微胶囊化膨胀型阻燃剂与有机蒙脱土协效阻燃乙烯-醋酸乙烯共聚物性能

李茁实; 程文华; 董春; 汪碧波; 金志健; 房权生; 胡源

doi:10.13801/j.cnki.fhclxb.20201105.002

微胶囊化膨胀型阻燃剂与有机蒙脱土协效阻燃乙烯-醋酸乙烯共聚物性能

doi: 10.13801/j.cnki.fhclxb.20201105.002

李茁实^1,,
程文华^2,,
董春^1,,
汪碧波^2,,
金志健¹,
房权生^1,,
胡源^2, ,

1.
宝胜科技创新股份有限公司，扬州 225800
2.
中国科学技术大学　火灾科学国家重点实验室，合肥 230026

基金项目: 国家自然科学基金重大项目课题(51991352)；江苏省科技成果转化专项(BA2018107)

详细信息

通讯作者:
胡源，博士，研究员，研究方向为新型阻燃剂和阻燃聚合物材料及安全工程相关材料　E-mail：yuanhu@ustc.edu.cn

中图分类号: TQ328.3
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- 被引次数: 0
出版历程
- 收稿日期: 2020-08-31
- 录用日期: 2020-10-16
- 网络出版日期: 2020-11-06
- 刊出日期: 2021-08-15

Synergistic properties of microencapsulated intumescent flame retardant-organically modified montmorillonite/ethylene-vinyl acetate copolymer composites

LI Zhuoshi^1
,,
CHENG Wenhua^2
,,
DONG Chun^1
,,
WANG Bibo^2
,,
JIN Zhijian¹,
FANG Quansheng^1
,,
HU Yuan^{2
, ,}

1.
Baosheng Science & Technology Co. Ltd., Yangzhou 225800, China
2.
State Key Laboratory of Science and Fire, University of Science and Technology of China, Hefei 230026, China

摘要

摘要: 通过纳米复合的方式，将微胶囊化的膨胀型阻燃体系—聚磷酸铵(APP)-季戊四醇(PER)与有机改性的片层蒙脱土(OMMT)用于协效阻燃乙烯-醋酸乙烯共聚物(EVA)。采用XRD、TEM、TGA、极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热仪、烟密度和动态机械热分析对微胶囊化APP(MCAPP)-微胶囊化PER(MCPER)-OMMT/EVA复合材料的结构与性能进行研究。研究结果表明，OMMT被完全剥离开，并以层离或插层的状态分散在EVA中；MCAPP-MCPER与OMMT之间存在明显的协效阻燃作用，用3wt%OMMT代替MCAPP-MCPER后，MCAPP-MCPER-OMMT/EVA复合材料的LOI值从25.5vol%提高到29.5vol%，垂直燃烧结果由V-2上升到V-0级别，残炭量也由14.5wt%增大到15.9wt%，烟密度由154.7 g/s降低到97.5 g/s，材料的阻燃性能得到有效提高。此外，万能拉伸测试及动态机械热分析测试表明，通过纳米复合制备的阻燃MCAPP-MCPER-OMMT/EVA复合材料具有更好的力学和动态热机械性能。
- 乙烯-醋酸乙烯酯 /
- 阻燃 /
- 纳米复合 /
- 协效作用 /
- 膨胀型阻燃剂
Abstract: Flame retardant ethylene-vinyl acetate (EVA) composites were prepared by combination of microencapsulated intumescent flame retardants-ammonium polyphosphate (APP)-pentaerythritol (PER) and organically modified montmorillonite (OMMT). The microencapsulated APP (MCAPP)-microencapsulated PER (MCPER)-OMMT/EVA composites were further characterized through XRD and TEM, confirming OMMT sheets are well dispersed in the matrix as exfoliated or intercalated nanocomposite state. Limiting oxygen index (LOI), TGA, underwriters laboratories 94 vertical burning (UL-94), cone and smoke density test results indicate the synergistic flame retardancy effect between MCAPP-MCPER and OMMT in MCAPP-MCPER-OMMT/EVA composites. Replacing the same amount of MCAPP-MCPER with 3wt% OMMT could improve the LOI value of the MCAPP-MCPER-OMMT/EVA composites from 25.5vol% to 29.5vol%. The UL-94 rating increases from V-2 to V-0. The char residue of MCAPP-MCPER-OMMT/EVA composites is improved from 14.5wt% to 15.9wt% and the smoke density significantly decreases from 154.7 g/s to 97.5 g/s. Besides, the mechanical property of MCAPP-MCPER-OMMT/EVA composites was tested by universal testing machine and dynamic thermomechanical analysis (DMA), the result shows that the flame-retardant MCAPP-MCPER-OMMT/EVA composites has better mechanical properties.
- ethylene-vinyl acetate /
- flame retardant /
- nanocomposite /
- synergistic effect /
- intumescent flame retardant

