, YANG Chenghao1,2,3, DONG Chaohong1,2,3()   

  1. 1. College of Textiles & Clothing, Qingdao University, Qingdao, Shandong 266071, China
    2. Institute of Functional Textiles and Advanced Materials, Qingdao University, Qingdao, Shandong 266071, China
    3. State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao University, Qingdao, Shandong 266071, China
  • Received:2023-07-25 Revised:2024-04-10 Online:2024-07-15 Published:2024-07-15
  • Contact: DONG Chaohong E-mail:dongzhh11@163.com

RichHTML

6

PDF (PC)

28

Abstract:

Objective Cotton fabric is one of the most common natural fabrics, and has excellent moisture absorption, breathability, thermal insulation and softness, which are widely used in clothing, household tems, military and other fields. Unfortunately, the limiting oxygen index of cotton fabric is only 18 %, and it is easily ignited in the air, causing fire accidents. In addition, the flame retardant durability of flame-retardant cotton fabrics is also very important. Hence, it is necessary to prepare efficient and durable flame-retardant cotton fabrics.

Method The ammonium phosphate (AHPA) flame retardant was prepared from phosphorus pentoxide and ethanolamine. The P/N-type flame retardant AHPA was heated to produce acidic substances such as polyphosphoric acid, which promoted the dehydration of the fabrics and formed a dense carbon layer. During this process, P/N-type flame retardant AHPA generated non-flammable gases, which isolated heat and oxygen, diluted combustible gases, and hindered flame spread. Flame retardant cotton fabrics were prepared by common rolling-baking-baking finishing process. The thermal stability and mechanical properties of flame retardant cotton fabrics were analyzed by vertical flammability test, limiting oxygen index test, thermogravimetric test, cone calorimetry test and universal material test.

Results The test results showed that the flame retardant AHPA was successfully synthesized,and the fiber surface had been successfully covered by the flame retardant. When the concentration of flame retardant AHPA was set to 300 g/L, the LOI value of flame retardant cotton fabric had been increased to 52.9 % from 18 %, with only 45 mm damaged carbon length. The heat release rate and total heat release of the treated cotton fabrics were decreased by 86.1 % and 31.5 %, respectively. The flame spread rate (FIGRA) and mean effective heat combustion (Mean-EHC) were decreased from 6 kW/(m2·s) and 23.5 MJ/kg to 0.3 kW/(m2·s) and 15.3 MJ/kg, respectively, representing 95 % and 34.9 % reductions in each perspective. The AHPA flame retardant worked to reduce the heat release and the combustion efficiency with improved safety. In nitrogen and air atmosphere, the carbon residue of flame-retardant cotton fabrics had been greatly increased compared to the pristine cotton fabric, indicating that the thermal stability of the flame-retardant treated cotton fabrics had been greatly improved. The breaking force of the finished cotton fabrics was decreased in both warp and weft directions. After 50 washing cycles, the LOI value of the flame retardant cotton fabrics maintained at about 31.6 %.

Conclusion In summary, the flame retardant AHPA endows cotton fabrics with efficient and durable flame retardant properties, self-extinguishing of fire, discontinuous smoldering phenomenon, and excellent washing durability. The flame retardant AHPA can be applied to cotton fabrics used for bedding, carpets, curtains and so on. In following-up research work, the mechanical strength of the flame retardant cotton fabrics needs be optimized, and the total smoke release should be reduced.

Key words: cotton fabric, flame retardant, flame retardant fabric, functional textile, phosphorus and nitrogen synergy, flame retardant property

CLC Number: 

  • TS195.5

Fig.1

Synthesis of AHPA"

Fig.2

FT-IR spectrum of AHPA"

Fig.3

NMR spectra of AHPA"

Fig.4

Vertical flammability diagram of flame retardant treated cotton fabrics with flame retardant of different mass concentrations"

Tab.1

Flame retardant properties of cotton fabrics at different flame retardant mass concentrations"

阻燃剂质量浓度/
(g·L-1)		 质量
增加率/
%		 续燃
时间/
s		 阴燃
时间/
s		 损毁
长度/
mm		 LOI值/
%
0(未处理棉织物) 0 8 13 300 18.0±0.2
100 12.21 0 0 63 37.5±0.2
200 20.23 0 0 53 47.9±0.2
300 28.24 0 0 45 52.9±0.1
400 33.35 0 0 42 54.3±0.1

Tab.2

Flame retardant properties of cotton fabrics under different impregnation temperatures"

浸渍
温度/℃		 质量增
加率/%		 续燃
时间/s		 阴燃
时间/s		 损毁
长度/mm		 LOI值/%
60 26.56 0 0 51 49.0±0.2
70 28.24 0 0 45 52.9±0.1
80 28.91 0 0 45 53.5±0.1
90 29.74 0 0 43 54.0±0.2

