锥形量热法研究阻燃聚丙烯的性能及阻燃机理
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摘要
锥形量热仪试验,试验环境与实际火情极为相似,试验结果与大型实物燃烧试验结果之间存在非常好的相关性,且可评价烟雾、CO、CO2等,操作简便,广泛应用于材料燃烧性能评价。KD膨胀型阻燃剂(KDIFR)和KDB膨胀型阻燃剂(KDBIFR)是耐水性很好的膨胀型阻燃剂,本文就以二者为主体,研究了膨胀型阻燃PP的的阻燃性能、烟雾评价和阻燃机理。主要做了以下工作：
1、KDIFR作为阻燃剂单独使用,使PP的热释放速率减缓、CO、CO2和总烟释放量降低,但总释热量增大,阻燃效果不明显。KDBIFR作为阻燃剂单独使用,使PP的热释放速率明显减缓、总释热量和CO2释放量降低,但CO和总烟量释放量增大,阻燃效果较好。多聚磷酸铵(APP)作为阻燃剂单独使用,使PP的热释放速率、总释热量和C02释放量稍有降低, CO释放量和总烟量升高,阻燃效果不明显。将KDIFR或KDBIFR与APP复合应用于PP中热释放速率分别下降60%和69%、释热总量降低29.1%和45.5%、总烟产量下降90%和20%,不滴落,膨胀性好,阻燃效果显著提高。
2、膨胀型阻燃聚丙烯中若合理地加入溴元素,可使热释放速率、总释热量显著降低,CO2释放量稍有降低,阻燃效果明显提高；但CO和总烟释放量较高,对于火灾中救生极为不利。含溴阻燃剂与适量的KDIFR并用具有较好的阻燃效果,但KDIFR过量使得燃烧初期的热释放速率、总热释放、CO、CO2和烟释放均增大显著,使阻燃效果迅速减弱。
3、采用分子筛(MS)作为协效剂与KDIFR复配使用,水平燃烧法和CONE测试结果均表明MS与KDIFR之间有一定的协同作用,添加2%的MS使KDIFR/PP体系的热释放速率、释热总量、C02释放量都有大幅度的下降,CO释放量稍有降低,但总烟释放量增大,阻燃效果较好。MS加入应适量,过量会适得其反。
Cone Calorimetry (CONE) is easy to carry on, the experimental environment is very similar to the the actual fare. There is good relevance between the CONE test and the large-scale material object burning test. CONE can evaluate the smog, CO, CO2 and so on. Therefore, the Cone Calorimetry is widely used in evaluating the combustion performance of materials. KD intumescent flame retardant (KDIFR) and KDB intumescent flame retardant (KDBIFR) have high water resistance. In this paper, the flame-retardant properties, smog evaluation and mechanism of the intumescent flame retardant PP were studied mainly on KDIFR and KDBIFR. Now our work as follow:
1. KDIFR used alone as a flame retardant, slow down the heat release rate of PP, decreased CO, CO2 release and total smoke production, but raised the total heat release remarkably, the flame-retardant effect is not obviously. KDBIFR used alone as a flame retardant, slow down the heat release rate of PP significantly, decreased the total heat release and CO2 release, but increased the CO release and the total smoke production, the flame-retardant effect is good. Ammonium polyphosphate (APP) as a flame retardant used alone, decreased the heat release rate, the total heat release and CO2 release slightly, increased CO release and the total smoke production, the flame-retardant effect is not obviously. KDIFR or KDBIFR was cooperated with APP in PP, which improved the fire-retardance of PP effectively, was no driping, have good intumescent. Cone calorimeter analyzed showed that the heat release rate reduced by 60% and 69%, the total heat release reduced by 29.1% and 45.5%, the total smoke production reduced by 90% and 20%.
2. If added bromine element reasonablely in the intumescent flame retardant PP system, the heat release rate and the total heat release derceased remarkably, the CO2 release reduced slightly, the flame-retardant improved observably. But the CO release and the total smoke production rasied. The lifesaving is extremely disadvantageous. Bromine-containing flame retardant with an appropriate amount of KDIFR has good flame-retardant effect, but excessive KDIFR increased the heat release rate, total heat release, CO, CO2 release and the total smoke production significantly in the initial combustion. So that the effect of the flame-retardant receded rapidly.
3. Molecular sieve (MS) was cooperated with KDIFR in PP had flame-retardant effect. The results of horizontal burning test and CONE showed that the synergistic effect between MS and KDIFR.The heat release rate, total heat release and CO2 release decreased largely when 2% MS added in KDIFR/PP system, the CO release reduced slightly, but the total smoke production increased, the flame-retardant effect is good. MS should be appropriate to join in KDIFR/PP system, excessive MS will produce exactly the opposite result.
