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- 2015
苯并噁嗪树脂及其玻璃纤维增强复合材料的阻燃改性
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Abstract:
应用聚磷酸铵(APP)对苯并噁嗪(BOZ)树脂及玻璃纤维(GF)/BOZ复合材料进行了阻燃改性, 结合热分析和微观形貌分析等研究了材料的阻燃机制.结果表明:APP可以明显提高BOZ树脂的阻燃性能, 随APP含量的提高, 树脂体系的极限氧指数逐渐提高, 添加量为3wt%时可使BOZ树脂的极限氧指数从基体的31.5%提高到34.5%, 并达到UL 94 V-0级.APP的加入使改性树脂体系的分解温度前移, 玻璃化转变温度略有下降, 改性树脂体系固化反应提前, 反应过程变得缓和.APP的加入使GF/BOZ复合材料的阻燃性能进一步提高, 10wt% GF/APP-BOZ复合材料的极限氧指数从GF/BOZ的51.0%提高到57.7%.微观形貌分析表明: APP的加入使APP-BOZ改性树脂及GF/APP-BOZ复合材料燃烧后生成更为致密的炭层, 从而使材料的阻燃性能得到提高. Ammonium polyphosphate (APP) was used as flame retardant to modify benzoxazine (BOZ) resin and glass fiber (GF) /BOZ composites. The flame retardant mechanism of material was investigated by thermal analysis and microstructure analysis. The results show that APP can significantly improve the flame retardancy of BOZ resin. With the increase of APP content, the limiting oxygen index of resin system increase gradually. The limiting oxygen index of 3wt% APP-BOZ resin increases from 31.5% of matrix to 34.5% and the UL 94 of V-0 is obtained. The APP-BOZ modified resins decompose earlier than BOZ resin, and the glass transition temperatures reduce a little. The curing reactions of modified resin system start at lower temperatures and operate more mildly. With the incorporation of APP, the flame retardancy of GF/BOZ composites gets further improved, and the limiting oxygen index of 10wt% GF/APP-BOZ composites increases from 51.0% of GF/BOZ to 57.7%. Microstructure analysis shows that APP can help to form denser char of APP-BOZ modified resins and GF/APP-BOZ composites to improve the flame retardancy. 国家自然科学基金(51103121,51203144);福建省自然科学基金(2015J01222);福建省科技创新平台建设计划(2014H2006);江苏省博士后科研资助计划(1402085B);常熟市科技发展计划科技成果转化专项(C2014C2)
| [1] | Grishchuk S, Sorochynska L, Vorster O C, et al. Structure, thermal, and mechanical properties of DDM-hardened epoxy/benzoxazine hybrids: Effects of epoxy resin functionality and ETBN toughening[J]. Journal of Applied Polymer Science, 2013, 127(6): 5082-5093. |
| [2] | Zhang T T, Men W W, Liu Y, et al. Synthesis and characterization of polybenzoxazine containing phosphorus[J]. Chinese Journal of Polymer Science, 2012, 30(2): 250-257. |
| [3] | Ling H, Gu Y. Flame retardancy of magnesium hydroxide in benzoxazine[J]. Polymer Materials Science & Engineering, 2013, 29(7): 76-79 (in Chinese). 凌鸿, 顾宜. 氢氧化镁阻燃聚聚苯并噁嗪[J]. 高分子材料科学与工程, 2013, 29(7): 76-79. |
| [4] | Ling H, Ye X Z, Gu Y. Modification of benzoxazine with aluminum hydroxide and flame retardancy improvement[J]. Journal of Materials Engineering, 2011(6): 5-10 (in Chinese). 凌鸿, 叶小舟, 顾宜. 氢氧化铝改性苯并噁嗪及阻燃性的研究[J]. 材料工程, 2011(6): 5-10. |
| [5] | Xia Y, Jin F, Mao Z, et al. Effects of ammonium polyphosphate to pentaerythritol ratio on composition and properties of carbonaceous foam deriving from intumescent flame-retardant polypropylene[J]. Polymer Degradation and Stability, 2014, 107: 64-73. |
| [6] | Matsuda N, Shirasaka H, Takayama K, et al. Thermal degradation and flame retardancy of ethylene-vinyl alcohol copolymer blended with ammonium polyphosphate[J]. Polymer Degradation and Stability, 2003, 79(1): 13-20. |
| [7] | Gerard C, Fontaine G, Bellayer S, et al. Reaction to fire of an intumescent epoxy resin: Protection mechanisms and synergy[J]. Polymer Degradation and Stability, 2012, 97(8):1366-1386. |
