Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (09): 113-120.doi: 10.13475/j.fzxb.20231001501

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Preparation and characterization of waterborne flame retardant polyurethane for microfiber synthetic leather

XIAO Ningning1,2, CHEN Zhijie2, OUYANG Yufu3, MENG Jingui3, SUN Yangyi1, QI Dongming1,2()   

  1. 1. Zhejiang Provincial Engineering Research Center for Green and Low Carbon Dyeing & Finishing, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing, Zhejiang 312030, China
    3. Zhejiang Meisheng New Material Co., Ltd., Shaoxing, Zhejiang 312030, China
  • Received:2023-10-08 Revised:2024-05-23 Online:2024-09-15 Published:2024-09-15
  • Contact: QI Dongming E-mail:dongmingqi@zstu.edu.cn

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Abstract:

Objective In order to solve the problems of non-flame retardancy, low strength and lack of toughness of polyurethane coating on microfiber synthetic leather, type of phosphate-containing bialcohols as reactive flame retardants were prepared. It was copolymerized with methylene diphenyl diisocyanate (MDI), polytetramethylene ether glycol (PTMEG) and 2,2-dimethylol butyric acid (DMBA) to prepare water borne flame retardant polyurethane (WPU) with good dispersion, stability and performance, which is used for coating microfiber synthetic leather.

Method A reactive flame retardant containing phosphorus was synthesized. It was characterized by Fourier transform infrared spectrometer (FT-IR) and nuclear magnetic resonance spectroscopy (1H NMR). Then, DHIMP was copolymerized with MDI, PTMEG and DMBA to obtain waterborne flame retardant polyurethane (P-WPU). P-WPU was prepared into coating slurry, and the soft and strong polyurethane coating was constructed on the surface of microfiber synthetic leather by double-side scraping, exchange curing and drying.

Results The water dispersion of P-WPU was good. The particle size of the dispersion increased with the increase of DHIMP mass fraction. With the introduction of DHIMP, the Young's modulus of P-WPU film was gradually increased. When the mass fraction of DHIMP was 13.9%, the mechanical properties of P-WPU reached the best. The LOI of microfiber leather was continuously increasing with the gradual increase of DHIMP mass fraction. The results of vertical combustion test illustrated that the microfiber leather coated by P-WPU with different DHIMP mass fractions had a certain degree of flame retardancy. When the mass fraction of DHIMP was 16.1%, the vertical damage length was 2.3 cm, the continuous burning time was 0.6 s, the smoldering time was 0.3 s, the number of droplets was reduced to 0-1, and the absorbent cotton was not ignited, demonstrating a good flame-retardant effect.

Conclusion 1) DHIMP was successfully prepared from p-hydroxybenzaldehyde, 3-amino-propanol and DOPO. 2) By introducing DHIMP as chain extender into waterborne polyurethane macromolecules, waterborne polyurethane with flame retardancy was successfully prepared. 3) The flexible and flame-retardant microfiber synthetic leather was prepared with P-WPU coating. The maximum limiting oxygen index was 28.6%, the vertical damage length was 2.3 cm, the follow-fire time was 0.6 s, and the smoldering time was 0.3 s.

Key words: microfiber synthetic leather, reactive flame retardant, waterborne polyurethane, flame retardant coating, coating strengthening, functional polymer

CLC Number: 

  • TQ325

Fig.1

Synthetic route and molecular structure diagram of DHIMP"

Fig.2

Synthetic route and molecular structure diagram of P-WPU"

Fig.3

FT-IR spectra of DOPO, HIMP and DHIMP"

Fig.4

Nuclear magnetic hydrogen spectrum of DHIMP"

Fig.5

Influence of DHIMP mass fraction on particle size of P-WPU emulsion"

Fig.6

DSC curves of P-WPU membranes with different DHIMP contents"

Tab.1

Mechanical property test results of P-WPU membranes"

DHIMP质
量分数/%		 断裂强
度/MPa		 断裂伸长
率/%		 弹性模量/
MPa
0 6.36 652.34 7.34
9.4 14.28 1 066.03 13.50
11.7 29.04 795.40 14.79
13.9 14.25 723.68 18.16
16.1 12.95 94.19 32.20

Tab.2

Influence of DHIMP mass fraction on flame retardancy of microfiber leather"

DHIMP质量
分数/%		 LOI
值/%		 损毁
长度/
cm		 续燃
时间/
s		 阴燃
时间/
s		 熔滴
数量/
个		 是否点燃
脱脂棉
0 18.1 30(烧尽) 12.6 0 8~9 是
9.4 23.2 18.8 6.2 0 7~8 是
11.7 24.8 12.5 3.4 2.2 5~6 是
13.9 26.7 5.9 1.9 1.1 2~3 否
16.1 28.6 2.3 0.6 0.3 0~1 否

