三位一体膨胀型阻燃剂诱导聚脲复合材料阻燃性能提升

王军; 胡闯; 王超; 张亚; 孙亚如; 阳平平; 刘彦

三位一体膨胀型阻燃剂诱导聚脲复合材料阻燃性能提升

王军¹,
胡闯¹,
王超¹,
张亚¹,
孙亚如^{1, 2},
阳平平^{1, 3, ,},
刘彦^{1, 2}

1.
北京理工大学重庆创新中心现代兵器技术实验室, 重庆 401120
2.
北京理工大学爆炸科学与安全防护全国重点实验室, 北京 100081
3.
南京航空航天大学飞行器先进设计技术国防重点学科实验室, 南京 210016

基金项目: 中央高校基本科研业务费(Nos.NS2024008, NJ2024003)；爆炸科学与安全防护全国重点实验室(北京理工大学, No.KFJJ24-06M)；国家自然科学基金(No. 12202066)；南京航空航天大学人才资助经费(No. 1001-YAH23034)

详细信息

通讯作者:
阳平平，博士，副教授，硕士生导师，研究方向为复合材料力学与先进防护复合材料　E-mail: P.Yang@nuaa.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2024-03-25
- 修回日期: 2024-05-27
- 录用日期: 2024-06-14
- 网络出版日期: 2024-07-02

Preparation of trinity intumescent flame retardants to enhance the flame retardancy of polyurea composites

WANG Jun¹,
HU Chuang¹,
WANG Chao¹,
ZHANG Ya¹,
SUN Yaru^{1, 2},
YANG Pingping^{1, 3
, ,},
LIU Yan^{1, 2}

1.
Modern Ordnance Technology Laboratory, Chongqing Innovation Center, Beijing Institute of Technology, Chongqing 401120, China
2.
State Key Laboratory of Explosion Science and Safety Protection, Beijing Institute of Technology, Beijing 100081, China
3.
Ministerial Key Discipline Laboratory of Advanced Design Technology of Aircraft, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China

Funds: The Fundamental Research Funds for the Central Universities (Nos. NS2024008, NJ2024003); the opening project of State Key Laboratory of Explosion Science and Safety Protection (Beijing Institute of Technology, No. KFJJ24-06M); the National Natural Science Foundation of China (No.12202066); the supporting funds for talents of Nanjing University of Aeronautics and Astronautics (No.1001-YAH23034)

摘要

摘要: 聚合物材料存在易燃、易被氧化的缺点，以及传统膨胀型阻燃体系存吸湿性大、阻燃效率较低、与基体相容性差等缺陷。结合气相阻燃、凝聚相阻燃的设计理念，制备出三位一体膨胀型阻燃剂(PTA-PA)。研究不同含量的PTA-PA对聚脲(PUA)的阻燃性能及力学的影响，分析材料在燃烧、热解过程中气相和凝聚相产物，探究PTA-PA阻燃剂的阻燃机制，建立膨胀型阻燃剂与复合材料热稳定性、阻燃性能和火灾安全性之间的关系。结果表明：和纯PUA相比，添加20.0wt% PTA-PA 的PUA复合材料(PUA-4)具有较高的热稳定性，800 ℃下残炭量为21.9%；PUA-4复合材料的垂直燃烧等级从V-2级提高到V-0级，LOI分别从22.2%提高到28.4%，线烧蚀率、热释放速率峰值和总热释放量分别降低19.8%，71.7%和18.3%。本研究为高性能阻燃聚合物复合材料的制备提供理论基础和事实依据。
- 聚脲 /
- 膨胀型阻燃剂 /
- 阻燃性能 /
- 阻燃机制 /
- 力学性能
Abstract: Polymeric materials are inherently flammable and prone to oxidation. Traditional intumescent flame retardants exhibit drawbacks, including significant moisture absorption, limited flame-retardant efficacy, and suboptimal matrix compatibility. To address these challenges, a trinity intumescent flame retardant (PTA-PA) was synthesized, integrating the principles of gas-phase and condensed-phase flame retardation. This study examined the influence of varying PTA-PA concentrations on the flame resistance and mechanical properties of polyurea (PUA). It entailed analyzing combustion and pyrolysis byproducts to elucidate the mechanism of flame retardance provided by these novel agents. Additionally, the study correlated the introduction of PTA-PA with enhancements in thermal stability, flame retardance, and overall fire safety of the composites. The findings indicate that the PUA composite with a 20.0wt% loading of PTA-PA (PUA-4) exhibits increased thermal stability, evidenced by a residual carbon content of 21.9% at 800℃. Notably, the vertical burn rating of PUA-4 improved from V-2 to V-0, the limiting oxygen index (LOI) rose from 22.2% to 28.4%, and the rates of line ablation, peak heat release, and total heat release diminished by 19.8%, 71.7%, and 18.3%, respectively. This investigation provides a theoretical and empirical foundation for developing advanced flame-retardant polymeric composites.
- polyurea composites /
- intumescent flame retardant /
- flame retardancy /
- flame retardant mechanism /
- mechanical properties