| [8] | Qu H Q, Wu W H, Hao J, et al. Intumescent flame retardancy and thermal degradation of epoxy resin filled with ammonium polyphosphate using thermogravimetric analysis-fourier transform infrared spectroscopy and thermogravimetric analysis-mass spectrometry[J]. Journal of Macromolecular Science Part B-Physics, 2014, 53(2): 278-295. |
| [9] | Standardization Administration of the People's Republic of China. GB/T 2406.2—2009 Plastics—Determination of burning behaviour by oxygen index Part 2: Ambient-temperature test[S]. Beijing: Standards Press of China, 2009 (in Chinese). 中国国家标准化管理委员会. GB/T 2406.2—2009 用氧指数法测定燃烧行为 第二部分:室温实验[S]. 北京: 中国标准出版社, 2009. |
| [10] | Underwriters Laboratories Incorporated. UL 94 Tests for flammability of plastic materials for parts in devices and appliances[S]. Northbrook, Illinois: Underwriters Laboratories Incorporated, 1996. |
| [11] | Agag T, Liu J, Graf R, et al. Benzoxazole resin: A novel class of thermoset polymer via smart benzoxazine resin[J]. Macromolecules, 2012, 45(22): 8991-8997. |
| [12] | Xu G, Shi T, Wang Q, et al. A facile way to prepare two novel dopo-containing liquid benzoxazines and their graphene oxide composites[J]. Journal of Applied Polymer Science, 2015, 132 (11): 41634. |
| [13] | Zhao X E, Meng Y F, Liu X Y. Combustion and explosion theory[M]. Beijing: Chemical Industry Press, 2011: 66 (in Chinese). 赵雪娥, 孟亦飞, 刘秀玉.燃烧与爆炸理论[M]. 北京: 化学工业出版社, 2011: 66. |
| [14] | Liu W H. Composites[M]. Harbin: Harbin Institute of Technology Press, 2011: 21 (in Chinese). 刘万辉. 复合材料[M].哈尔滨:哈尔滨工业大学出版社, 2011: 21. |
| [15] | Gu Y. Benzoxazine resin — A new kind of thermosetting engineering plastics[J]. Thermosetting Resin, 2002, 17(2): 31-34 (in Chinese). 顾宜. 苯并噁嗪树脂——一类新型热固性工程塑料[J]. 热固性树脂, 2002, 17(2): 31-34. |
| [16] | Pan L L, Li G Y, Su Y, et al. Fire retardant mechanism analysis between ammonium polyphosphate and triphenyl phosphate in unsaturated polyester resin[J]. Polymer Degradation and Stability, 2012, 97(9): 1801-1806. |
| [17] | Duquesne S, Le B M, Bourbigot S, et al. Mechanism of fire retardancy of polyurethanes using ammonium polyphosphate[J]. Journal of Applied Polymer Science, 2001, 82 (13): 3262-3274. |
| [18] | Matsuda N, Shirasaka H, Takayama K, et al. Thermal degradation and flame retardancy of ethylene-vinyl alcohol copolymer blended with ammonium polyphosphate[J]. Polymer Degradation and Stability, 2003, 79(1): 13-20. |
| [19] | Gu J W, Zhang G C, Dong S L, et al. Study on preparation and fire-retardant mechanism analysis of intumescent flame-retardant coatings[J]. Surface and Coatings Technology, 2007, 201(18): 7835-7841. |
| [20] | Kimura H, Matsumoto A, Ohtsuka K. Glass fiber-reinforced composite based on benzoxazine resin[J]. Journal of Applied Polymer Science, 2009, 114(2): 1256-1263. |
| [21] | Liu F, Zhao X N, Chen Y H. Resin of phenolic modification benzoxazine and its properties of composite [J]. Acta Materiae Compositae Sinica, 2008, 25(5): 57-63 (in Chinese). 刘锋, 赵西娜, 陈轶华. 酚醛改性苯并噁嗪树脂及其复合材料性能[J]. 复合材料学报, 2008, 25(5): 57-63. |
| [22] | Li J J, Ou Y X. Flame retardant theories[M]. Beijing: Science Press, 2013: 27 (in Chinese). 李建军, 欧育湘. 阻燃理论[M]. 北京: 科学出版社, 2013: 27. |
| [23] | Takeichi T, Kawauchi T, Agag T. High performance polybenzoxazines as a novel type of phenolic resin[J]. Polymer Journal, 2008, 40 (12): 1121-1131. |
| [24] | Wang D W, Wang F. Research progress of modification for benzoxazine resin[J].China Adhesives, 2013, 22(1): 51-55 (in Chinese). 王登武, 王芳. 苯并噁嗪树脂改性研究进展[J]. 中国胶粘剂, 2013, 22(1): 51-55. |
