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10wt%、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 was prepared 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 when the total amount of PBS and LPR is 10wt% 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 decreases the viscosity of PC composites first and then increases, which confirms the generation of cross-linking reaction. The notched impact 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(HRR) (a)、总热释放量(THR) (b)、烟释放速率(SPR) (c)、总生烟量(TSP) (d)曲线
Figure 3. Heat release rate (HRR)(a), total heat release (THR) (b), smoke production rate (SPR) (c), total smoke production (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和SEM图像：(((a)~(f)), ((a1)~(f1)))分别为顶部和侧面残炭外观形貌；((a2)~(f2)) SEM图像
Figure 4. Digital photos and SEM images 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 after the cone calorimeter: (((a)-(f)), ((a1)-(f1))) Top and side morphologies; ((a2)-(f2)) SEM image
图 5 PC及其复合材料残炭的EDS图谱(a)和FTIR图谱(b)
Figure 5. EDS spectra (a) and FTIR spectra (b) of the char residue for PC and its composites
图 6 温度扫描流变法测定的 PC及其复合材料的复合黏度曲线(a)和360~400℃的局部放大图(b)
Figure 6. Complex viscosity curves (a) and local magnification (b) at 360-400℃ for PC and its composites by temperature-scanning rheology
图 7 PC及其复合材料主要降解产物的GC图谱
Figure 7. 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. 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图像
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-硼酚醛树脂(LPR)/聚碳酸酯(PC)复合材料的组成
Table 1. Composition of PBS-boron-phenolic resin (LPR)/polycarbonate (PC) composites
Sample 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 0.0 
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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
Sample T5%/℃ Tmax/℃ Residue/wt% 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%—5wt% decomposition temperature in the first; Tmax—Maximum decomposition temperature.
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表 3 PC和PBS-LPR/PC复合材料的极限氧指数(LOI)和UL-94数据
Table 3. Limiting oxygen index (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
Sample TTI/s pHRR/(kW·m−2) THR/(MJ·m−2) pSPR/(m2·s−1) TSP/m2 MARHE/(kW·m−2) FPI/(m2·s·kW−1) CHR/wt% PC 138 590 65.9 0.22 16.8 172 0.223 19.1 10%LPR/PC 115 218 49.2 0.10 18.2 109 0.528 21.6 2.5%PBS-7.5%LPR/PC 129 153 43.1 0.07 10.7 65 0.843 38.1 5%PBS-5%LPR/PC 107 149 40.7 0.08 8.4 67 0.718 32.8 7.5%PBS-2.5%LPR/PC 135 139 33.4 0.08 5.9 54 0.969 30.0 10%PBS/PC 114 212 51.8 0.07 9.7 93 0.538 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. 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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