基于酚醛/聚乙烯醇缩丁醛(PF/PVB)树脂体系开展阻燃改性研究,以乙醇为溶剂,分别采用苯并噁嗪树脂(BOZ)、10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)和羟基乙叉二膦酸(HEDP)这3种改性剂对PF/PVB树脂进行阻燃改性研究,制备了成膜性良好、阻燃性和热稳定性优异的改性酚醛树脂薄膜。结果表明:使用3种改性剂阻燃改性酚醛树脂薄膜的极限氧指数(LOI值)从19.8%分别提高到22.2%、22.4%和26.6%,600℃残炭率分别从31.8%提高到39.9%、45.7%和42.6%,3种阻燃改性剂具有不同的阻燃机理。当体系配比为PF/PVB/HEDP=60/40/5时,树脂薄膜具有最佳的阻燃性能。
Based on phenolic/polyvinyl butyral (PF/PVB) resin system,the flame retardant modification was studied by using ethanol as the solvent and adding three modifiers,benzoxazine resin (BOZ),10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxazo-10-phosphoxafe-10-oxide (DOPO-HQ) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP).Modified phenolic resin films with excellent film forming property,flame retardancy and thermal stability were prepared.The results showed that the limiting oxygen indexes (LOI) of the phenolic resin films prepared by three modifiers were increased from 19.8% to 22.2%,22.4% and 26.6%,respectively,and the carbon residue rates at 600℃ were increased from 31.8% to 39.9%,45.7% and 42.6%,respectively.The three flame retardant modifiers had different flame retardant mechanisms.When the ratio of PF/PVB/HEDP was 60/40/5,the resin film had the best flame retardant property.
[1] 朱永茂,杨小云,王文浩,等.2020—2021年世界塑料工业进展(Ⅲ):热固性树脂[J].塑料工业,2022,50(5):32-55.
[2] 曹维宇,杨学萍,张藕生.我国高性能高分子复合材料发展现状与展望[J].中国工程科学,2020,22(5):112-120.
[3] Dewangan M K,Panigrahi S K.Factors influencing the ballistic impact mechanisms of textile composite materials:a review[J].Polymer Advanced Technologies,2021,32(5):1901-1923.
[4] 周书助,尹绍峰,黄启忠,等.PVB改性酚醛树脂对PEMFC碳纸的影响[J].高科技纤维与应用,2017,42(2):32-36,49.
[5] 王伟伟.酚醛树脂增韧增强改性的研究[D].天津:天津工业大学,2019.
[6] 张丽青,张国利,王伟伟,等.聚乙烯醇缩丁醛改性酚醛树脂的耐热与增韧性能[J].高分子材料科学与工程,2021,37(6):85-93.
[7] 许国娟,贾晨辉,陈敬菊,等.酚醛树脂的耐冲击增韧改性及其固化动力学研究[J].复合材料科学与工程,2022(4):104-110.
[8] Cao G P,Chen W J,Liu X B.Synthesis and thermal properties of the thermosetting resin based on cyano functionalized benzoxazine[J].Polymer Degradation and Stability,2007,93(3):739-744.
[9] Li Shengfang.Synthesis of benzoxazine-based phenolic resin containing furan groups[J].Chinese Chemical Letters,2010,21(7):868-871.
[10] 张通,龙丽娟,何文涛,等.9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物阻燃聚乳酸的性能研究[J].高分子学报,2019,50(1):71-81.
[11] 徐文静,龙丽娟,徐国敏,等.DOPO衍生物/聚乳酸复合材料的热降解、阻燃及力学性能[J].复合材料学报,2021,38(9):2841-2854.
[12] 曹俊,梁兵.DOPO型无卤阻燃环氧树脂体系研究进展[J].化工新型材料,2011,39(8):7-9,14.
[13] 霍思奇.DOPO基本征型阻燃环氧树脂体系的设计制备及其性能研究[D].武汉:武汉理工大学,2018.
[14] 张宝营,董运勤,刘雪艳,等.阻燃改性酚醛树脂泡沫的制备及性能[J].合成树脂及塑料,2021,38(4):18-20,50.
[15] 姜鹏.新型含磷阻燃剂的合成及其阻燃聚乳酸复合材料的研究[D].北京:北京化工大学,2016.
[16] 冀克俭,邓卫华,张银生,等.新型酚醛树脂固化过程的表征研究[J].工程塑料应用,2003(4):44-47.
[17] 朱新生,谢洪德,程嘉琪,等.谈有机材料的耐热性与阻燃性关系[J].火灾科学,2001(2):103-107.
[18] 曾彬,李茂东,朱志平,等.HEDP的热分解特性及其阻垢性能评价[J].工业水处理,2013,33(6):47-50.
[19] 高生.含硅、硼苯并噁嗪树脂的合成及其可再加工性、阻燃性研究[D].济南:山东大学,2019.
PDF
