酚醛树脂耐热改性的研究进展

doi:10.19936/j.cnki.2096-8000.20210828.019

摘要/Abstract

摘要： 酚醛树脂具有优异的耐热抗烧蚀性能、良好的力学性能、突出的阻燃性能,在航空航天、摩擦材料、防火阻燃等领域得到了广泛地应用。提高酚醛树脂的耐热性一直是业内研究的热点,本文对近年来酚醛树脂的耐热改性方法进行了综述,包括结构改性、纳米掺杂、捕捉挥发分、可陶瓷化,其中,重点总结了结构改性方法。最后,对该领域所存在的问题进行了概述,并展望了其发展前景。

关键词: 酚醛树脂, 残炭率, 耐热性, 改性, 复合材料

Abstract: With excellent heat resistance and ablative property, good mechanical properties and outstanding flame retardant properties, phenolic resin is widely used in aerospace, friction materials, fire retardant and other fields. Improving the heat resistance of phenolic resin has always been a hotspot in the industry. This article reviews the heat resistance modification methods of phenolic resin in recent years, including structural modification, nano-doping, volatile capture, and ceramicization. The structural modification method is highlighted. Finally, the problems existing in this field are summarized and their development prospects are prospected.

Key words: phenolic resin, char yield, heat resistance, modification, composites

中图分类号:

TB332

许国娟, 陈敬菊, 潘天池, 张力. 酚醛树脂耐热改性的研究进展[J]. 复合材料科学与工程, 2021, 0(8): 120-128.

XU Guo-juan, CHEN Jing-ju, PAN Tian-chi, ZHANG Li. Research progress in heat-resistant modification of phenolic resin[J]. COMPOSITES SCIENCE AND ENGINEERING, 2021, 0(8): 120-128.