Fig.7

TG (a) and DTG (b) curves of P-WPU membranes with different DHIMP mass fractions"

Fig.8

Combustion diagram of WPU and P-WPU on surface of microfiber leather"

[1] 高强, 范浩军, 颜俊, 等. 三维超疏水超细纤维绒面革的仿生构建[J]. 纺织学报, 2022, 43(10): 126-132.
doi: 10.13475/j.fzxb.20210807107
GAO Qiang, FAN Haojun, YAN Jun, et al. Biomimetic construction of three-dimensional superhydrophobic microfiber suede[J]. Journal of Textile Research, 2022, 43(10): 126-132.
doi: 10.13475/j.fzxb.20210807107
[2] DUO Yongchao, QIAN Xiaoming, ZHAO Baobao, et al. Micro/nano microfiber synthetic leather base with different nanofiber diameters[J]. Journal of Industrial Textiles, 2019. DOI: 10.1177/1528083719858763.
[3] WANG Shijie, DU Lei, ZHU Ping, et al. Influence of hydroxyl-terminated phosphoramidates on the flame retardancy of microfiber synthetic leather[J]. Polymer Degradation and Stability, 2022. DOI: 10.1016/j.polymdegradstab.2022.109897.
[4] 朵永超, 钱晓明, 赵宝宝, 等. 超细纤维合成革基布的制备及其性能[J]. 纺织学报, 2020, 41(9): 81-87.
DUO Yongchao, QIAN Xiaoming, ZHAO Baobao, et al. Preparation and properties of microfiber synthetic leather fabric[J]. Journal of Textile Research, 2020, 41(9):81-87.
[5] 樊高晴. 蓖麻油基水性聚氨酯的制备及其在颜料印花中的应用[D]. 杭州: 浙江理工大学, 2023: 4-30.
FAN Gaoqing. Preparation of castor oil-based aqueous polyurethane and its application in pigment printing[D]. Hangzhou: Zhejiang Sci-Tech University, 2023: 4-30.
[6] 孙国强, 杨建军, 吴庆云, 等. 内交联型自消光水性聚氨酯树脂的制备及其性能[J]. 纺织学报, 2023, 44(7): 151-158.
SUN Guoqiang, YANG Jianjun, WU Qingyun, et al. Preparation and properties of internal crosslinked self-matting waterborne polyurethane resin[J]. Journal of Textile Research, 2023, 44(7): 151-158.
[7] 庞明科, 王淑花, 史晟, 等. 废旧聚对苯二甲酸乙二醇酯纤维醇解制备阻燃水性聚氨酯及其应用[J]. 纺织学报, 2023, 44(2): 214-221.
PANG Mingke, WANG Shuhua, SHI Sheng, et al. Preparation of flame retardant waterborne polyurethane by fiber alcohol lysis of waste polyethylene tere-phthalate[J]. Journal of Textile Research, 2023, 44(2): 214-221.
[8] LU Shaolin, FENG Yechang, ZHANG Peikun, et al. Preparation of flame-retardant polyurethane and its applications in the leather industry[J]. Polymers, 2021, 13(11): 1730-1730.
[9] COBOS M, PAGALDAY E, PUYADENA M, et al. Waterborne hybrid polyurethane coatings containing casein as sustainable green flame retardant through different synthesis approaches[J]. Progress in Organic Coatings, 2023. DOI: 10.1016/j.porgcoat.2022.107278.
[10] 肖云超, 杨雅茹, 郭健鑫, 等. 高温自交联抗熔滴阻燃涤纶织物的制备及其性能[J]. 纺织学报, 2023, 44(11): 151-159.
doi: 10.13475/j.fzxb.20220906301
XIAO Yunchao, YANG Yaru, GUO Jianxin, et al. Preparation and properties of high temperature self-crosslinking flame-retardant polyester fabric[J]. Journal of Textile Research, 2023, 44(11): 151-159.
doi: 10.13475/j.fzxb.20220906301
[11] MARCIN Z, ALEKSANDER P, SŁAWOMIR M, et al. Bio-based rigid polyurethane foams modified with phosphorus flame retardants[J]. Polymers, 2021, 14(1): 102-102.
[12] 陈智杰, 蒋继康, 虞一浩, 等. 硅磷改性碳酸钙的合成及其在聚酰胺涂层中应用[J]. 纺织学报, 2023, 44(4): 146-153.
CHEN Zhijie, JIANG Jikang, YU Yihao, et al. Synthesis of silicon phosphorus modified calcium carbonate and its application in polyamide coating[J]. Journal of Textile Research, 2023, 44(4): 146-153.