1、KDIFR作为阻燃剂单独使用,使PP的热释放速率减缓、CO、CO2和总烟释放量降低,但总释热量增大,阻燃效果不明显。KDBIFR作为阻燃剂单独使用,使PP的热释放速率明显减缓、总释热量和CO2释放量降低,但CO和总烟量释放量增大,阻燃效果较好。多聚磷酸铵(APP)作为阻燃剂单独使用,使PP的热释放速率、总释热量和C02释放量稍有降低, CO释放量和总烟量升高,阻燃效果不明显。将KDIFR或KDBIFR与APP复合应用于PP中热释放速率分别下降60%和69%、释热总量降低29.1%和45.5%、总烟产量下降90%和20%,不滴落,膨胀性好,阻燃效果显著提高。
2、膨胀型阻燃聚丙烯中若合理地加入溴元素,可使热释放速率、总释热量显著降低,CO2释放量稍有降低,阻燃效果明显提高；但CO和总烟释放量较高,对于火灾中救生极为不利。含溴阻燃剂与适量的KDIFR并用具有较好的阻燃效果,但KDIFR过量使得燃烧初期的热释放速率、总热释放、CO、CO2和烟释放均增大显著,使阻燃效果迅速减弱。
3、采用分子筛(MS)作为协效剂与KDIFR复配使用,水平燃烧法和CONE测试结果均表明MS与KDIFR之间有一定的协同作用,添加2%的MS使KDIFR/PP体系的热释放速率、释热总量、C02释放量都有大幅度的下降,CO释放量稍有降低,但总烟释放量增大,阻燃效果较好。MS加入应适量,过量会适得其反。
Cone Calorimetry (CONE) is easy to carry on, the experimental environment is very similar to the the actual fare. There is good relevance between the CONE test and the large-scale material object burning test. CONE can evaluate the smog, CO, CO2 and so on. Therefore, the Cone Calorimetry is widely used in evaluating the combustion performance of materials. KD intumescent flame retardant (KDIFR) and KDB intumescent flame retardant (KDBIFR) have high water resistance. In this paper, the flame-retardant properties, smog evaluation and mechanism of the intumescent flame retardant PP were studied mainly on KDIFR and KDBIFR. Now our work as follow:
1. KDIFR used alone as a flame retardant, slow down the heat release rate of PP, decreased CO, CO2 release and total smoke production, but raised the total heat release remarkably, the flame-retardant effect is not obviously. KDBIFR used alone as a flame retardant, slow down the heat release rate of PP significantly, decreased the total heat release and CO2 release, but increased the CO release and the total smoke production, the flame-retardant effect is good. Ammonium polyphosphate (APP) as a flame retardant used alone, decreased the heat release rate, the total heat release and CO2 release slightly, increased CO release and the total smoke production, the flame-retardant effect is not obviously. KDIFR or KDBIFR was cooperated with APP in PP, which improved the fire-retardance of PP effectively, was no driping, have good intumescent. Cone calorimeter analyzed showed that the heat release rate reduced by 60% and 69%, the total heat release reduced by 29.1% and 45.5%, the total smoke production reduced by 90% and 20%.
2. If added bromine element reasonablely in the intumescent flame retardant PP system, the heat release rate and the total heat release derceased remarkably, the CO2 release reduced slightly, the flame-retardant improved observably. But the CO release and the total smoke production rasied. The lifesaving is extremely disadvantageous. Bromine-containing flame retardant with an appropriate amount of KDIFR has good flame-retardant effect, but excessive KDIFR increased the heat release rate, total heat release, CO, CO2 release and the total smoke production significantly in the initial combustion. So that the effect of the flame-retardant receded rapidly.
3. Molecular sieve (MS) was cooperated with KDIFR in PP had flame-retardant effect. The results of horizontal burning test and CONE showed that the synergistic effect between MS and KDIFR.The heat release rate, total heat release and CO2 release decreased largely when 2% MS added in KDIFR/PP system, the CO release reduced slightly, but the total smoke production increased, the flame-retardant effect is good. MS should be appropriate to join in KDIFR/PP system, excessive MS will produce exactly the opposite result.
引文
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[13]Shih-Hsuan Chiu,Wun-Ku Wang, Dynamic flame retardancy of polypropylene filled with ammonium polyphosphate, pentaerythritol and melamine additives[J]. Polym Degrad Stab 1998,39:1951-1955
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[16]张志龙,郑裕堃,古连宝等,膨胀型无卤阻燃聚乙烯材料的研究[J].塑料,2000,29(3)：15-21
[17]徐晓楠,新型膨胀型阻燃聚丙烯的研制及性能研究[D].北京：北京理工大学化工与材料学院,1998
[18]马志领,赵文革,郝风春等,磷氮协同阻燃作用机理研究[J].河北大学学报,2000,20(4)：400-404
[19]Xie R.C, Qu B.J, Synergistic effects of expandable graphite with some halogen-free flame retardants in polyolefin blends[J]. Polym Degrad Stab,2001,71(3),375-380
[20]Bost Howard W, Flame-resistant Polyolefin compositions US.P 4043975
[21]Snyder, John L, Fire retardant wire coatingt US P.4038237
[22]Simons. Donald M, Flame retardant filled polyproylene compositions containing carbon black and a cured intumescent flame retardant US.P.4328139
[23]Brady.D.G, Flame retardant polyolefins US.P.4096113
[24]Grace Chigwada, Panchatapa Jash, David D. Jiang, Charles A. Wilkie, Fire retardancy of vinyl ester nanocomposites:Synergy with phosphorus-based fire retardants[J]. Polym Degrad Stab,2005, 89:85-100
[25]舒中俊,漆宗能,聚合物及其复合材料火灾危险与对策[J].工程塑料与应用,1999,11：37-39
[26]李斌,孙才英,张秀成,用锥形量热仪研究聚乙烯膨胀阻燃体系的燃烧性[J].高等学校化学学报,1999,20(1),146-149
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