参考文献

[1] 黄发荣, 万里强. 酚醛树脂及其应用[M]. 北京: 化学工业出版社, 2011: 11-13.
[2] 程功, 肖军. 高超音速飞行器热防护材料技术分析[J]. 航空制造技术, 2015, 58(s2): 43-45.
[3] 李琳, 朱小飞, 杨科, 等. 国内外战术导弹外防护涂层技术现状与发展趋势[J]. 航空制造技术, 2016, 59(14): 47-51.
[4] 冯志海, 师建军, 孔磊, 等. 航天飞行器热防护系统低密度烧蚀防热材料研究进展[J]. 材料工程, 2020, 48(8): 14-24.
[5] BIAN C, WANG S J, LIU Y H, et al. Thermal stability of phenolic resin: New insights based on bond dissociation energy and reactivity of functional groups[J]. RSC Advances, 2016, 6: 55007-55016.
[6] 张新航, 张海鹏, 胡大宁, 等. 硼酚醛树脂在固体火箭发动机防热内衬中的应用[J]. 航天制造技术, 2018(2): 15-18.
[7] 何筑华. 硼改性酚醛树脂在摩擦材料上的应用[J]. 贵州化工, 1999, 24(3): 11-12.
[8] 张力, 张以河, 姚亚琳, 等. 硼酚醛树脂及其复合材料的研究进展[J]. 玻璃钢/复合材料, 2018(3): 107-116.
[9] 林松竹, 崔巍, 贾若琨, 等. 高残炭硼酚醛树脂的制备[J]. 应用化学, 2017, 34(6): 631-635.
[10] 王雷, 卢家骐, 郑莉, 等. 耐高温硼酚醛生产研究[J]. 玻璃钢/复合材料, 2009(2): 68-71.
[11] 邱军, 王国建, 冯悦兵. 不同硼含量硼改性酚醛树脂的合成及其性能[J]. 同济大学学报: 自然科学版, 2007, 35(3): 381-384.
[12] WANG S, JING X, WANG Y, et al. High char yield of aryl boron-containing phenolic resins: The effect of phenylboronic acid on the thermal stability and carbonization of phenolic resins[J]. Polymer degradation and stability, 2014, 99: 1-11.
[13] WANG S, JING X, WANG Y, et al. Synthesis and characterization of novel phenolic resins containing aryl-boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties[J]. Polymers for advanced technologies, 2014, 25(2): 152-159.
[14] 井新利, 王淑娟, 司晶晶, 等. 含芳基硼酚醛树脂及其制备方法: CN 103289033[P]. 2013-04-08.
[15] WANG S, XING X, ZHANG X, et al. Room-temperature fully recyclable carbon fibre reinforced phenolic composites through dynamic covalent boronic ester bonds[J]. Journal of Materials Chemistry A, 2018, 6(23): 10868-10878.
[16] WANG C, ZHANG B, LUO Z, et al. Preparation and properties of a novel addition-curable phenolic resin containing boron element[J]. Polymers for Advanced Technologies, 2018, 29(12): 3014-3019.
[17] LIU Y, JING X. Pyrolysis and structure of hyperbranched polyborate modified phenolic resins[J]. Carbon, 2007, 45(10): 1965-1971.
[18] XU P, JING X. High carbon yield thermoset resin based on phenolic resin, hyperbranched polyborate, and paraformaldehyde[J]. Polymers for Advanced Technologies, 2011, 22(12): 2592-2595.
[19] XU P, JING X. Pyrolysis of hyperbranched polyborate modified phenolic resin[J]. Polymer Engineering & Science, 2010, 50(7): 1382-1388.
[20] LIU Y, JING X. Miscibility, morphology, and thermal properties of hyperbranched polyborates modified phenolic resins[J]. Journal of Polymer Science Part B: Polymer Physics, 2008, 46(19): 2012-2021.
[21] 张文涛, 李昊, 罗振华, 等. 硅氧烷改性线性酚醛的合成与性能研究[J]. 高分子通报, 2014(10): 77-85.
[22] LI S, HAN Y, CHEN F, et al. The effect of structure on thermal stability and anti-oxidation mechanism of silicone modified phenolic resin[J]. Polymer Degradation and Stability, 2016, 124: 68-76.
[23] LI S, CHEN F, HAN Y, et al. Enhanced compatibility and morphology evolution of the hybrids involving phenolic resin and silicone intermediate[J]. Materials Chemistry and Physics, 2015, 165: 25-33.
[24] LI S, LI H, LI Z, et al. Polysiloxane modified phenolic resin with co-continuous structure[J]. Polymer, 2017, 120: 217-222.
[25] 郑知敏, 胡继东, 赵彤, 等. 聚硅氧硅氮烷改性烯丙基酚醛杂化树脂的研究[J]. 有机硅材料, 2007, 21(5): 253-257.
[26] ZHAO H, ZHAO J, LI H, et al. Preparation and characterization of polyborosiloxanes and their blends with phenolic resin as shapeable ceramic precursors[J]. Chinese Journal of Polymer Science, 2014, 32(2): 187-196.
[27] 张斌, 孙明明, 张绪刚, 等. 聚硼硅氧烷改性酚醛树脂耐高温胶粘剂的制备及性能[J]. 高分子材料科学与工程, 2008, 24(6): 152-155.
