Effect of modified chicken eggshell and intumescent flame retardant on flame retardancy and smoke suppression of thermoplastic polyurethane elastomer
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摘要: 为了提高热塑性聚氨酯弹性体(TPU)的阻燃抑烟性能，以废弃鸡蛋壳(CES)为原料，采用沸石咪唑酯骨架材料-8 (ZIF-8)对其改性，合成了ZIF-8-CES杂化物。与纯TPU相比，当TPU中添加20wt%膨胀型阻燃剂(IFR)和5wt%ZIF-8-CES时，TPU复合材料的热释放速率峰值(pHRR)和烟释放速率峰值(pSPR)分别降低到242 kW·m−2和0.151 m2·s−1，极限氧指数(LOI)值到达31.5%，垂直燃烧(UL-94)达到了V-0级，ZIF-8-CES与IFR在TPU中具有较好的协效阻燃效果。这主要是由于ZIF-8-CES与IFR在高温下生成氧化锌、磷酸钙和亚磷酸钙，起到催化成炭和增强炭层的作用，从而提高了TPU复合材料的阻燃、抑烟性能。
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关键词:
- 鸡蛋壳 /
- 沸石咪唑酯骨架材料-8 /
- 热塑性聚氨酯弹性体 /
- 阻燃 /
- 抑烟
Abstract: In order to improve the flame retardant and smoke suppression properties of thermoplastic polyurethane elastomer (TPU), ZIF-8-CES hybrid was synthesized by using waste chicken eggshell (CES) as raw material and modified by zeolitic imidazolate framework-8 (ZIF-8). Compared with pure TPU, when 20wt% intumescent flame retardant (IFR) and 5wt% ZIF-8-CES are added to TPU, the peak heat release rate (pHRR) and peak smoke release rate (pSPR) of TPU composites are reduced to 242 kW·m−2 and 0.151 m2·s−1, respectively. The limiting oxygen index (LOI) value reached 31.5%, and the vertical combustion (UL-94) reached V-0 level. ZIF-8-CES and IFR have good synergistic flame retardant effect in TPU. This is mainly because ZIF-8-CES and IFR generate zinc oxide, calcium phosphate and calcium phosphite at high temperatures, which play a role in catalyzing carbon formation and enhancing the carbon layer, thereby improving the flame retardant and smoke suppression properties of TPU composites. -
图 1 热塑性聚氨酯弹性体(TPU)复合材料制备示意图
Figure 1. Schematic diagram of preparation process of thermoplastic polyurethane elastomer (TPU) composites
IFR—Inrumescent flame retardant; ZIF-8—Zeolitic imidazolate framework-8; CES—Chicken eggshell
图 2 废弃鸡蛋壳(CES)、ZIF-8和ZIF-8-CES的XRD谱图
Figure 2. XRD patterns of waste CES, ZIF-8 and ZIF-8-CES
图 4 CES (a) 和ZIF-8-CES (b) 的SEM图像和水接触角(WCA)；(c) ZIF-8-CES的EDS分析；(d) ZIF-8-CES的粒径分布；(e) 5wt%ZIF-8-CES-20wt%IFR/TPU复合材料断面的SEM图像
Figure 4. SEM images and water contact angle (WCA) of CES (a) and ZIF-8-CES (b); (c) EDS analysis of ZIF-8-CES; (d) Particle size distribution of ZIF-8-CES; SEM images of fracture surface of 5wt%ZIF-8-CES-20wt%IFR/TPU (e)
图 6 纯TPU和TPU复合材料的TGA曲线 (a)、DTG曲线 (b)
Figure 6. TGA (a) and DTG (b) curves of neat TPU and TPU composites
图 7 TPU和TPU复合材料的极限氧指数(LOI)值和UL-94等级
Figure 7. Limiting oxygen index (LOI) value and UL-94 of neat TPU and TPU composites
图 8 TPU和TPU复合材料的热释放速率(HRR) (a)、总热释放(THR) (b)、烟生成速率(SPR) (c) 和总生烟量(TSP) (d) 曲线
Figure 8. Heat release rate (HRR) (a), total heat release (THR) (b), smoke generation rate (SPR) (c) and total smoke production (TSP) (d) curves of TPU and TPU composites
图 9 TPU和TPU复合材料残炭的拉曼光谱
Figure 9. Raman spectra of residual char of TPU and TPU composites
ID—Intensity of peak D; IG—Intensity of peak G
图 10 5wt%ZIF-8-CES-20wt%IFR/TPU残炭的XRD图谱
Figure 10. XRD pattern of residual char of 5wt%ZIF-8-CES-20wt%IFR/TPU
图 11 TPU和TPU复合材料残炭的数码照片和SEM图像
Figure 11. Digital photos and SEM images of char residue of TPU and TPU composites
表 1 TPU和TPU复合材料的配方
Table 1. Formula of TPU and TPU composites
Sample TPU/wt% IFR/wt% CES/wt% ZIF-8/wt% ZIF-8-CES/wt% TPU 100 0 0 0 0 25wt%IFR/TPU 75 25 0 0 0 5wt%CES-20wt%IFR/TPU 75 20 5 0 0 5wt%ZIF-8-CES-20wt%IFR/TPU 75 20 0 0 5 2wt%ZIF-8-3wt%CES-20wt%IFR/TPU 75 20 3 2 0 5wt%ZIF-8-20wt%IFR/TPU 75 20 0 5 0 
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表 2 纯TPU和TPU复合材料TAG和DTG数据
Table 2. Data of TGA and DTG of neat TPU and TPU composites
Sample T5%/℃ Tmax/℃ Char residue at 700℃/% TPU 323.1 422.2 4.3 25wt%IFR/TPU 268.7 371.5 9.8 5wt%CES-20wt%IFR/TPU 273.7 367.5 14.7 5wt%ZIF-8-CES-20wt%IFR/TPU 281.4 364.2 16.3 2wt%ZIF-8-3wt%CES-20wt%IFR/TPU 280.4 368.7 14.9 5wt%ZIF-8-20wt%IFR/TPU 270.1 363.8 14.8 Notes：T5%—5wt% mass loss temperature; Tmax—Maximum mass loss temperature.
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表 3 纯TPU和TPU复合材料燃烧试验数据
Table 3. Date from combustion tests of neat TPU and TPU composites
Sample pHRR/(kW·m−2) THR/(MJ·m−2) pSPR/(m2·s−1) TSP/m2 TPU 1574 189.2 0.151 16.0 25wt%IFR/TPU 905 105.1 0.074 8.9 5wt%ZIF-8-CES-20wt%IFR/TPU 242 66.5 0.031 6.3 Notes: pHRR —Peak of heat release rate; pSPR—Peak of smoke produce rate.
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