Fig.5

FT-IR spectra of cotton fabrics before and after flame retardant treatment"

Fig.6

SEM images of cotton fabric before (a) and after (b)flame retardant treatment"

Fig.7

EDS image of flame-retardant treated cotton fabric"

Fig.8

CCT carbon residue diagram of cotton fabrics before (a) and after (b) flame retardant treatment"

Tab.3

Cone calorimeter test data"

样品 TTI/
s		 pk-HRR/
(kW·m-2)		 tpk-HRR/
s		 THR/
(MJ·m-2)		 TSP/
m2		 残余质量
分数/%		 FIGRA/
(kW·m-2·s-1)		 平均有效燃烧热/
(MJ·kg-1)
未处理棉织物 20±1 228.0±0.5 38±1 9.84±0.01 0.102±0.001 3.2±0.2 6 23.5±0.9
阻燃处理棉织物 — 31.6±0.7 104±2 6.74±0.02 0.399±0.001 14.5±0.2 0.3 15.3±1.4

Fig.9

Conical calorimetric test data of cotton fabric before and after flame retardant treatment. (a) HRR; (b) THR; (c) Residual weight; (d) TSP; (e) COP; (f) CO2P"

Tab.4

TG data in N2 and air atmospheres"

测试气氛 样品 Tonset/℃ Tmax/℃ Rmax/(%·℃-1) 790 ℃时的残炭量/%
氮气 未处理棉织物 270 365 1.60 0.6
阻燃处理棉织物 214 259 0.55 37.1
空气 未处理棉织物 261 375 0.95 0
阻燃处理棉织物 208 273 0.56 8.0

Fig.10

TG(a)and DTG(b)curves of cotton fabrics in N2 and air atmosphere before and after flame retardant treatment"

Tab.5

Breaking strength of cotton fabrics before and after flame retardant treatment"

阻燃剂质量浓度/
(g·L-1)		 断裂强力/N
经向 纬向
(未处理棉织物) 442.65±5.51 420.78±5.29
100 414.74±1.74 333.92±6.87
200 395.46±2.00 260.34±7.02
300 404.23±4.45 261.97±9.63
400 404.67±4.03 269.28±8.05

Fig.11

Vertical flammability diagram of flame retardant treated cotton fabric with different washing cycles"

Fig.12

Flame retardant properties of flame retardant treated cotton fabrics after different washing cycles"

