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- 2018
笼状季戊四醇磷酸酯-可膨胀石墨协同阻燃天然橡胶
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Abstract:
以笼状季戊四醇磷酸酯（PEPA）和可膨胀石墨（EG）构成协同阻燃体系添加到天然橡胶（NR）中制备EG-PEPA/NR复合材料。通过极限氧指数（LOI）和垂直燃烧（UL-94）测试、热失重和锥形量热分析、拉伸测试及残炭的SEM观察和FTIR检测，考察了不同质量配比的PEPA和EG对EG-PEPA/NR复合材料阻燃性能和力学性能的影响。结果表明，当PEPA与EG以33：7的质量比添加到NR中时，EG-PEPA/NR复合材料的阻燃性能和力学性能最好。EG-PEPA/NR复合材料的LOI达到28.1%，UL-94达到V-0级，600℃时残炭量从27.5%提高到33.6%，总热释放量和热释放速率峰值分别为96.2 MJ·m-2和512.4 kW·m-2，相比于纯NR分别降低了22.2%和40.3%，拉伸强度和断裂伸长率也分别达到13.8 MPa和368%。 The synergistic flame retardant system consisting of cage pentaerythritol phosphate (PEPA) and expandable graphite (EG) was added to the natural rubber (NR) to prepare EG-PEPA/NR composites. The effects of PEPA and EG with different mass ratios on the flame retardancy and mechanical properties of EG-PEPA/NR composites were investigated by limiting oxygen index(LOI) and vertical combustion(UL-94) test, thermogravimetric analysis, cone calorimetry, tensile test and carbon residue SEM and FTIR. The results show that the flame retardancy and mechanical properties of EG-PEPA/NR composites perform the best when PEPA to EG with the mass ratio of 33:7 are added to NR. Its LOI reaches 28.1% and the UL-94 reaches V-0 level. The amount of carbon residue increases from 27.5% to 33.6% at 600℃. The peaks of total heat release and heat release rate are 96.2 MJ·m-2 and 512.4 kW·m-2, respectively, decreasing by 22.2% and 40.3% compared to the pure NR sample. The tensile strength and elongation of EG-PEPA/NR at break also reach 13.8 MPa and 368%, respectively. 辽宁省百千万人才工程（[2017]62）；辽财指高端人才（[2016]864）；沈阳市科技计划项目（17-51-6-00）
| [1] | WANG N, HU L D, HEERALAL V B, et al. Effect of tea saponin-based intumescent flame retardant on thermal stability, mechanical property and flame retardancy of natural rubber composites[J]. Journal of Thermal Analysis & Calorimetry, 2016, 128(2):1-10. |
| [2] | WANG N, WU Y H, MI L, et al. The influence of silicone shell on double-layered microcapsules in intumescent flame-retardant natural rubber composites[J]. Journal of Thermal Analysis & Calorimetry, 2014, 118(1):349-357. |
| [3] | WANG N, XU G, WU Y H, et al. The influence of expandable graphite on double-layered microcapsules in intumescent flame-retardant natural rubber composites[J]. Journal of Thermal Analysis and Calorimetry, 2016, 123(2):1239-1251. |
| [4] | CHEN L, WANG Y Z. A review on flame retardant technology in China part I:Development of flame retardants[J]. Polymers for Advanced Technologies, 2010, 21(1):1-26. |
| [5] | 刘继纯, 陈权, 井蒙蒙, 等. 有机蒙脱土/聚苯乙烯复合材料的燃烧性能与阻燃机制[J]. 复合材料学报, 2011, 28(6):50-58. LIU J C, CHEN Q, JING M M, et al. Fire performance and flame-retardant mechanism of organic montmorillonite/polystyrene composites[J]. Acta Materiae Compositae Sinica, 2011, 28(6):50-58(in Chinese). |
| [6] | 张鑫, 杨荣, 邹国享, 等. 含硅阻燃大分子相容剂的制备及其在无卤阻燃聚乙烯复合材料中的协效作用[J]. 复合材料学报, 2015, 32(6):1618-1624. ZHANG X, YANG R, ZOU G H, et al. Preparation of silicon-containing flame-retardant macromolecular compatibilizer and its synergistic effects on halogen-free flame-retardant polyethylene composites[J]. Acta Materiae Compositae Sinica, 2015, 32(6):1618-1624(in Chinese). |
| [7] | YE L, MIAO Y, YAN H, et al. The synergistic effects of boroxo siloxanes with magnesium hydroxide in halogen-free flame retardant EVA/MH blends[J]. Polymer Degradation & Stability, 2013, 98(4):868-874. |
| [8] | 刘继纯, 常海波, 李晴媛, 等. Mg(OH)2/聚苯乙烯复合材料的阻燃机制[J]. 复合材料学报, 2012, 29(5):32-40. LIU J C, CHANG H B, LI Q Y, et al. Flame retardant mechanism of Mg(OH)2/polystyrene composites[J]. Acta Materiae Compositae Sinica, 2012, 29(5):32-40(in Chinese). |