[28] LI S, CHEN F, ZHANG B, et al. Structure and improved thermal stability of phenolic resin containing silicon and boron elements[J]. Polymer Degradation and Stability, 2016, 133: 321-329.
[29] 郭安儒, 李杰, 刘畅, 等. 有机硅改性硼酚醛树脂的研制[J]. 高等学校化学学报, 2016, 37(12): 2284-2290.
[30] YUN J, CHEN L, ZHAO H, et al. Boric acid as a coupling agent for preparation of phenolic resin containing boron and silicon with enhanced char yield[J]. Macromolecular Rapid Communications, 2019, 40(17): 1800702.
[31] ZHANG L, ZHANG Y, WANG L, et al. Phenolic resin modified by boron-silicon with high char yield[J]. Polymer Testing, 2019, 73: 208-213.
[32] WANG F, HUANG Z, ZHANG G, et al. Preparation and thermal stability of heat-resistant phenolic resin system constructed by multiple heat-resistant compositions containing boron and silicon[J]. High Performance Polymers, 2017, 29(4): 493-498.
[33] GUO Z, LI H, HAN W, et al. Thermal stability of novolac cured with polyborosilazane[J]. Journal of applied polymer science, 2013, 128(5): 3356-3364.
[34] GUO Z, LI H, LIU Z, et al. Preparation, characterization and thermal properties of titanium-and silicon-modified novolac resins[J]. High Performance Polymers, 2013, 25(1): 42-50.
[35] 王冬. 聚硼硅氧烷与聚钛硼硅氧烷改性酚醛树脂及陶瓷化研究[D]. 北京: 北京化工大学, 2015.
[36] ZHANG Y, SHEN S, LIU Y. The effect of titanium incorporation on the thermal stability of phenol-formaldehyde resin and its carbonization microstructure[J]. Polymer degradation and stability, 2013, 98(2): 514-518.
[37] 李咸龙, 石振海, 张多太. 耐高温钼改性酚醛树脂胶粘剂的制备及耐热性研究[J]. 粘接, 2009(4): 55-58.
[38] 王于刚, 史铁钧, 李忠. 锆改性酚醛树脂的合成与表征[J]. 化学推进剂与高分子材料, 2009, 7(4): 37-39.
[39] 张衍, 荆建芬, 王井岗, 等. 高碳酚醛树脂的结构改性[J]. 玻璃钢/复合材料, 2001(1): 10-11.
[40] 张衍, 王井岗, 刘育建, 等. 新型高残碳酚醛树脂的性能研究[J]. 宇航材料工艺, 2003, 33(5): 35-39.
[41] 胡良全. 结构改性酚醛树脂基材料性能研究[J]. 固体火箭技术, 1997, 20(1): 57-61.
[42] 陈鸯飞. 高成炭率酚醛树脂的制备及其在C/C复合材料中的应用[D]. 长沙: 湖南大学, 2013.
[43] 沈红. 杯芳烃改性低粘度高残炭酚醛树脂的研究[D]. 成都: 四川大学, 2004.
[44] 彭进, 张琳琪, 邹文俊, 等. 双马来酰亚胺改性酚醛树脂的合成研究[J]. 金刚石与磨料磨具工程, 2003(2): 45-47.
[45] 曹鹏, 齐暑华, 理莎莎, 等. 双马来酰亚胺改性酚醛树脂的制备及其性能研究[J]. 中国胶粘剂, 2011, 20(12): 16-19.
[46] 罗振华, 杨明, 刘峰, 等. 一种耐高温加成固化型酚醛树脂作为复合材料基体的评价[J]. 复合材料学报, 2009, 26(1): 13-18.
[47] 张大勇, 刘晓辉, 李欣, 等. 改性邻苯二甲腈酚醛树脂胶黏剂的研究[J]. 化学与黏合, 2014, 36(6): 421-423.
[48] 郭恒, 雷雅杰, 赵鑫, 等. 双酚 A 型双邻苯二甲腈/酚醛树脂共混体系研究[J]. 热固性树脂, 2011, 26(6): 31-34.
[49] XU S, HAN Y, GUO Y, et al. Allyl phenolic-phthalonitrile resins with tunable properties: Curing, processability and thermal stability[J]. European Polymer Journal, 2017, 95: 394-405.
[50] AUGUSTINE D, MATHEW D, NAIR C P R. Phenol-containing phthalonitrile polymers-synthesis, cure characteristics and laminate properties[J]. Polymer international, 2013, 62(7): 1068-1076.
[51] YANG X, LI K, XU M, et al. Designing a low-temperature curable phenolic/benzoxazine-functionalized phthalonitrile copolymers for high performance composite laminates[J]. Journal of Polymer Research, 2017, 24(11): 195.
[52] YANG Y, MIN Z, YI L. A novel addition curable novolac bearing phthalonitrile groups: Synthesis, characterization and thermal properties[J]. Polymer Bulletin, 2007, 59(2): 185-194.
[53] ZHANG B, LUO Z, ZHOU H, et al. Addition-curable phthalonitrile-functionalized novolac resin[J]. High Performance Polymers, 2012, 24(5): 398-404.
[54] 魏化震, 王成国, 王海庆. 高交联密度酚醛树脂的合成[J]. 塑料工业, 2003, 31(2): 16-18.
[55] 陈鸯飞, 陈智琴, 刘洪波. 酚醛树脂结构对其热解成炭特性的影响[J]. 高分子材料科学与工程, 2009, 25(5): 71-74.
[56] 齐风杰, 李锦文, 魏化震, 等. 烧蚀复合材料用酚醛树脂的结构表征及性能[J]. 热固性树脂, 2008, 23(5): 31-33.
[57] 姜丽, 王继华, 韩志东. 国内氧化石墨烯/酚醛树脂复合材料的研究进展[J]. 哈尔滨理工大学学报, 2017(2): 12-17.
