阻燃功能化氮化硼杂化物的制备及其在环氧树脂中的应用

林黎明; 王正洲

阻燃功能化氮化硼杂化物的制备及其在环氧树脂中的应用

林黎明¹,
王正洲^{1, 2, ,}

1.
同济大学　材料科学与工程学院, 上海 201804
2.
同济大学　先进土木工程材料教育部重点实验室材料, 上海 201804

基金项目: 国家自然科学基金(21975185)

详细信息

通讯作者:
王正洲，博士，研究员，博士生导师，研究方向为聚合物阻燃材料研究，　E-mail: zwang@tongji.edu.cn

中图分类号: TB332
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- 文章访问数: 54
- HTML全文浏览量: 32
- 被引次数: 0
出版历程
- 收稿日期: 2024-03-07
- 修回日期: 2024-04-08
- 录用日期: 2024-04-14
- 网络出版日期: 2024-05-29

Preparation of flame-retardant functionalized boron nitride hybrids and their properties in epoxy resin

LIN Liming¹,
WANG Zhengzhou^{1, 2
, ,}

1.
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
2.
Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China

Funds: National Natural Science Foundation of China (No.21975185)

摘要

摘要: 氮化硼(BN)因表面呈惰性与环氧树脂(EP)相容性较差，而且其阻燃效率也不高。通过将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物(DMZ)与Fe(NO₃)₃反应得到的配位化合物(FeD)在BN表面进行原位生长，制备出阻燃功能化氮化硼(FeD/BN)。将FeD/BN加入到EP中，制备导热阻燃的EP复合材料。通过极限氧指数(LOI)、垂直燃烧(UL-94)测试和锥形量热测试对复合材料的阻燃性能进行了研究，发现含有15%的FeD/BN的EP复合材料(15(Fe/B)/EP)的LOI为33.2%，达到了UL-94的V-0级；该复合材料峰值热释放速率(pHRR)、总热释放量(THR)和总烟释放量(TSR)相较于纯EP分别降低28.2%、18.9%和30.1%。导热系数测试表明， 15(Fe/B)/EP的导热系数相较于纯EP的导热系数提高了235%。此外，与纯EP相比，该复合材料的拉伸强度与冲击强度都有所提高。
- 阻燃功能化氮化硼 /
- 环氧树脂 /
- 导热性能 /
- 阻燃性能 /
- 力学性能
Abstract: Boron nitride (BN) exhibited poor compatibility with epoxy resin (EP) due to its inert surface, and its flame-retardant efficiency in EP was low. In this study, a coordination compound (FeD) was synthesized by a reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative (DMZ) and Fe(NO₃)₃. FeD was grown in situ on the surface of BN to prepare a flame-retardant functionalized boron nitride hybrid (FeD/BN). FeD/BN was incorporated into EP to prepare thermally conductive and flame-retardant EP composites. Limiting oxygen index (LOI) and vertical burning (UL-94) tests indicate that EP composite with 15 wt% FeD/BN achieves a V-0 rating in the UL-94 test with a LOI value of of 33.2%. Cone calorimetry test results show that the peak heat release rate, total heat release and total smoke release of the composite decrease by 28.2%, 18.9% and 30.1%, respectively compared to those of pure EP. Thermal conductivity of 15(Fe/B)/EP is 235% higher than that of pure EP. Tensile and impact strengths of 15(Fe-B)/EP are enhanced compared with those of pure EP.
- flame-retardant functionalized boron nitride hybrid /
- epoxy resin /
- thermally conductive performance /
- flame retardancy /
- mechanical properties

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图 1 FeD的制备过程示意图

Figure 1. Schematic illustration of preparation of FeD

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图 2 FeD/BN的制备过程示意图

Figure 2. Schematic illustration of preparation of FeD/BN

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图 3 BN、FeD和FeD/BN的(a) FT-IR，(b) XRD

Figure 3. (a) FT-IR images and (b) XRD images of BN, FeD, and FeD/BN

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图 4 (a) BN和(b) FeD/BN的SEM图；FeD/BN的EDS图：(c) B，(d) C，(e) N，(f) O，(g) P和(h) Fe

Figure 4. SEM images of (a) BN and (b) FeD/BN; EDS images of FeD/BN: (c) B, (d) C, (e) N, (f) O, (g) P, and (h) Fe

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图 5 EP复合材料的LOI和UL-94等级

Figure 5. LOI and UL-94 results of EP composites

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图 6 EP复合材料的燃烧行为，(a) HRR曲线，(b) THR曲线和(c) TSP曲线