| [9] | 付琬璐, 王娜, 史胜南. 阻燃涂料的产业现状及发展方向[J]. 弹性体, 2017, 27(5):78-82. FU W L, WANG N, SHI S N. Recent situation and development trend of flame retardant polymeric coatings[J]. China Elastomerics, 2017, 27(5):78-82(in Chinese). |
| [10] | 宋艳, 许亮, 李锦春, 等. 新型磷氮型阻燃剂的制备及其阻燃聚氨酯泡沫塑料[J]. 复合材料学报, 2016, 33(11):2461-2467. SONG Y, XU L, LI J C, et al. Synthesis of novel flame retardant containing phosphorus and nitrogen and its application in retardant polyurethane foam plastic[J]. Acta Materiae Compositae Sinica, 2016, 33(11):2461-2467(in Chinese). |
| [11] | SARANNYA V, SIVASAMY P, MATHAN N D, et al. Study of thermal properties of intumescent additive:Pentaerythritol phosphate alcohol[J]. Journal of Thermal Analysis and Calorimetry, 2010, 102(3):1071-1077. |
| [12] | 邱桂花, 姜兴三, 于名讯. 含磷阻燃剂PEPA的结构与性能研究[J]. 化工新型材料, 2012, 40(8):55-57. QIU G H, JIANG X S, YU M X. Structure and property of flame retardant PEPA[J]. New Chemical Materials, 2012, 40(8):55-57(in Chinese). |
| [13] | 孙立婧, 白静兰, 张琪, 等. PEPA改性聚氨酯-酰亚胺泡沫塑料的性能研究[J]. 化工新型材料, 2016, 44(1):159-161. SUN L Q, BAI J L, ZHANG Q, et al. Research of PEPA modified polyurethane-imide foam[J]. New Chemical Materials, 2016, 44(1):159-161(in Chinese). |
| [14] | 邓前军, 张五一, 陈东初, 等. PM/PEPA协同阻燃硬质聚氨酯泡沫塑料的性能研究[J]. 塑料工业, 2014, 42(5):74-76. DENG Q J, ZHANG W Y, CHEN D C, et al. Study on properties of synergistic flame-retardant rigid polyurethane foam plastics by PM/PEPA[J]. China Plastics Industry, 2014, 42(5):74-76(in Chinese). |
| [15] | 吴岩, 张素爽. 可膨胀石墨/硬质聚氨酯复合材料的制备与性能[J]. 黑龙江科技大学学报, 2015, 25(3):251-255. WU Y, ZHANG S S. Study on preparation and properties of expandable graphite/rigid polyurethane foam composite[J]. Journal of Heilongjiang University of Science & Technology, 2015, 25(3):251-255(in Chinese). |
| [16] | 中国国家标准化管理委员会. 橡胶燃烧性能的测定:GB/T 10707-2008[S]. 北京:中国标准出版社, 2008. Standardization Administration of the People's Republic of China. Rubber:Determination of the burning:GB/T 10707-2008[S]. Beijing:China Standards Press, 2008(in Chinese). |
| [17] | American Society for Testing and Materials International. Standard test method for tensile properties of plastics:ASTM D638-99[S]. West Conshohocken:ASTM International, 2002. |
| [18] | FENG J, HAO J, DU J, et al. Flame retardancy and thermal properties of solid bisphenol a bis (diphenyl phosphate) combined with montmorillonite in polycarbonate[J]. Polymer Degradation and Stability, 2010, 95(10):2041-2048. |
| [19] | SHI L, LI Z M, XIE B H, et al. Flame retardancy of different-sized expandable graphite particles for high-density rigid polyurethane foams[J]. Polymer International, 2006, 55(8):862-871. |
| [20] | GAO F, TONG L, FANG Z. Effect of a novel phosphorous-nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly(butylene terephthalate)[J]. Polymer Degradation & Stability, 2006, 91(6):1295-1299. |
| [21] | 王娜, 栾鸿赫, 张静, 等. 介孔分子筛和Cr2O3协同膨胀阻燃体系对阻燃天然橡胶性能的影响[J]. 复合材料学报, 2017, 34(5):963-969. WANG N, LUAN H H, ZHANG J, et al. Synergistic effects of mesoporous molecular sieve and Cr2O3 with intumesce flame retardant on properties of flame-retarded natural rubber[J]. Acta Materiae Compositae Sinica, 2017, 34(5):963-969(in Chinese). |
| [22] | JIN J, DONG Q X, SHU Z J, et al. Flame retardant properties of polyurethane/expandable praphite composites[J]. Procedia Engineering, 2014, 71:304-309. |
| [23] | DUAN H J, KANG H Q, ZHANG W Q, et al. Core-shell structure design of pulverized expandable graphite particles and their application in flame-retardant rigid polyurethane foams[J]. Polymer International, 2014, 63(1):72-83. |
