磷钼酸盐中金属离子对聚丙烯阻燃效率的提升

doi:10.15541/jim20190529

无机材料学报 ›› 2020, Vol. 35 ›› Issue (9): 1029-1033.DOI: 10.15541/jim20190529

磷钼酸盐中金属离子对聚丙烯阻燃效率的提升

李一敏¹(),王成乐²,李娟²()

1.中国石油化工股份有限公司镇海炼化分公司, 宁波 315207
2.中国科学院宁波材料技术与工程研究所, 宁波市高分子材料重点实验室, 宁波 315201

收稿日期:2019-10-16 修回日期:2019-12-09 出版日期:2020-09-20 网络出版日期:2020-03-03
作者简介:李一敏(1984-), 女, 工程师. E-mail: liym.zhlh@sinopec.com
LI Yimin (1984-), female, engineer. E-mail: liym.zhlh@sinopec.com
基金资助:
国家自然科学基金(51473178);宁波市科技创新团队项目(2015B11005)

Improvement of Metal Caions in Polyoxometalate on Flame Retardant Efficiency of Polypropylene

LI Yimin¹(),WANG Chengle²,LI Juan²()

1. Sinopec Zhenhai Refining & Chemical Company, Ningbo 315207, China
2. Ningbo Key Laboratory of Polymer Materials, Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, China

Received:2019-10-16 Revised:2019-12-09 Published:2020-09-20 Online:2020-03-03
Supported by:
National Natural Science Foundation of China(51473178);Program for Ningbo Science and Technology Innovation Team(2015B11005)

摘要/Abstract

摘要：

多金属氧酸盐是一类新型催化剂, 在很多领域表现出良好的应用价值。改变多金属氧酸盐的金属离子类型可以调节其性能。本研究将磷钼酸(PMA)阴离子与三种不同的金属(镍(Ni)、钠(Na)、锌(Zn))离子反应形成磷钼酸盐(PMos), 将其作为催化剂提升膨胀阻燃聚丙烯(PP)的阻燃效率。结果表明, 单独添加膨胀阻燃剂(IFR)时, 添加量达到25wt%才能使PP复合材料的阻燃等级达到UL-94 V0级别, 然而在PP/IFR中添加0.5wt%的磷钼酸钠(NaPMo)或磷钼酸锌(ZnPMo)后, 仅需添加14.5wt%IFR即可使PP复合材料达到UL-94 V0级别, 而同样的配方下, 磷钼酸镍(NiPMo)只能使PP复合材料达到UL-94 V1级别。不同的金属离子在PP/IFR中具有不同的催化活性, 其中NaPMo和ZnPMo与IFR的匹配性较好, NiPMo较差。PMos通过促进IFR反应, 缓和燃烧过程的热释放速率, 并且形成阻隔作用更优良的炭层, 提高PP与IFR的匹配性, 进而提高了其在UL-94测试中的阻燃效率。

关键词: 磷钼酸盐, 金属离子, 协同, 成炭, 阻燃效率

Abstract:

Polyoxometalate is a new type of catalyst, which has good application in many fields. The properties of phosphomolybdate (PMo) can be regulated by changing the metal cations. In this work, phosphomolybdic acid (PMA) anions were reacted with three different metal ions (Ni, Na and Zn) to form PMos, which were used as catalysts to improve the flame retardant efficiency of polypropylene/intumescent flame retardant (PP/IFR). The results show that the PP composites can obtain the UL-94 V0 grade of flame retardant efficiency by adding 25wt% IFR. However, if PMo is introduced into PP/IFR system, only 14.5wt% IFR and 0.5wt% sodium phosphomolybdate (NaPMo) or sodium phosphomolybdate (ZnPMo) are needed for PP to achieve the UL-94 V0 grade. While under the same formulation, nickel phosphomolybdate (NiPMo) can only make PP composite obtain the UL-94 V1 grade. Different metal ions have different catalytic activities in PP/IFR, among which NaPMo and ZnPMo match with IFR better than NiPMo. PMos can promote the reactions among IFR, slow down the heat release rate during combustion, and form a char layer with better barrier effect, so as to improve the matching of PP and IFR, and improve the flame retardant efficiency in the UL-94 test.

Key words: phosphomolybdate, metal caion, synergism, charring, flame retardant efficiency

中图分类号:

TQ322

李一敏,王成乐,李娟. 磷钼酸盐中金属离子对聚丙烯阻燃效率的提升[J]. 无机材料学报, 2020, 35(9): 1029-1033.