Figure 6. Combustion behavior: (a) HRR curves, (b) THR curves and (c) TSP curves of EP composites

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图 7 EP复合材料经CCT后的残炭照片

Figure 7. Images of residues of EP composites after CCT tests

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图 8 EP复合材料残炭的SEM图：(a) EP，(b) 15 BN/EP，(c) 15(Fe/B)/EP，(d) 15(Fe-B)/EP，(e) 15 FeD/EP；15(Fe/B)/EP复合材料的EDS图：(f) B，(g) C，(h) N，(i) O，(j) P，(k) Fe

Figure 8. SEM images of residues of EP composites: (a) EP, (b) 15 BN/EP, (c) 15(Fe/B)/EP, (d) 15(Fe-B)/EP, (e) 15 FeD/EP; EDS images of residuals of 15(Fe/B)/EP: (f) B, (g) C, (h) N, (i) O, (j) P, (k) Fe

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图 9 EP复合材料的TG曲线(N₂氛围)

Figure 9. TG curves of EP composites (N₂ atmosphere)

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图 10 EP复合材料残炭的拉曼光谱：(a) EP，(b) 15 BN/EP，(c) 15(Fe/B)/EP，(d) 15(Fe-B)/EP，(e) 15 FeD/EP；

Figure 10. Raman spectra of residues of EP composites after CCT tests: (a) EP, (b) 15 BN/EP, (c) 15(Fe/B)/EP, (d) 15(Fe-B)/EP, (e) 15 FeD/EP

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图 11 EP复合材料的导热系数

Figure 11. Thermal conductivity of EP composites

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图 12 复合材料的力学性能：(a) 拉伸强度和断裂伸长率，(b) 冲击强度

Figure 12. Mechanical properties of EP composites: (a) tensile strength and elongation at break, (b) impact strength

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图 13 EP复合材料的SEM图：(a) EP，(b) 15 BN/EP，(c) 15(Fe/B)/EP，(d) 15 FeD/EP

Figure 13. SEM images of EP composites: (a) EP, (b) 15 BN/EP, (c) 15(Fe/B)/EP, (d) 15 FeD/EP

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表 1 EP复合材料的配方

Table 1. Formulations of EP composites

Sample	EP/wt%	DDM/wt%	FeD/BN/wt%	BN/wt%	FeD/wt%
EP	80	20	0	0	0
5(Fe/B)/EP	76	19	5	0	0
10(Fe/B)/EP	72	18	10	0	0
15(Fe/B)/EP	68	17	15	0	0
15(Fe-B)/EP	68	17	0	11.38	3.62
15 BN/EP	68	17	0	15	0
15 FeD/EP	68	17	0	0	15
Notes: FeD/BN：FeD functionalized BN; 15 (Fe/B)/EP: epoxy composite with 15 wt% FeD/BN; 15(Fe-B)/EP: epoxy composite with 15 wt% FeD and BN compound (the compound ratio is calculated according to the load ratio); 15 FeD/EP: epoxy composite with 15 wt% FeD

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表 2 EP及其复合材料的CCT测试结果

Table 2. CCT test results of EP composites

Sample	TTI/s	pHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	TSR/(m²·m⁻²)
EP	85	1026	111	2770
15 BN/EP	125	932	105	2143
15(Fe/B)/EP	109	737	90	1937
15(Fe-B)/EP	102	873	99	2146
15 FeD/EP	99	606	91	1655
Notes: TTI: time to ignition; pHRR: peak of heat release rate; THR: total heat release; TSR: total smoke rate

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表 3 本工作和其它类似导热阻燃EP复合材料的性能比较^{[17, 18, 29, 30]}

Table 3. Comparison of this work and other typical thermal conductive and flame retardant EP composites^{[17, 18, 29, 30]}

Filler	Size	Loading	TC/(W·m⁻¹·K⁻¹)	LOI/%	pHRR	Tensile strength	Year
h-BN	1~2 μm	2wt%	0.23	34.3	−44.7%	\	2023
h-BN	3~5 μm	12.1vol%	1.04	\	−68.9%	\	2023
h-BN	1~2 μm	16wt%	0.69	\	−58.2%	+31.3%	2023
h-BN	5 μm	11.3wt%	0.47	33.2	−28.2%	+4.4%	This work
Notes: TC: thermal conductivity; LOI: limiting oxygen index; pHRR: peak of heat release rate

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