[1] 孙玉发, 周向东. 棉用新型含磷氮阻燃剂的合成及其应用[J]. 纺织学报, 2019, 40(12): 79-85.
doi: 10.13475/j.fzxb.20180903207
SUN Yufa, ZHOU Xiangdong. Synthesis and application of new phosphorus-nitrogen-containing flame retardants for cotton[J]. Journal of Textile Research, 2019, 40 (12): 79-85.
doi: 10.13475/j.fzxb.20180903207
[2] 钱耀威, 殷连博, 李家炜, 等. 聚乙烯基膦酸/多乙烯多胺层层自组装阻燃棉织物的制备及其性能[J]. 纺织学报, 2023, 44(9): 144-152.
QIAN Yaowei, YIN Lianbo, LI Jiawei, et al. Preparation and properties of flame retardant cotton fabrics by layer-by-layer assembly of polyvinylphosphonic acid and polyethylene poly-amine[J]. Journal of Textile Research, 2023, 44(9): 144-152.
[3] 张姣姣, 李雨洋, 刘云, 等. 棉/粘胶混纺织物的阻燃抗菌整理[J]. 纺织学报, 2021, 42(7): 31-38.
ZHANG Jiaojiao, LI Yuyang, LIU Yun, et al. Flame retardant and antibacterial treatments for cotton-viscose blended fabrics[J]. Journal of Textile Research, 2021, 42(7): 31-38.
[4] SUN L, XIE Y T, WU J M, et al. A novel P/N-based flame retardant synthesized by one-step method toward cotton materials and its flame-retardant mechanism[J]. Cellulose, 2021, 28(5): 3249-3264.
[5] ZHANG J J, CHEN B, LIU J, et al. Multifunctional antimicrobial and flame retardant cotton fabrics modified with a novel N,N-di(ethyl phosphate) biguanide[J]. Cellulose, 2020, 27(12): 7255-7269.
[6] ZHANG S, HORROCKS A R. Substantive intumescence from phosphorylated 1,3-propanediol derivatives substituted on to cellulose[J]. Journal of Applied Polymer Science, 2003, 90(12): 3165-3172.
[7] LIU X H, ZHANG Q Y, CHENG B W, et al. Durable flame retardant cellulosic fibers modified with novel, facile and efficient phytic acid-based finishing agent[J]. Cellulose, 2018, 25: 799-811.
[8] LEE D H, JANG J. Synergistic flame-retardant finishing of cotton using dichlorotriazinyl phosphonate and triethanolamine[J]. Fibers and Polymers, 2020, 21: 343-349.
[9] MAGOVAC E, JORDANOV I, GRUNLAN J C, et al. Environmentally-benign phytic acid-based multilayer coating for flame retardant cotton[J]. Materials, 2020. DOI:10.3390/ma13235492.
[10] SURYAPRABHA T, SETHURAMAN M G. Fabrication of a superhydrophobic and flame-retardant cotton fabric using a DNA-based coating[J]. Journal of Materials Science, 2020, 55: 11959-11969.
[11] 李金凤, 蒋巍. 阻燃剂的复配协效技术及纺织品的阻燃整理[J]. 高分子通报, 2022, 273(1): 46-55.
LI Jinfeng, JIANG Wei. Synergistic technology of flame retardants and flame retardant finishing of textiles[J]. Polymer Bulletin, 2022, 273(1): 46-55.
[12] 黄益婷, 程献伟, 关晋平, 等. 磷/氮阻燃剂对涤纶/棉混纺织物的阻燃整理[J]. 纺织学报, 2022, 43(6): 94-99,106.
HUANG Yiting, CHENG Xianwei, GUAN Jinping, et al. Phosphorus/nitrogen-containing flame retardant for flame retardant finishing of polyester/cotton blended fabric[J]. Journal of Textile Research, 2022, 43(6): 94-99,106.
[13] 李静, 陈华钢. 溶胶-凝胶涂覆棉织物的制备及其阻燃性能[J]. 印染助剂, 2020, 37(10): 18-21.
LI Jing, CHEN Huagang. Preparation and flame retardant properties of sol-gel coated cotton fabrics[J]. Textile Auxiliaries, 2020, 37(10): 18-21.
[14] LV Z, HU Y T, GUAN J P, et al. Preparation of a flame retardant, antibacterial, and colored silk fabric with chitosan and vitamin B2 sodium phosphate by electrostatic layer by layer assembly[J]. Materials Letters, 2019, 24: 136-139.
[15] WAN C Y, LIU M S, LIU S D, et al. An efficient and durable DOPO/H3PO4-based flame retardant for cotton fabric[J]. Cellulose, 2021, 28: 7421-7434.
[16] GOU T T, WU X, ZHAO Q Y, et al. Novel phosphorus/nitrogen-rich oligomer with numerous reactive groups for durable flame-retardant cotton fabric[J]. Cellulose, 2021, 28(11): 7405-7419.
[17] WAN C Y, ZHANG G X, ZHANG F X. A novel guanidine ammonium phosphate for preparation of a reactive durable flame retardant for cotton fabric[J]. Cellulose. 2020, 27(6): 3469-3483.
[18] CHEN Y, WANG D F, LIU S D, et al. A novel P-N-based flame retardant with multi-reactive groups for treatment of cotton fabrics[J]. Cellulose, 2020, 27(15):9075-9089.
[19] ZHENG D D, ZHOU J F, ZHONG L, et al. A novel durable and high-phosphorous-containing flame retardant for cotton fabrics[J]. Cellulose, 2016, 23(3): 2211-2220.
[20] WANG D F, ZHONG L, ZHANG C, et al. A novel reactive phosphorous flame retardant for cotton fabrics with durable flame retardancy and high whiteness due to self-buffering[J]. Cellulose, 2018, 25(10): 5479-5497.
[21] LU Y, JIA Y L, ZHANG G X, et al. An eco-friendly intumescent flame retardant with high efficiency and durability for cotton fabric[J]. Cellulose, 2018, 25(9): 5389-5404.
[22] NIE S B, JIN D, YANG J N, et al. Fabrication of environmentally-benign flame retardant cotton fabrics with hydrophobicity by a facile chemical modifi-cation[J]. Cellulose, 2019, 26(8): 5147-5158.
[23] TIAN P X, LU Y, WANG D F, et al. Synthesis of a new N-P durable flame retardant for cotton fabrics[J]. Polymer Degradation and Stability, 2019, 165: 220-228.
