Journal of Textile Research ›› 2021, Vol. 42 ›› Issue (07): 11-18.doi: 10.13475/j.fzxb.20210200108

• Invited Column: New Flame Retardant Technology for Textile Materials • Previous Articles     Next Articles

Preparation and properties of synergistic flame retardant copolyamide 6 fiber with phosphaphenanthrene group

LIU Ke, CHEN Shuang, XIAO Ru()   

  1. Key Laboratory of High-Performance Fibers & Products, Ministry of Education, Donghua University, Shanghai 201620, China
  • Received:2021-02-01 Revised:2021-04-21 Online:2021-07-15 Published:2021-07-22
  • Contact: XIAO Ru E-mail:xiaoru@dhu.edu.cn

RichHTML

30

PDF (PC)

179

Abstract:

In order to improve the flame retardancy of polyamide 6 (PA6) fibers,a flame retardant was synthesized by copolymerization with 10-(2,5-dicarboxyl phenoxyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPODP) and combination of molybdenum disulfide (MoS2) or zinc sulfide (ZnS), the flame retardant PA6 fibers were prepared via melt spinning. The structure, properties, and the flame-retardant mechanism of the co-PA6 and its fibers were also studied. The results show that the DOPODP had been introduced into PA6 molecular chains, the flame retardancy of the copolymer was improved, but the melting temperature and crystallization temperature were reduced. The synergistic flame retardant PA6 achieved a V-0 rating according to the UL94 criterion with an LOI value greater than 30%. The study of the flame-retardant mechanism indicated that the DOPODP in PA6 mainly take effects in gas phase, DOPODP could decompose to phosphorus radicals. In addition, with the introduction of synergistic flame retardants, the char content of flame retardant PA6 was increased. Compared with PA6 fiber, the mechanical properties of flame retardant PA6 fibers were decreased, and the LOI value of the fabrics increased.

Key words: polyamide 6, flame retardant agent, molybdenum disulfide, zinc sulfide, copolymerization, flame retardant fiber, functional fiber

CLC Number: 

  • TQ323.6

Fig.1

Preparation process of PA6-DOPODP"

Tab.1

Experiment formula of PA6-DOPODP/MoS2/ZnS "

试样编号 质量分数/%
DOPODP MoS2 ZnS
0# 0 0 0
1# 3 0 0
2# 5 0 0
3# 7 0 0
4# 9 0 0
5# 9 2 0
6# 9 0 2

Fig.2

FT-IR spectra of DOPODP and DOPODP-DMDA salt"

Fig.3

FT-IR spectra of samples"

Fig.4

Structure and NMR spectrum of sample 4#. (a) Structure; (b) 1H-NMR spectrum; (c) 31P-NMR spectrum "

Tab.2

Element analysis results of PA6-DOPODP"

试样
编号 		元素含量/% 磷含量/% 反应
比/%
C H N O 理论 实测
0# 63.02 9.94 12.20 14.84 — — —
1# 63.13 9.70 11.86 14.99 0.230 0.221 96.09
2# 63.21 9.67 11.89 14.86 0.387 0.371 95.87
3# 63.45 9.53 11.80 14.71 0.536 0.512 95.52
4# 63.59 9.48 11.75 14.55 0.697 0.635 91.10

Tab.3

Relative viscosity, molecular weight and molecular weight distribution of PA6-DOPODP/MoS2/ZnS "

试样编号 相对黏度 数均分子量/(g·mol-1) 多分散性指数
0# 2.52 2.19×104 1.76
1# 2.55 2.27×104 1.79
2# 2.47 2.18×104 1.82
3# 2.45 2.12×104 1.84
4# 2.37 1.92×104 1.97
5# 2.42 — —
6# 2.39 — —

Tab.4

DSC results of PA6-DOPODP/MoS2/ZnS "