HTML全文

图 1 三位一体膨胀型阻燃剂(PTA-PA)合成示意图

Figure 1. Synthesis process of trinity intumescent flame retardant (PTA-PA)

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图 2 (a)FT-IR光谱、(b)-(d) PTA-PA的XPS光电子能谱、(e) XRD图谱和(f) PTA-PA的¹H-NMR图谱

Figure 2. (a)FT-IR spectra, (b)-(d) XPS spectra of PTA-PA, (e) XRD patterns and (f) ¹H-NMR spectra of PTA-PA

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图 3 PTA-PA微观形貌: (a)SEM图像和(b)TEM图像

Figure 3. Microtopography of PTA-PA: (a) SEM image and (b) TEM image

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图 4 PTA-PA阻燃剂和PUA复合材料的(a) TGA和(b) DTG曲线

Figure 4. (a)TGA and(a) DTG curves of PTA-PAand PUA composite

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图 5 PUA复合材料的 (a)热释放速率(HRR)和(b)总热释放速率(THR)曲线

Figure 5. (a) HRR and (b) THR of PUA and its composites

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图 6 PUA复合材料其它性能：(a)密度(ρ)、(b)导热率(λ)、(c)断裂伸长率(ε_t)和(d)断裂强度(σ_t)

Figure 6. Other properties results for PUA composites: (a) density (ρ), (b)thermal conductivity (λ), (c) elongation at break (ε_t), and (d)tensile strength (σ_t)

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图 7 样品PUA-4的TG-IR分析: (a)Gram-Schmidt曲线;(b)Gram-Schmidt曲线峰值下FTIR光谱;(c)全过程NH₃吸收光谱;(d)全过程饱和烷烃吸收光谱

Figure 7. TG-IR of PUA-4: (a) Gram-Schmidt curve; (b) FTIR of sample at the peaks of Gram-Schmidt curve; (c) whole process absorption spectrum of NH3; (d) whole process absorption spectrum of saturated alkane

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图 8 PUA复合材料炭层拉曼光谱谱图

Figure 8. Raman spectroscopy of the PUA composite residual char.

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图 9 PUA复合材料锥形量热测试后残炭的数码照片图: (a) 主视图和(b) 俯视图

Figure 9. Digital pictures of char residues of PUA composites: (a) profile view and (b) top view.

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图 10 锥型量热仪测试后的PUA复合材料残炭SEM图

Figure 10. SEM images of the residual char after cone calorimeter tests.

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图 11 PUA复合材料阻燃机制示意图Fig.11 Flame retardancy mechanism of PUA composite

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表 1 喷涂耐烧蚀绝热材料配方

Table 1. 1 Formulation of sprayed ablation resistant material

Sample	Component A/ wt%	Component B/ wt%	PTA-PA/wt%
PUA	66.7	33.3	-
PUA-1	63.3	31.7	5.0
PUA-2	60.0	30.0	10.0
PUA-3	56.7	28.3	15.0
PUA-4	53.3	26.7	20.0
Notes: PUA−Neat polyurea; PTA-PA−Flame retardant.

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表 2 PUA复合材料LOI、UL-94、氧乙炔烧蚀和锥形量热仪测试数据

Table 2. Results of LOI, UL-94, OTA and cone calorimeter testsfor EVA composites

Sample	UL-94		LOI	LAR	PHRR	TPHRR	THR	FPI	FGI	TTI
Sample	Dripping	Rating	%	mm/s	kW/m²	s	MJ/m²	m²·s/kW	kW/m²·s	s
PUA	Y	V-2	22.2	0.853	654	158	68.3	0.032	4.139	21
PUA-1	Y	V-2	24.1	0.774	454	168	68.0	0.042	2.702	19
PUA-2	Y	V-2	26.5	0.701	326	227	66.9	0.055	1.436	18
PUA-3	N	V-0	27.0	0.695	268	264	66.0	0.063	1.015	17
PUA-4	N	V-0	28.4	0.684	185	329	55.8	0.092	0.562	17
Notes: N−No; Y−Yes; LOI−Limiting oxygenindex; LAR−Linear ablation rate; PHRR−Peak heat release rate; TPHRR−Peak time corresponding to the heat release rate; THR−Total heat release; FPI−Fire performance index (FPI = TTI/PHRR); FGI−Fire growth index(FGI = PHRR/T PHRR); TTI−Ignition time.

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