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图 1 OMMT粉体和MCAPP-MCPER-OMMT3/EVA纳米复合材料的XRD图谱

Figure 1. XRD patterns of OMMT and MCAPP-MCPER-OMMT3/EVA composites

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图 2 MCAPP-MCPER-OMMT3/EVA纳米复合材料在不同放大倍数下的TEM图像

Figure 2. TEM images of MCAPP-MCPER-OMMT3/EVA composites at different magnifications ((a) 200 nm; (b) 20 nm)

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图 3 MCAPP-MCPER-OMMT/EVA复合材料的热释放速率曲线 (a) 和总热释放量曲线 (b)

Figure 3. Heat release rate (a) and total heat release (b) curves of MCAPP-MCPER-OMMT/EVA composites

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图 4 MCAPP-MCPER-OMMT/EVA复合材料的烟密度曲线

Figure 4. Smoke density curves of MCAPP-MCPER-OMMT/EVA composites

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图 5 MCAPP-MCPER-OMMT/EVA复合材料的TG曲线 (a) 和DTG曲线 (b)

Figure 5. TG (a) and DTG (b) curves of MCAPP-MCPER-OMMT/EVA composites

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图 6 MCAPP-MCPER-OMMT/EVA复合材料的tanδ和储能模量与温度的关系

Figure 6. Temperature dependence of tanδ and storage modules of MCAPP-MCPER-OMMT/EVA composites

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表 1 微胶囊化聚磷酸铵(MCAPP)-微胶囊化季戊四醇(MCPER)-有机蒙脱土(OMMT)/乙烯-醋酸乙烯共聚物(EVA)阻燃复合材料的配方及其相应的阻燃测试结果

Table 1. Formulations and flame retardant test results of microencapsulated ammonium polyphosphate (MCAPP)-microencapsulated pentaerythritol (MCPER)-organically modified montmorillonite (OMMT)/ethylene-vinyl acetate (EVA) composites

Sample	EVA/wt%	MCAPP/wt%	MCPER/wt%	OMMT/wt%	LOI/%	UL-94
EVA	100	0	0	0	17.0	NR
MCAPP-MCPER/EVA	75	16.67	8.33	0	25.5	V-2
MCAPP-MCPER-OMMT0.5/EVA	75	16.33	8.17	0.5	26.0	V-2
MCAPP-MCPER-OMMT1/EVA	75	16.00	8.01	1.0	26.5	V-2
MCAPP-MCPER-OMMT1.5/EVA	75	15.67	7.83	1.5	27.5	V-2
MCAPP-MCPER-OMMT2/EVA	75	15.33	7.67	2.0	28.0	V-0
MCAPP-MCPER-OMMT3/EVA	75	14.67	7.33	3.0	29.5	V-0
MCAPP-MCPER-OMMT5/EVA	75	13.33	6.67	5.0	26.5	NR
Notes: LOI—Limiting oxygen index; UL-94—Underwriters laboratories 94 vertical burning; NR—No rating.

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表 2 MCAPP-MCPER-OMMT/EVA复合材料的锥形量热仪测试数据

Table 2. Cone data of MCAPP-MCPER-OMMT/EVA composites

Sample	TTI/s	T_p/s	PHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	Average HRR/(kW·m⁻²)	Residues/wt%
EVA	48	145	1 503.31	89.90	495.4	0.2
MCAPP-MCPER/EVA	24	280	298.95	81.33	188.6	14.5
MCAPP-MCPER-OMMT3/EVA	15	100	192.16	73.52	138.4	15.9
Notes: TTI—Time to ignition; PHRR—Peak of heat release rate; T_p—Time to PHRR; THR—Total heat release; Average HRR—Average heat release rate.

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表 3 MCAPP-MCPER-OMMT/EVA复合材料的TGA数据

Table 3. TGA data of MCAPP-MCPER-OMMT/EVA composites

Sample	T_−5wt%/℃	T_1max/℃	T_2max/℃	Residues at 700℃/wt%
EVA	335.6	350.0	471.9	0.4
MCAPP-MCPER/EVA	304.8	355.7	472.6	9.9
MCAPP-MCPER-OMMT3/EVA	311.9	356.7	474.5	13.1
Notes: T_−5wt%—Onset degradation temperature; T_1max and T_2max—Maximum decomposition temperature in the first and second stage.

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表 4 MCAPP-MCPER-OMMT/EVA复合材料的力学性能

Table 4. Mechanical properties of MCAPP-MCPER-OMMT/EVA composites

Sample	Tensile strength/MPa	Elongation at break/%
EVA	18.6±1.5	889.3±39
MCAPP-MCPER/EVA	8.1±0.7	731.0±30
MCAPP-MCPER-OMMT3/EVA	11.0±0.9	780.8±35

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