[13] DING Haiyang, XIA Chenglong, WANG Jifu, et al. Inherently flame-retardant flexible bio-based polyurethane sealant with phosphorus and nitrogen-containing polyurethane prepolymer[J]. Journal of Materials Science, 2016, 51(10): 5008-5018.
[14] ZHU Jun, LI Jie, CAI Wenyu, et al. Synthesis and application of a phosphorus-containing waterborne polyurethane based polymeric dye with excellent flame retardancy[J]. Progress in Organic Coatings, 2020, 140(C): 105525-105525.
[15] 许黛芳. 磷酸改性芳纶对聚氨酯硬质泡沫阻燃抑烟性能的影响[J]. 纺织学报, 2020, 41(5): 30-37.
XU Daifang. Effect of phosphoric acid modified aramid on flame retardant smoke suppression performance of polyurethane rigid foam[J]. Journal of Textile Research, 2020, 41(5): 30-37.
[16] CUI Yumeng, ZHANG Bo, ZHOU Mengwei, et al. Preparation and characterization of UiO-66-NH2adsorbed triethyl phosphate: flame retardancy and smoke suppression for epoxy resins[J]. Journal of Vinyl and Additive Technology, 2023. DOI: 10.1002/vnl.22079.
[17] CHEN Mingjun, CHEN Chunrong, TAN Yi, et al. Inherently flame-retardant flexible polyurethane foam with low content of phosphorus-containing cross-linking agent[J]. Industrial & Engineering Chemistry Research, 2014, 53(3): 1160-1171.
[18] 任嘉玮, 张圣明, 吉鹏, 等. 磷硅改性阻燃抑熔滴聚酯纤维的制备及其性能[J]. 纺织学报, 2023, 44(2): 1-10.
REN Jiawei, ZHANG Shengming, JI Peng, et al. Preparation and properties of phosphorus-silicon modified flame retardant and anti-melt droplet polyester fiber[J]. Journal of Textile Research, 2023, 44(2): 1-10.
[19] KIM H, KU B C, GOH M, et al. Synthesis and characterization of phosphorus-and sulfur-containing aromatic polyimides for high refractive index[J]. Polymer, 2018 (136): 143-148.
[20] WU Gang, LI Jinqing, LUO Yunjun, et al. Flame retardancy and thermal degradation mechanism of a novel post-chain extension flame retardant waterborne polyurethane[J]. Polymer Degradation and Stability, 2016, 123: 36-46.
[21] WANG Hui, WANG Shuang, DU Xiaosheng, et al. Synthesis of a novel flame retardant based on DOPO derivatives and its application in waterborne polyurethane[J]. RSC Advances, 2019, 9(13): 7411-7419.
[22] 陈智杰, 虞一浩, 符晔, 等. 柔性阻燃聚酰胺湿法涂层织物的制备及其性能[J]. 纺织学报, 2021, 42(11): 110-116.
doi: 10.13475/j.fzxb.20201105607
CHEN Zhijie, YU Yihao, FU Ye, et al. Preparation and properties of flexible flame retardant polyamide wet coated fabric[J]. Journal of Textile Research, 2021, 42(11): 110-116.
doi: 10.13475/j.fzxb.20201105607
[23] WANG Peng, CHEN Lei, XIAO Hang. Flame retardant effect and mechanism of a novel DOPO based tetrazole derivative on epoxy resin[J]. Journal of Analytical and Applied Pyrolysis, 2019, 139: 104-113.
doi: 10.1016/j.jaap.2019.01.015
[24] 冯静静, 柴春鹏, 葛震, 等. 耐静水压阻燃水性聚氨酯织物涂层剂的制备及其性能[J]. 纺织学报, 2016, 37(5): 92-96.
FENG Jingjing, CHAI Chunpeng, GE Zhen, et al. Preparation and properties of hydrostatic pressure flame retardant waterborne polyurethane fabric coating agent[J]. Journal of Textile Research, 2016, 37(5): 92-96.
[25] CUI Mengjie, LI Jing, CHEN Xudong, et al. A halogen-free, flame retardant, waterborne polyurethane coating based on the synergistic effect of phosphorus and silicon[J]. Progress in Organic Coatings, 2021. DOI: 10.1016/j.porgcoat.2021.106359.
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