试样编号 熔融温度/℃ 熔融焓/(J·g-1) 结晶温度/℃ 结晶度/%
0# 221.3 71.7 182.7 37.6
1# 218.4 56.7 179.4 29.7
2# 214.8 56.3 176.4 29.5
3# 211.5 55.4 171.4 29.1
4# 209.5 52.5 157.9 27.6
5# 210.1 53.4 179.9 28.5
6# 209.1 57.3 166.7 30.6

Tab.5

Vertical burning and LOI values test results"

试样编号 垂直燃烧 LOI值/%
是否引燃脱脂棉 级别
0# 是 V-2 23.5±0.2
1# 是 V-2 24.1±0.2
2# 是 V-2 25.2±0.2
3# 是 V-2 26.5±0.2
4# 是 V-2 27.6±0.2
5# 否 V-0 30.3±0.2
6# 否 V-0 30.7±0.2

Fig.5

HRR curves of PA6-DOPODP/MoS2/ZnS "

Tab.6

Cone calorimetric data"

试样
编号 		TTI/
s 		p-HRR/
(kW·m-2) 		THR/
(MJ·m-2) 		av-EHC/
(MJ·kg-1) 		SEA/
(m2·kg-1) 		残炭
量/%
0# 62 1 132 136 37 210 0.19
4# 51 868 105 28 436 3.11
5# 52 785 92 27 394 6.52
6# 53 766 94 27 366 6.37

Fig.6

Py-GC/MS spectra of DOPODP, sample 0# and 4# "

Tab.7

Thermogravimetry data of PA6-DOPODP/MoS2/ZnS "

试样编号 初始热分解温度/℃ 最大热分解温度/℃ 残炭量/%
0# 380.3 453.3 0.1
1# 374.7 417.9 3.2
2# 370.7 413.3 3.4
3# 368.4 412.8 3.8
4# 365.9 403.1 4.9
5# 366.7 404.3 6.9
6# 367.5 422.1 8.3

Fig.7

SEM images of char residues of samples"

Fig.8

Raman spectra of char residues of sample"

Fig.9

SEM images of surface and cross-section of samples"

Tab.8

Mechanical properties of fibers"

试样编号 断裂强度/(cN·dtex-1) 断裂伸长率/%
0# 4.3 57.8
1# 4.0 66.9
2# 3.7 63.5
3# 3.5 66.3
4# 3.3 55.6
5# 2.6 46.2
6# 2.3 32.3

Tab.9

Flame retardancy of fabrics"

