将富勒烯(C60)与蒙脱土(MMT)复配,作为膨胀型阻燃剂(IFR)的协效剂用于聚丙烯(PP)的热稳定和阻燃改性中,通过对比不同比例的C60和MMT在PP基体中的热性能和阻燃性能的差异,探索C60与MMT协同效应对PP热稳定性和阻燃性能影响及其作用机理。结果表明:C60的自由基捕捉能力和MMT的炭层效应之间存在较好的协效作用,1%的C60/MMT就可使PP/IFR的氧化诱导时间(OIT)和极限氧指数(LOI)分别提升了14.3min和约2.9%,并且可有效地降低锥形量热测试中的最大热释放速率,并延长最大热释放速率对应的时间,且残炭也变得更为致密连续。
The compound of fullerene (C60) and montmorillonite (MMT) was used as a synergist for the flame retardancy of polypropylene(PP).By comparing the difference of thermal and flame retardant properties of C60 and MMT in PP matrix,the synergistic effects of C60 and MMT on PP thermal properties and flame retardancy were investigated.It was found that there was an optimal synergy ratio between C60 and MMT,and 1wt% C60/MMT can increase the oxidation induction time (OIT) and LOI of the PP/IFR system by 14.3min and 2.9%,respectively.In the cone calorimetry test,the addition of C60/MMT can effectively reduce the maximum heat release rate,and prolonged the time corresponding to the maximum heat release rate of the PP/IFR system,and the carbon residue was more dense and continuous.The carbon layer effect of MMT was applied while exerting the free radical trapping effect of C60,and a complete dense crosslinked carbon layer structure was formed in situ in the polymer.
[1] Kashiwagi T,Du F,Douglas J F,et al.Nanoparticle networks reduce the flammability of polymer nanocomposites[J].Nature Materials,2005,4(12):928.
[2] Sain M,Park S H,Suhara F,et al.Flame retardant and mechanical properties of natural fibre-PP composites containing magnesium hydroxide[J].Polymer Degradation and Stability,2004,83(2):363-367.
[3] Kroto H W,Heath J R,O'Brien S C,et al.C60:buckminsterfullerene[J].Nature,1985,318(6042):162-163.
[4] Krusic P J,Wasserman E,Keizer P N,et al.Radical reactions of C60[J].Science,1991,254(5035):1183-1185.
[5] Fang Z P,Song P A,Tong L F.Thermal degradation and flame retardancy of polypropylene/C60 nanocomposites[J].Thermochimica Acta,2008,473:106-108.
[6] Song P A,Zhu Y,Tong L F,et al.C60 reduces the flammability of polypropylene nanocomposites by in situ forming a gelled-ball network[J].Nanotechnology,2008,19(22):225707.
[7] Song P,Liu H,Shen Y,et al.Fabrication of dendrimer-like fullerene (C60)-decorated oligomeric intumescent flame retardant for reducing the thermal oxidation and flammability of polypropylene nanocomposites[J].Journal of Materials Chemistry,2009,19(9):1305-1313.
[8] Wan D,Zhang Z,Wang Y,et al.Dependence of microstructures and melt behaviour of polypropylene/fullerene C60 nanocomposites on in situ interfacial reaction[J].Soft Matter,2011,7(11):5290-5299.
[9] 韩黎刚,郭正虹,方征平.偶联改性富勒烯对氢氧化铝填充聚乙烯阻燃性能和热稳定性的影响[J].高分子材料科学与工程,2015,31(12):54-56.
[10] Pan Y,Han L,Guo Z,et al.Improving the flame-retardant efficiency of aluminum hydroxide with fullerene for high-density polyethylene[J].Journal of Applied Polymer Science,2017,134(9):44551.
[11] Zhao L,Song P,Cao Z,et al.Thermal stability and rheological behaviors of high-density polyethylene/fullerene nanocomposites[J].Journal of Nanomaterials,2012,2012:5.
[12] Zhao L,Cao Z,Fang Z,et al.Influence of fullerene on the kinetics of thermal and thermo-oxidative degradation of high-density polyethylene by capturing free radicals[J].Journal of Thermal Analysis and Calorimetry,2013,114(3):1287-1294.
[13] 李莹,王向东.膨胀型阻燃剂和有机蒙脱土协同阻燃聚丙烯的研究[J].中国塑料,2010,24(7):87-91.
[14] 吕斌,段徐宾,高党鸽,等.硅烷偶联剂改性蒙脱土的制备及性能研究[J].陕西科技大学学报(自然科学版),2014,32(3):9-14.
[15] 瞿英俊,许向彬,赵博,等.膨胀阻燃剂/蒙脱土协同作用对聚丙烯性能的影响[J].工程塑料应用,2009,37(2):28-31.
[16] 赖登旺,李笃信,杨军,等.季铵盐复配硅烷偶联剂改性蒙脱土的制备及表征[J].硅酸盐通报,2014;33(6):1298-302.
[17] 中国石油和化学工业协会.塑料用氧指数法测定燃烧行为第2部分:室温试验:GB/T 2406.2—2009[S].北京:中国标准出版社,2-3.
[18] International Organization for Standardization.Reaction-to-fire tests:heat release,smoke production and mass loss rate part1:heat release rate (cone calorimeter method) and smoke production rate (dynamic measurement):ISO5660-1:2015[S].Geneva:International Standard,2015,7-9.
[19] Zhao L,Guo Z,Ran S,et al.The effect of fullerene on the resistance to thermal degradation of polymers with different degradation processes[J].Journal of Thermal Analysis and Calorimetry,2014,115(2):1235-1244.
