Synergistic flame-retardant effects of zinc borate in intumescent flame retardant applied on polyoxymethylene

doi:10.16265/j.cnki.issn1003-3033.2020.05.003

Abstract

Abstract: In order to improve flame retardancy of IFR on POM, compound ZB-IFR samples were prepared by blending ZB with commonly used IFR (ammonium polyphosphate-melamine-pentaerythritol), and ZB-IFR/POM flame-retardant composites were made with melt blending method. Then synergistic flame-retardant effects of ZB-IFR on POM were studied by using limiting oxygen index (LOI), vertical combustion (UL-94), thermogravimetric analysis (TGA), scanning electron microscope (SEM), CONE calorimeter and Thermogravimetric-infrared (TG-IR). The results show that when 1% ZB is added, LOI of obtained 1.0ZB-IFR/POM can reach 55% and UL-94 grade is V-0. And after thermal expansion, the composite has a high char residual content with a compact and stable char layer, and its heat release rate (HRR), mass loss and smoke emission are the smallest during combustion process, so its fire performance index (FPI) is relatively high. Besides, IFR / POM without ZB emits more CO₂ during thermal decomposition than 1.0ZB-IFR/POM, indicating that ZB addition can effectively hinder full combustion of flame-retardant composites, exhibiting good synergistic flame-retardant effects.

Key words: intumescent flame retardant (IFR), polyoxymethylene (POM), zinc borate (ZB), synergistic flame retardant, cone calorimeter (CONE)

CLC Number:

X937

LIU Huiping, LIU Yuting, WANG Han, LIN Xiaolan, LIAO Huiying. Synergistic flame-retardant effects of zinc borate in intumescent flame retardant applied on polyoxymethylene[J]. China Safety Science Journal, 2020, 30(5): 14-20.

References

[1] 张青,陈英红,武慧智. 聚磷酸铵基复合膨胀型阻燃剂的制备及其对聚甲醛的阻燃作用[J]. 塑料科技,2009(11): 31-33.
ZHANG Qing, CHEN Yinghong, WU Huizhi. Preparation of ammonium polyphosphate based compound flame retardant and its flame retardation on polyoxymethylene[J]. Plastic Science and Technology, 2009(11): 31-33.
[2] 刘鹏波,徐闻,李英杰. 聚甲醛阻燃的研究[J]. 高分子材料科学与工程,2004,20(6): 120-123.
LIU Pengbo, XU Wen, LI Yingjie. A study on flame retardation polyoxymethylene[J]. Polymer Materials Science and Engineering, 2004, 20(6): 120-123.
[3] 刘婧妍,裘漂漂,张小东,等. 超疏水三嗪系膨胀阻燃剂的制备及其应用[J]. 塑料科技,2014,42(7): 114-118.
LIU Jingyan, QIU Piaopiao, ZHANG Xiaodong, et al. Preparation of superhydrophobic triazine intumescent flame retardant and its application [J]. Plastic Science and Technology, 2014, 42(7): 114-118.
[4] 刘惠平,刘章蕊,王春荣,等. m(APP)-m(PER)-m(MEL)比率对水性膨胀型防火涂料阻燃性能的影响[J].中国安全科学学报,2013,23(6): 45-51.
LIU Huiping, LIU Zhangrui, WANG Chunrong, et al. Influence of m (APP) -m (PER) -m (MEL) ratio on flame retardancy of aqueous intumescent fire resistive coating[J]. China Safety Science Journal, 2013, 23(6): 45-51.
[5] 颜龙,徐志胜.户外耐烃类火灾膨胀型隧道防火涂料的制备及性能研究[J].中国安全生产科学技术,2014,10(10): 118-123.
YAN Long,XU Zhisheng. Study on preparation and performance of intumescent fire retardant coating for tunnel lining against hydrocarbon fire outdoors[J].Journal of Safety science and Technology,2014,10(10): 118-123.
[6] HARASHINA Hatsuhiko, TAJIMA Yoshihisa, ITOH Takahito. Synergistic effect of red phosphorus, novolac and melamine ternary combination on flame retardancy of poly(oxymethylene) [J]. Polymer Degradation and Stability,2006,91(9): 1 996-2 002.
[7] 田一政,李武斌,刘常进,等.聚甲醛的阻燃研究新进展[J].塑料工业,2011,39(9): 1-4.
TIAN Yizheng,LI Wubin,LIU Changjin, et al. Recent progress in flame retardant polyoxymethylene[J].China Plastics Industry,2011,39(9): 1-4.
[8] 林晓兰,刘惠平,张晋桢,等. 硼酸锌复配阻燃体系阻燃聚甲醛的研究[J]. 消防科学与技术,2018,37(1): 80-83.
LIN Xiaolan, LIU Huiping, ZHANG Jinzhen. Study on zinc borate/APP-MEL-PER composites flame retardant polyoxymethylene [J]. Fire Science and Technology, 2018, 37(1): 80-83.
[9] JIMENEZ M, DUQUESNE S, BOURBIGOT S. Intumescent fire protective coating: toward a better understanding of their mechanism of action[J]. Theimochimica Acta, 2006, 449: 16-26.
[10] USTA N. Investigation of fire behavior of rigid polyurethane foams containing fly ash and intumescent flame retardant by using a cone calorimeter[J]. Journal of Applied Polymer Science, 2012, 124: 3 372-3 382.
[11] 王圣程,张云峰,禄利刚,等. 协同改性聚氨酯保温材料的阻燃性能[J]. 中国安全科学学报,2017,27(12): 14-19.
WANG Shengcheng, ZHANG Yunfeng, LU Ligang, et al. Flame-retardant properties of polyurethane insulation material modified collaboratively [J]. China Safety Science Journal, 2017,27(12): 14-19.
[12] TANG Shuo, QIAN Lijun, QIU Yong, et al. Synergistic flame retardant effect and mechanisms of boron/phosphorus compounds on epoxy resins[J]. Polymers for Advanced Technologies, 2018, 29(1):641-648.
[13] FENG Caimin, ZHANG Yi, LIANG Dong, et al. Influence of zinc borate on the flame retardancy and thermal stability of intumescent flame retardant polypropylene composites[J]. Journal of Analytical and Applied Pyrolysis, 2015, 115:224-232.
[14] LONG Yan, XU Zhisheng, WANG Xinghua. Synergistic flame retardant and smoke suppression effects of zinc borate in transparent intumescent fire retardant coatings applied on wood substrates[J]. Journal of Thermal Analysis and Calorimetry, 2018, 136:1 563-1 574.
[15] LIU Li, ZHAO Xiaolong, MA Cuiyong, et al. Smoke suppression properties of carbon black on flame retardant thermoplastic polyurethane based on ammonium polyphosphate[J]. Journal of Thermal Analysis and Calorimetry, 2016, 126(3): 1 821-1 830.
[16] 周玲.三聚氰胺及其类似物红外、拉曼和SERS的理论解析[D]. 武汉:湖北大学,2014.
ZHOU Ling. Theoretical analysis on the infrared, raman spectra and SERS of melamine and its analogues[D]. Wuhan:Hubei University, 2014.