试样
编号 		续燃时间/
s 		阴燃时间/
s 		损毁长度/
cm 		是否引燃
脱脂棉 		LOI值/
%
0# 31.5 0.0 14.2 是 22.1±0.2
4# 1.2 0.0 4.7 否 27.5±0.2
5# 1.3 0.0 3.2 否 29.3±0.2
6# 1.9 0.0 4.8 否 29.7±0.2
[1] ZHANG S M, FAN X S, XU C C, et al. An inherently flame-retardant polyamide 6 containing a phosphorus group prepared by transesterification polymerization[J]. Polymer, 2020, 207:122890.
doi: 10.1016/j.polymer.2020.122890
[2] GROH K J, BACKHAUS T, CARNEY-ALMROTH B, et al. Overview of known plastic packaging-associated chemicals and their hazards[J]. Science of the Total Environment, 2019, 651:3253-3268.
doi: 10.1016/j.scitotenv.2018.10.015
[3] LIU K, LI Y Y, TAO L, et al. Synjournal and characterization of inherently flame retardant polyamide 6 based on a phosphine oxide derivative[J]. Polymer Degradation and Stability, 2019, 163:151-160.
doi: 10.1016/j.polymdegradstab.2019.03.004
[4] LIU K, LI Y Y, TAO L, et al. Preparation and characterization of polyamide 6 fibre based on a phosphorus-containing flame retardant[J]. RSC Advances, 2018, 8(17):9261-9271.
doi: 10.1039/C7RA13228J
[5] LEE S H, OH S W, LEE Y H, et al. Preparation and properties of flame-retardant epoxy resins containing reactive phosphorus flame retardant[J]. Journal of Engineered Fibers and Fabrics, 2020, 15:1-8.
[6] WEI P, LOU H J, WANG W, et al. Synjournal and properties of wholly aromatic phosphorus-containing thermotropic liquid crystal copolyesters with excellent fibre formation ability[J]. Liquid Crystals, 2020, 48(4):466-475.
doi: 10.1080/02678292.2020.1789768
[7] ZHANG J B, WANG X L, HE Q X, et al. A novel phosphorus-containing poly(1,4-cyclohexylenedimethylene terephthalate) copolyester: synjournal, thermal stability, flammability and pyrolysis behavior[J]. Polymer Degradation and Stability, 2014, 108:12-22.
doi: 10.1016/j.polymdegradstab.2014.06.003
[8] SHI X X, JIANG S H, ZHU J Y, et al. Establishment of a highly efficient flame-retardant system for rigid polyurethane foams based on bi-phase flame-retardant actions[J]. RSC Advances, 2018, 8(18):9985-9995.
doi: 10.1039/C7RA13315D
[9] PENG H Y, WANG D, ZHANG L P, et al. Amorphous cobalt borate nanosheets grown on MoS2 nanosheet for simultaneously improving the flame retardancy and mechanical properties of polyacrylonitrile composite fiber[J]. Composites Part B: Engineering, 2020, 201:108298.
doi: 10.1016/j.compositesb.2020.108298
[10] LI A J, XU W Z, WANG G S, et al. Novel strategy for molybdenum disulfide nanosheets grown on titanate nanotubes for enhancing the flame retardancy and smoke suppression of epoxy resin[J]. Journal of Applied Polymer Science, 2018, 135(15):46064.
doi: 10.1002/app.46064
[11] JASNA V C, ANILKUMAR T, NAIK A A, et al. Chlorinated styrene butadiene rubber/zinc sulfide: novel nanocomposites with unique properties-structural, flame retardant, transport and dielectric properties[J]. Journal of Polymer Research, 2018, 25(6):144.
doi: 10.1007/s10965-018-1536-0
[12] 周卫东, 余小伟, 陈龙, 等. 纤维级复合阻燃PA6的制备及其热稳定性研究[J]. 合成纤维工业, 2020, 43(3):16-21.
ZHOU Weidong, YU Xiaowei, CHEN Long, et al. Preparation and thermal stability of fiber-grade composite flame retardant PA6[J]. China Synthetic Fiber Industry, 2020, 43(3):16-21.
[13] MOURGAS G, GIEBEL E, SCHNECK T, et al. Syntheses of intrinsically flame-retardant polyamide 6 fibers and fabrics[J]. Journal of Applied Polymer Science, 2019, 136(31):47829.
doi: 10.1002/app.v136.31
[14] GE H, WANG W, PAN Y, et al. An inherently flame-retardant polyamide containing a phosphorus pendent group prepared by interfacial polymerization[J]. RSC Advances, 2016, 6(85):81802-81808.
doi: 10.1039/C6RA17108G
[15] LI Y Y, LIN Y Z, SHA K, et al. Preparation and characterizations of flame retardant melamine cyanurate/polyamide 6 composite fibers via in situ polymerization[J]. Textile Research Journal, 2017, 87(5):561-569.
doi: 10.1177/0040517516632478