LI Yimin,WANG Chengle,LI Juan. Improvement of Metal Caions in Polyoxometalate on Flame Retardant Efficiency of Polypropylene[J]. Journal of Inorganic Materials, 2020, 35(9): 1029-1033.

图/表 8

表1 PP复合材料的阻燃性能

Table 1 Flame retardant properties of PP composites

No.	PP /wt%	IFR /wt%	Synergists /wt%	UL-94 3.2 mm	LOI
S1	100.0	0	No	NC	17.2
S2	85.0	15.0	No	NC	23.1
S3	85.0	14.5	0.5(NiPMo)	V-1	26.1
S4	85.0	14.5	0.5(NaPMo)	V-0	26.8
S5	85.0	14.5	0.5(ZnPMo)	V-0	27.0
S6	75.0	25.0	No	V-0	28.3

图1 PMos的红外光谱(a)和TGA曲线(b)

Fig. 1 TGA curves (a) and FT-IR spectra (b) of different PMos

图2 PP复合材料的红外热成像图片

Fig. 2 Photographs of infrared thermal imaging for PP composites

图3 PP复合材料在(a)氮气和(b)空气中测试得到的TGA曲线

Fig. 3 TGA curves of PP composites tested in (a) N2 and (b) air

图4 PP复合材料的(a)热释放速率和(b)总热释放量随时间的变化

Fig. 4 Change of (a) HRR and (b) THR with time for PP composite at a heat flux of 35 kW/m2

表2 锥形量热测试具体数据

Table 2 Data from cone calorimeter test

No.	TTI/s	PHRR/(kW·m^-2)	t_PHRR/s	THR/(MJ·m^-2)
S1	50	706.3	175	107.3
S2	45	383.9	294	109.5
S3	40	344.0	353	106.9
S4	43	407.8	363	112.8
S5	43	390.2	356	110.0

图5 PP复合材料锥形量热测试后的炭层照片

Fig. 5 Photos of char layers for PP composites after cone calorimeter test (a-e): S1-S5

图6 PP复合材料锥形量热测试后的炭层SEM照片

Fig. 6 SEM images of char layers for PP composites after cone calorimeter test (a-d): S2-S5

参考文献 12

[1]	ZHOU YOU, LIU XIU, WANG FANG,et al. Effect of metal oxides on fire resistance and char formation of intumescent flame retardant coating. Journal of Inorganic Materials, 2014,29(9):1267-1272.
[2]	CHEN XIAN-FENG, HUANG CHU-YUAN, SHI YONG-QIAN,et al. MoO₃-ZrO₂ solid acid for enhancement in the efficiency of intumescent flame retardant. Powder Technology, 2019,344(15):581-589. DOI URL
[3]	QIN ZHAO-LU, LI DING-HUA, YANG RONG-JIE. Preparation of ammonium polyphosphate coated with aluminium hydroxide and its application in polypropylene as flame retardant. Journal of Inorganic Materials, 2015,30(12):972-978.
[4]	YE LEI, ZHANG YUN-JIE, WANG SHU-HONG,et al. Synergistic effects and mechanism of ZnCl₂ on intumescent flame-retardant polypropylene. Journal of Thermal Analysis and Calorimetry, 2014,115:1065-1071.
[5]	DITTRICH BETTINA, WARTIG KAREN-ALESSA, HOFMANN DANIEL,et al. Flame retardancy through carbon nanomaterials: carbon black, multiwall nanotubes, expanded graphite, multi-layer graphene and graphene in polypropylene. Polymer Degradation and Stability, 2013,98(8):1495-1505.
[6]	SHEN YIN-LONG, GONG WEI-GUANG, ZHENG BAI-CUN,et al. Synergistic effect of Ni-based bimetallic catalyst with intumescent flame retardant on flame retardancy and thermal stability of polypropylene. Polymer Degradation and Stability, 2016,129(7):114-124.
[7]	GAO YAN-SHAN, ZHANG YU, WILLIAMS GARETH R,et al. Layered double hydroxide-oxidized carbon nanotube hybrids as highly efficient flame retardant nanofillers for polypropylene. Scientific Report, 2016,6:35502.
[8]	HU YA-PENG, WANG XIANG-MEI, LI JUAN. Regulating effect of exfoliated clay on intumescent char structure and flame retardancy of polypropylene composites. Industrial & Engineering Chemistry Research. 2016,55:5892-5901.
[9]	CHEN YA-JUN, XU LI-FENG, WU XING-DE,et al. The influence of nano ZnO coated by phosphazene/triazine bi-group molecular on the flame retardant property and mechanical property of intumescent flame retardant poly (lactic acid) composites. Thermochimica Acta, 2019,679:178336.
[10]	LIU YUAN, WANG QI. Catalytic action of phospho-tungstic acid in the synthesis of melamine salts of pentaerythritol phosphate and their synergistic effects in flame retarded polypropylene. Polymer Degradation and Stability, 2006,91(11):2513-2519.
[11]	CHEN SHENG-JIAO, LI JUAN, ZHU YING-KE,et al. Increasing the efficiency of intumescent flame retardant polypropylene catalyzed by polyoxometalate based ionic liquid. Journal of Materials Chemistry A, 2013,1:15242-15246.
[12]	WANG CHENG-LE, LI JUAN, DING PENG. Roles of supermolecule structure of melamine phosphomolybdate intumescent flame retardant polypropylene composites. Journal of Analytical and Applied Pyrolysis, 2016,119(5):139-146.

