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