[16] LEVCHIK S V, WEIL E D. Combustion and fire retardancy of aliphatic nylons[J]. Polymer International, 2000, 49(10):1033-1073.
doi: 10.1002/(ISSN)1097-0126
[17] YOUNIS A A. Optimization of mechanical, thermal, and ignition properties of polyester fabric using urea and phosphoric acid[J]. Journal of Industrial Textiles, 2020, 49(6):791-808.
doi: 10.1177/1528083718798636
[18] DUAN X C, YU B, YANG T H, et al. In situ polymerization of nylon 66/reduced graphene oxide nanocomposites[J]. Journal of Nanomaterials, 2018, 2018:1047985.
[1] XU Kai, TIAN Xing, CAO Ying, HE Yaqi, XIA Yanzhi, QUAN Fengyu. Preparation and property of flame retardant polyester/calcium alginate fiber composites [J]. Journal of Textile Research, 2021, 42(07): 19-24.
[2] LIN Shenggen, LIU Xiaohui, SU Xiaowei, HE Ju, REN Yuanlin. Preparation and properties of Lyocell fibers and fabrics modified with new phytic acid based flame retardant [J]. Journal of Textile Research, 2021, 42(07): 25-30.
[3] GU Weiwen, WANG Wenqing, WEI Lifei, SUN Chenying, HAO Dan, WEI Jianfei, WANG Rui. Influence of carbon dots on properties of flame retardant poly(ethylene terephthalate) [J]. Journal of Textile Research, 2021, 42(07): 1-10.
[4] XING Yusheng, HU Yi, CHENG Zhongling. Preparation and properties of Si/TiO2 composite carbon nanofibers [J]. Journal of Textile Research, 2021, 42(03): 36-43.
[5] JIN Linlin, TIAN Junkai, LI Jiawei, QI Dongming, SHEN Xiaowei, WU Chuntao. Synthesis and properties of biodegradable polyglycolic acid oligomer modified polyester [J]. Journal of Textile Research, 2021, 42(01): 16-21.
[6] LIAO He, WANG Jianning, ZHANG Dongjian, GAN Xuehui, ZHANG Yumei, WANG Huaping. Numerical simulation of interface distribution of side-by-side bi-component melt in orifice [J]. Journal of Textile Research, 2021, 42(01): 30-34.
[7] DUO Yongchao, QIAN Xiaoming, ZHAO Baobao, QIAN Yao, ZOU Zhiwei. Preparation and properties of microfiber synthetic leather base [J]. Journal of Textile Research, 2020, 41(09): 81-87.
[8] GUO Zengge, JIANG Zhaohui, JIA Zhao, PU Congcong, LI Xin, CHENG Bowen. Influence of pressure on rheological behavior of polyethylene terephthalate-polyamide 6 copolymer/polyamide 6 blends [J]. Journal of Textile Research, 2019, 40(12): 27-31.
[9] ZHANG Jiao, GAO Xuefeng, WANG Yuzhou, LIU Haihui, ZHANG Xingxiang. Preparation and properties of polyamide 66/amino-functionalized multi-walled carbon nanotubes fibers [J]. Journal of Textile Research, 2019, 40(11): 1-8.
[10] PAN Weinan, XIANG Hengxue, ZHAI Gongxun, NI Mingda, SHEN Jiaguang, ZHU Meifang. Influence of relative molecular weight of copolyamide 6/66 on crystallization and rheological properties thereof [J]. Journal of Textile Research, 2019, 40(09): 8-14.
[11] REN Yuanlin, JIANG Li'na, HUO Tongguo, TIAN Tian. Research progress of halogen-free flame retardancy and smoke suppression of polyacrylonitrile [J]. Journal of Textile Research, 2019, 40(07): 182-188.
[12] WU Jiao, YU Husheng, WAN Xingyun, TIAN Ping, LI Huimin, HOU Xiaoxin. Preparation and properties of anti-bacterial, anti-mite and anti-mildew functional modified viscose fibers [J]. Journal of Textile Research, 2019, 40(07): 19-23.
[13] CHENG Tong, YAO Yongbo, CHEN Zhongli, JIN Hong, WU Kaijian, WANG Lejun, LIU Yining, ZHANG Yumei. Preparation of flame retardant aromatic polysulfonamide/cellulose fibers with N-methylmorpholine-N-oxide monohydrate as solvent [J]. Journal of Textile Research, 2019, 40(07): 1-76.
[14] QIN Yimin. Physicochemical properties and bioactivities of chitosan fibers [J]. Journal of Textile Research, 2019, 40(05): 170-176.
[15] WANG Yan, WANG Lianjun, CHEN Jianfang. Preparation and properties of guanidine-containing antibacterial polyester fibers [J]. Journal of Textile Research, 2019, 40(04): 26-31.
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