doi: 10.1016/j.polymdegradstab.2019.04.024
[24] DONG C H, HE P S, LU Z, et al. Preparation and properties of cotton fabrics treated with a novel antimicrobial and flame retardant containing triazine and phosphorus components[J]. J Therm Anal Calorim, 2018, 131(2): 1079-1087.
[25] JIA Y L, HU Y W, ZHENG D D, et al. Synthesis and evaluation of an efficient, durable, and environmentally friendly flame retardant for cotton[J]. Cellulose, 2017, 24(2): 1159-1170.
[26] DONG C H, LU Z, ZHANG F J, et al. Combustion behaviors of cotton fabrics treated by a novel nitrogen-and phosphorus-containing polysiloxane flame retar-dant[J]. J Therm Anal Calorim, 2016, 123(1): 535-544.
[27] CHEN Y, LIAO Y, WAN C Y, et al. Synthesis of a novel PN reactive ammonium phosphate-based flame retardant for durable finishing of cotton fabric[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022. DOI: 10.1016/j.colsurfa.2021.127967.
[1] XU Yusong, ZHOU Jie, GAN Jiayi, ZHANG Tao, ZHANG Xianming. Preparation of phosphorus and nitrogen containing waterborne polyurethane and its application in polyester fabrics for flame retardant finishing [J]. Journal of Textile Research, 2024, 45(07): 112-120.
[2] WU Yuhang, WEI Jianfei, GU Weiwen, WANG Yuping, ZHANG Anying, WANG Rui. Preparation and properties of flame retardant modified polyethylene terephthalate by in-situ polymerization [J]. Journal of Textile Research, 2024, 45(06): 1-10.
[3] MA Yiping, FAN Wuhou, HU Xiao, WANG Bin, LI Linhua, LIANG Juan, WU Jinchuan, LIAO Zhengke. Preparation and application of durable aqueous organic-inorganic hybrid fluorine-free water-repellant finishing agents [J]. Journal of Textile Research, 2024, 45(06): 113-119.
[4] CHENG Xianwei, LIU Yawen, GUAN Jinping, CHEN Rui. Preparation and flame-retardant performance of coated polyamide 6 fabrics with biomass phytic acid modified polyurethane [J]. Journal of Textile Research, 2024, 45(06): 120-126.
[5] LI Qianqian, GUO Xiaoling, CUI Wenhao, XU Yuzhen, WANG Linfeng. Preparation and performance of antibacterial polyester knitted fabric for automotive seats [J]. Journal of Textile Research, 2024, 45(06): 127-133.
[6] HAN Hua, HU Anran, SUN Yiwen, DING Zuowei, LI Wei, ZHANG Caiyun, GUO Zengge. Fabrication of antibacterial polymers coated cotton fabrics with I2 release for wound healing [J]. Journal of Textile Research, 2024, 45(05): 113-120.
[7] XUE Baoxia, YANG Se, ZHANG Chunyan, LIU Jing, LIU Yong, CHENG Wei, ZHANG Li, NIU Mei. Preparation and properties of cotton fabric with poly(N-isopropylacrylamide) antibacterial hydrogel [J]. Journal of Textile Research, 2024, 45(05): 129-137.
[8] HE Fang, GUO Yan, HAN Chaoxu, LIU Mingshen, YANG Ruirui. Composite technology and properties of fabrics for automotive seat [J]. Journal of Textile Research, 2024, 45(05): 79-84.
[9] XIANG Jiaojiao, LIU Hao, OUYANG Shenshen, MA Wanbin, CHAI Liqin, ZHOU Lan, SHAO Jianzhong, LIU Guojin. Preparation of cotton fabrics with both double-sided structural colored effect and high hydrophobicity by one-step method [J]. Journal of Textile Research, 2024, 45(04): 111-119.
[10] WANG Xiaomeng, LI Tingting, SHIU Bingchiuan, LIN Jiahorng, LOU Chingwen. Preparation and application of durable and multifunctional photothermal flame retardant fabrics [J]. Journal of Textile Research, 2024, 45(04): 120-125.
[11] HU Ziqiang, LUO Xiaolei, WEI Lulin, LIU Lin. Synergistic flame retardant finishing of polyester/cotton blended fabric with phytic acid/chitosan [J]. Journal of Textile Research, 2024, 45(04): 126-135.
[12] YUAN Ye, ZHANG Anying, WEI Lifei, GAO Jianwei, CHEN Yong, WANG Rui. Synthesis kinetics and properties of phosphorus containing flame retardant polyethylene terephthalate [J]. Journal of Textile Research, 2024, 45(04): 50-58.
[13] LI Lili, YUAN Liang, TANG Yuxia, YANG Wenju, WANG Hao. Tea pigment dyeing of cotton fabric modified with polydopamine/chitosan and its antibacterial and anti-ultraviolet properties [J]. Journal of Textile Research, 2024, 45(03): 106-113.
[14] FANG Jin, ZHANG Guangzhi, XU Zhenzhen. Research progress in applied research on click chemistry for preparation of functional textiles [J]. Journal of Textile Research, 2024, 45(03): 227-235.
[15] TIAN Boyang, WANG Xiangze, YANG Yiwen, WU Jing. Preparation and thermal management properties of asymmetric structured fibrous membranes [J]. Journal of Textile Research, 2024, 45(02): 11-20.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed   
No Suggested Reading articles found!
京ICP备14006648号
Copyright 2021 © Editorial office of Journal of Textile Research
Supported by Beijing Magtech Co.Ltd