[1]	孙强强, 陈子璇, 杨子玥, 王毅梦, 曹宝月. 金属镍铜负载钒氧化物的高效电解产氢性能[J]. 无机材料学报, 2023, 38(6): 647-655.
[2]	王世怡, 冯爱虎, 李晓燕, 于云. Fe₃O₄负载Ti₃C₂T_x对Pb(II)的吸附性能研究[J]. 无机材料学报, 2023, 38(5): 521-528.
[3]	江依义, 沈旻, 宋半夏, 李南, 丁祥欢, 郭乐毅, 马国强. 双功能电解液添加剂对锂离子电池高温高电压性能的影响[J]. 无机材料学报, 2022, 37(7): 710-716.
[4]	曹志军, 李在均. 钌-生物质碳人工酶的制备及在比色检测杀虫剂毒死蜱残留中的应用[J]. 无机材料学报, 2022, 37(5): 554-560.
[5]	安伟佳, 李静, 王淑瑶, 胡金山, 蔺在元, 崔文权, 刘利, 解珺, 梁英华. Fe(III)/rGO/Bi₂MoO₆复合光催化剂制备及光催化芬顿协同降解苯酚[J]. 无机材料学报, 2021, 36(6): 615-622.
[6]	张瑞鸿, 魏鑫, 卢占会, 艾玥洁. 基于机器学习训练金属离子吸附能预测模型的研究[J]. 无机材料学报, 2021, 36(11): 1178-1184.
[7]	谢雪, 吴建荣, 蔡晓军, 郝俊年, 郑元义. 光热/pH响应B-CuS-DOX纳米药物用于化疗-光热协同治疗肿瘤[J]. 无机材料学报, 2021, 36(1): 81-87.
[8]	王苹,李心宇,时占领,李海涛. Ag与Ag₂O协同增强TiO₂光催化制氢性能的研究[J]. 无机材料学报, 2020, 35(7): 781-788.
[9]	张翊青,张淑娟,万正睿,莫晗,王念贵,周立群. RuFe纳米粒子修饰片状BiVO₄协同催化氨硼烷水解产氢[J]. 无机材料学报, 2020, 35(7): 809-816.
[10]	王祥学, 李星, 王佳琦, 朱洪涛. 氮化碳基纳米复合材料在重金属去除方面研究进展[J]. 无机材料学报, 2020, 35(3): 260-270.
[11]	李周, 肖翀. 异层等价离子双掺杂策略优化BiCuSeO的热电性能[J]. 无机材料学报, 2019, 34(3): 294-300.
[12]	张翊青, 刘梨, 张淑娟, 万正睿, 刘红英, 周立群. NH₂-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢[J]. 无机材料学报, 2019, 34(12): 1316-1324.
[13]	南辉, 王文利, 韩建华, 尹学文, 周宇, 赵晓冲, 林红. 基于FeI₂/Ni²⁺溶液还原制备低成本的高导电性及催化性纸张石墨[J]. 无机材料学报, 2017, 32(9): 997-1003.
[14]	赵晓婵, 房艳, 房春晖, 周永全, 戈海文, 朱发岩. 石墨烯包覆分子筛复合电极材料的制备及其性能研究[J]. 无机材料学报, 2017, 32(4): 386-392.
[15]	杨修春. 离子交换和热处理对贵金属掺杂硅酸盐玻璃光致发光的影响[J]. 无机材料学报, 2016, 31(10): 1039-1045.

磷钼酸盐中金属离子对聚丙烯阻燃效率的提升

Improvement of Metal Caions in Polyoxometalate on Flame Retardant Efficiency of Polypropylene

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 12

相关文章 15

编辑推荐

Metrics

本文评价