[58] 田建团, 张炜, 郭亚林. 酚醛树脂/蒙脱土纳米复合材料的制备及研究进展[J]. 玻璃钢/复合材料, 2007(1): 49-53.
[59] 苏志强, 刘云芳. 碳纳米管改性酚醛树脂的研究[J]. 炭素技术, 2002(1): 3-11.
[60] 车剑飞, 肖迎红, 陆怡平, 等. 纳米粒子改性硼酚醛树脂的研究[J]. 塑料工业, 2001, 29(6): 15-16.
[61] 钱春香, 赵洪凯, 熊佑明, 等. 纳米 TiO₂粒子改性硼酚醛树脂的热性能分析[J]. 功能材料, 2006, 37(7): 1114-1117.
[62] 程建国, 胡良全, 藤惠平. 纳米炭粉改进碳/酚醛材料层间性能研究[J]. 玻璃钢/复合材料, 2003(4): 31-33.
[63] 孙燚, 涂晨辰, 谈娟娟, 等. 氧化石墨烯改性热固性酚醛树脂的热性能研究[J]. 玻璃钢/复合材料, 2018(1): 89-93.
[64] HU Y, CHEN Z, WU C, et al. The synthesis and research of glass fiber felts coated with graphene oxide/phenolic resin binder[J]. Fibers and Polymers, 2019, 20(4): 732-738.
[65] CHEN J, ZHANG W, LIU J, et al. Improved thermal stability of phenolic resin by graphene-encapsulated nano-SiO₂ hybrids[J]. Journal of Thermal Analysis and Calorimetry, 2019, 135(4): 2377-2387.
[66] 王志, 崔学林, 柴国强, 等. 碳纳米管改性钡酚醛树脂的制备及性能[J]. 消防科学与技术, 2017, 36(10): 1415-1417.
[67] 冯青平, 谢续明. 多壁碳纳米管改性热固性酚醛树脂的研究[J]. 玻璃钢/复合材料, 2007(3): 25-27.
[68] 王井岗, 黄晓松, 刘育建, 等. 新型高残碳酚醛树脂的研究Ⅰ. 高残碳酚醛树脂的合成及其残碳率[J]. 宇航材料工艺, 2001, 31(6): 47-50.
[69] 张衍, 刘育建, 王井岗. 新型改性剂对酚醛树脂成碳性能影响的研究[J]. 宇航材料工艺, 2004, 34(2): 38-40.
[70] 柯瑞林, 邹雄, 王金合, 等. 陶瓷化高分子复合材料研究进展[J]. 绝缘材料, 2018, 51(12): 1-5, 10.
[71] HUANG Z X, DING J, QIN Y, et al. Studies on pyrolysis behaviour of boron-containing phenolic resin/high-silica fiberglass fabric ceramifying composites[J]. Advanced Materials Research, 2013, 716: 304-309.
[72] QIN Y, DING J, HUANG Z X, et al. Microstructure and oxidation resistance of muscovite-glass frits loaded high silica cloth/boron-containing phenol-formaldehyde resin-based ceramifying composites[J]. Applied Mechanics and Materials, 2013, 319: 34-38.
[73] DING J, HUANG Z, LUO H, et al. The role of microcrystalline muscovite to enhance thermal stability of boron-modified phenolic resin, structural and elemental studies in boron-modified phenolic resin/microcrystalline muscovite composite[J]. Materials Research Innovations, 2015, 19(8): 605-610.
[74] 刘天祥. 可陶瓷化酚醛泡沫的制备与性能研究[D]. 武汉: 武汉理工大学, 2017.
[75] 黄志雄, 丁杰, 秦岩, 等. ZrSi₂/硼酚醛泡沫的制备及其裂解产物的增强机制[J]. 复合材料学报, 2016(10): 2174-2180.
[76] WANG F, HUANG Z, QIN Y, et al. Thermal behavior of phenolic-based ceramizable composites modified by nano-aluminum oxide[J]. High Performance Polymers, 2016, 28(9): 1096-1101.
[77] 秦岩, 饶志龙, 刘慧娟, 等. 可瓷化酚醛复合材料烧蚀隔热性能研究[J]. 玻璃钢/复合材料, 2012(s1): 52-55.
[78] 傅华东, 秦岩, 王辉, 等. 2.5D石英纤维增强硼酚醛树脂可陶瓷化复合材料的制备与烧蚀性能[J]. 复合材料学报, 2020, 37(4): 767-774.
[79] 范珊珊, 石敏先, 孟盼, 等. 助熔剂对陶瓷化硼酚醛复合材料热行为及微观结构的影响[J]. 复合材料学报, 2017(1): 60-66.
[80] SHI M, CHEN X, FAN S, et al. Fluxing agents on ceramification of composites of MgO-Al₂O₃-SiO₂/boron phenolic resin[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2018, 33(2): 381-388.
[81] SHI M X, FAN S S, LUO W, et al. Pyrolysis behaviour of boron phenolic resin-based ceramicable composites by introducing of MgO-Al₂O₃-SiO₂[J]. Advanced Materials Research, 2017, 1142: 138-145.
[82] HE D, SHI M, YANG Y, et al. Effect of inorganic components on properties of ceramizable phenolic resin matrix composites[J]. Materials Science and Engineering, 2019, 472(1): 012044.
[83] ZOU Z, QIN Y, TIAN Q, et al. The influence of zirconia fibre on ablative composite materials[J]. Plastics, Rubber and Composites, 2019, 48(5): 185-190.
[84] 谢永旺, 李峥, 夏雨, 等. 可陶瓷化酚醛树脂基复合材料烧蚀隔热性能研究[J]. 首都师范大学学报: 自然科学版, 2019, 40(5): 52-56.
[85] WANG J, JIANG N, GUO Q, et al. Study on the structural evolution of modified phenol-formaldehyde resin adhesive for the high-temperature bonding of graphite[J]. Journal of nuclear materials, 2006, 348(1-2): 108-113.