Preparation and Properties of thin-wall flame-retardant polycarbonate materials with low heat release and smoke
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摘要: 兼具低烟低热和薄壁阻燃的无卤无氟聚碳酸酯(PC)的制备是该领域面临的一个挑战。以八甲基环四硅氧烷和硼酸为原料，通过缩聚反应制备了一种聚硼硅氧烷(PBS)阻燃剂，将其与硼酚醛树脂(LPR)复配制备了PBS-LPR/PC复合材料。结果表明，在PBS和LPR总添加量为10 wt%，质量比3∶1时，在PC中表现出最佳的协同阻燃效果，1.6 mm厚的PC样品能够通过UL-94垂直燃烧测试的V-0级别。与PC相比，该样品的峰值放热率(pHRR)、峰值产烟率(pSPR)、总热释放(THR)和总烟生成(TSP)分别降低了76%、64%、49%和65%。阻燃机制研究表明PBS和PC的交联成炭以及LPR的原位成炭是阻燃性能提高的主要原因。7.5%PBS-2.5%LPR/PC的缺口冲击强度是PC的2.3倍，材料表现出高韧的特性。Abstract: The preparation of halogen-free and fluorine-free thin-wall flame-retardant polycarbonate (PC) with low smoke and heat release was a challenge in the field. Polyborosiloxane (PBS) flame retardant wasprepared by polycondensation reaction between octamethyl cyclotetrasiloxane and boric acid, and then compounded with boron-phenolic resin (LPR) to prepare PBS-LPR/PC composites. The results show that whenthe total amount of PBS and LPR is 10 wt% and the mass ratio is 3∶1, the best flame-retardant effect is shown in PC, the 1.6 mm thick PC sample can pass UL-94 V-0 rating. Compared with that of pure PC, the peak heat release rate (pHRR), the peak smoke production rate (pSPR), the total heat release (THR)and the total smoke production (TSP) of sample reduces by 76%, 64%, 49% and 65%, respectively. The investigation on flame-retardant mechanism show that LPR decrease the viscosity of PCcomposites first and then increase, which confirms the generation of cross-linking reaction. The notched ipact strength of 7.5%PBS-2.5%LPR/PC is 2.3 times that of PC, which makes the material show high toughness.
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Key words:
- Polycarbonate /
- borosiloxane /
- phenolic resin /
- thin-walled flame retardant /
- low smoke and low heat
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图 2 PC及其复合材料在氮气气氛下的TGA(a) 和DTG(b) 曲线
Figure 2. TGA (a) and DTG (b) curves of PC and its composites under nitrogen atmosphere
图 3 锥形量热测试得到的PC及PBS-LPR/PC复合材料的热释放速率(a), 总热释放量(b), 烟释放速率(c),总生烟量曲线(d)
Figure 3. HRR(a), THR(b),SPR(c), TSP(d) curves of PC and PBS-LPR/PC composites obtained by cone calorimeter
图 4 PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)复合材料锥形量热测试后残炭的数码照片，SEM照片和EDS分析；a,a1表示顶部和侧面残炭形貌，a2表示SEM照片
Figure 4. Morphologies、SEM images and EDS analysis of char residues from PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)composites of digital photos,SEM photos and EDS analysis after the cone calorimeter;a,a1 represent the top and side Morphologies,a2 indicates the SEM images
图 5 PC复合材料残炭的EDS (a)和FTIR(b)谱图
Figure 5. EDS (a) and FTIR (b) spectra of the char residue for PC composites
图 6 温度扫描流变法测定的 PC复合材料的复合黏度曲线(a)和360-400℃的局部放大图(b)
Figure 6. The plots for complex viscosities (a) and local magnification (b) at 360-400℃ for PC composites with by temperature-scanning rheology.
图 7 PC及其复合材料主要降解产物的GC谱图
Figure 7. The GC spectrogram of PC and its composites mainly degraded products
图 8 PBS-LPR/PC复合材料的阻燃机制示意图
Figure 8. Schematic illustration for the flame-retardant mechanism of PBS/LPR/PC composites
图 9 PC和PBS-LPR/PC复合材料的缺口冲击强度
Figure 9. The notched impact strength of PC and PBS-LPR/PC composites
图 10 PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)的缺口冲击淬断面的SEM照片
Figure 10. SEM images of notched impact cross section of PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)
表 1 PBS-LPR/PC复合材料的组成
Table 1. Composition of PC and PBS-LPR/PC composites
Samples PC /wt% PBS/wt% LPR /wt% PC 100.0 0.0 0.0 10%LPR/PC 90.0 0.0 10.0 2.5%PBS-7.5%LPR/PC 90.0 2.5 7.5 5%PBS-5%LPR/PC 90.0 5.0 5.0 7.5%PBS-2.5%LPR/PC 90.0 7.5 2.5 10%PBS/PC 90.0 10.0 0 Notes: LPR−Phenolic Resin; PC—Polycarbonate. 
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表 2 PC和PBS-LPR/PC复合材料在氮气气氛下的热稳定性数据
Table 2. Thermal stability data of PC and PBS-LPR/PC composites in nitrogen atmosphere
Samples T5% /℃ Tmax /℃ Residue /% PC 476 521 24.0 PBS 219 407 2.8 LPR 148 573 69.7 10%LPR/PC 452 517 28.3 2.5%PBS-7.5%LPR/PC 445 515 27.5 5%PBS-5%LPR/PC 408 516 26.4 7.5%PBS-2.5%LPR/PC 378 512 24.3 10%PBS/PC 394 512 24.4 Notes: T5%−5% decomposition temperature in the first; Tmax−Maximum decomposition temperature
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表 3 PC和PBS-LPR/PC复合材料的LOI和UL-94数据
Table 3. LOI and UL-94 data of PC and PBS-LPR/PC composites
Sample LOI /% UL-94/ (1.6 mm) t1 /s t2 /s Dripping Rating PC 27.2 19.5±2.2 4.6±1.7 Yes V-2 10%LPR/PC 28.8 18.6±16.5 0.9±0.2 Yes V-2 2.5%PBS-7.5%LPR/PC 35.8 27.2±22.1 24.8±21.0 Yes NR 5%PBS-5%LPR/PC 32.1 6.2±4.2 2.6±1.9 No V-0 7.5%PBS-2.5%LPR/PC 36.1 4.9±2.7 1.7±1.1 No V-0 10%PBS/PC 32.9 3.1±1.1 5.6±5.6 Yes V-2 Notes: t1−Self-extinguishing time after the first ignition;t2−Self-extinguishing time after the second ignition.
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表 4 PC及PBS-LPR/PC复合材料的锥形量热测试数据
Table 4. Data of cone calorimeter for PC and PBS-LPR/PC composites
Samples PC 10%LPR/PC 2.5%PBS-7.5%LPR/PC 5%PBS-5%LPR/PC 7.5%PBS-2.5%LPR/PC 10%PBS/PC TTI /s 138 115 129 107 135 114 pHRR/(kW·m−2) 590 218 153 149 139 212 THR/(MJ·m−2) 65.9 49.2 43.1 40.7 33.4 51.8 pSPR/(m2·s−1) 0.22 0.10 0.07 0.08 0.08 0.07 TSP/m2 16.8 18.2 10.7 8.4 5.9 9.7 MARHE/(kW·m−2) 172 109 65 67 54 93 FPI/(m2·s·kW−1) 0.223 0.528 0.843 0.718 0.969 0.538 CHR/% 19.1 21.6 38.1 32.8 30.0 18.4 Notes: TTI−Time to ignition; pHRR−Peak heat release rate; THR−Total heat release at 600 s; pSPR−Peak smoke production rate; TSP−Total smoke production at 600 s; MARHE−Maximum average heat release rate; FPI−Fire performance index; CHR−Char residue.
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表 5 GC/MS测定PC及其复合材料主要降解产物组成
Table 5. The composition of the main degradation products from PC and its composites obtained by GC/MS measurements.
Number Structure PC 10%LPR/PC 7.5%PBS-2.5%LPR/PC 10%PBS/PC 1 CO2、H2O 0.7 0.6 1.04 0.5 2 
5.8 3.1 1.26 2.3 3 
5.6 13.6 11.6 24.6 4 
2.6 5.2 4.1 6.2 5 
3.6 0 2.6 0.9 7 
4.1 10.7 1.3 3.7 8 
17.9 2.0 0 9.3 Monophenolics 40.3 35.2 21.9 47.5 11 
56.1 61.1 72.3 31.9 6 
0.5 3.2 4.8 6.3 9 
2.8 0.3 0.4 0.7 10 
0.1 0.2 0.2 0.4 12 
0 0 0.4 5.2
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