-OH磷杂菲阻燃剂的合成及其阻燃环氧树脂的性能研究
详细信息 查看官网全文
- 英文论文题名：Synthesis of α-OH phosphaphenanthrene-based Flame Retardant and Its Application in Epoxy Resins
- 论文作者：游歌云 ; 黄兴鹏 ; 李珊 ; 罗志荣 ; 陈盛余
- 英文论文作者：YOU Ge-Yun ; HUANG Xing-Peng ; Li Shan ; Luo Zhi-Rong ; Chen Sheng-Yu ; Guangxi Key Laboratory of Western Guangxi Regional Ecological Environment Analysis and Pollution Control ; College of Chemistry and Environmental Engineering ; Baise University
- 年：2017
- 作者机构：桂西区域生态环境分析与污染控制实验室百色学院化学与环境工程学院;
- 论文关键词：合成 ; 磷杂菲 ; 环氧树脂 ; 阻燃性能 ; 机械性能
- 英文论文关键词：synthesis ; phosphaphenanthrene ; epoxy resin ; flame retardancy ; mechanical property
- 会议召开时间：2017-04-21
- 会议录名称：全国阻燃剂研发与应用技术交流研讨会论文集
- 语种：中文
- 分类号：TQ314.248
- 学会代码：CJGL
- 会议名称：全国阻燃剂研发与应用技术交流研讨会
- 会议地点：中国浙江杭州
- 主办单位：中国国际科技促进会
- 学会名称：北京城建联企业管理咨询中心
- 页数：9
- 文件大小：1016k
- 原文格式：D
- 会议级别：全国
摘要
将DOPO分别与苯甲醛、对硝基苯甲醛反应,制备两种-OH磷杂菲阻燃剂PBH和PBN,并以不同磷含量添加到环氧树脂DGEBA中,采用4,4‘-二氨基二苯砜固化,制得阻燃环氧固化物。通过极限氧指数(LOI)及垂直燃烧(UL-94)测试研究了材料的阻燃性能,并通过热重分析(TGA)测试研究了材料的热稳定性和成炭生成能力。同时,通过三点弯曲和冲击强度测试对材料的机械性能作了评估。研究结果表明,含硝基的PBN对环氧树脂具有优异的残炭生成促进作用,而PBH对环氧树脂体现出比DOPO更优异的阻燃性能,当体系磷含量为1.5 wt%时,PBH-1.5/DGEBA/DDS通过UL-94 V-0级,LOI值达32.7%;同时,通过结构优化所得-OH磷杂菲衍生物PBH和PBN,在同等磷含量下,降低了DOPO结构对环氧树脂的三点弯曲强度和冲击强度的负面影响。
Two α-OH phosphaphenanthrene-based flame retardants PBH and PBN were synthesized by DOPO with benzaldehyde and p-nitrobenzaldehyde,respectively.According to different phosphorus amount,PBH and PBN were applied in DGEBA resins,and cured by 4,4'-diaminodiphenylsulfone(DDS),to prepare flame-retardant thermosets.The flame retardancy,thermal properties,mechanical properties of these modified thermosets were investigated by limiting oxygen index(LOI),vertical burning(UL-94) tests,thermogravimetric analysis(TGA),flexural strength and Izod impact strength tests,respectively.The result showed that nitro-containing PBN did excellent char forming effect on epoxy resins,PBH exhibited more excellent flame retardancy than that of commercial DOPO,PBH-1.5/DGEBA/DDS with phosphorus content of 1.5wt% could reach the highest levels of UL 94 v-0 rating,and obtain LOI value as high as 32.7%.Meanwhile,PBH and PBN exhibited less negative effect than DOPO on the flexural strength and Izod impact strength of DGEBA/DDS.
Two α-OH phosphaphenanthrene-based flame retardants PBH and PBN were synthesized by DOPO with benzaldehyde and p-nitrobenzaldehyde,respectively.According to different phosphorus amount,PBH and PBN were applied in DGEBA resins,and cured by 4,4'-diaminodiphenylsulfone(DDS),to prepare flame-retardant thermosets.The flame retardancy,thermal properties,mechanical properties of these modified thermosets were investigated by limiting oxygen index(LOI),vertical burning(UL-94) tests,thermogravimetric analysis(TGA),flexural strength and Izod impact strength tests,respectively.The result showed that nitro-containing PBN did excellent char forming effect on epoxy resins,PBH exhibited more excellent flame retardancy than that of commercial DOPO,PBH-1.5/DGEBA/DDS with phosphorus content of 1.5wt% could reach the highest levels of UL 94 v-0 rating,and obtain LOI value as high as 32.7%.Meanwhile,PBH and PBN exhibited less negative effect than DOPO on the flexural strength and Izod impact strength of DGEBA/DDS.
引文
[1]范学忠,张蓓,环氧树脂产业发展现状及趋势,中国石油和化工经济分析,2014(05):56-58.
[2]Zhang L,Wang Y,Liu Q,et al.Synergistic effects between silicon-containing flame retardant and DOPO on flame retardancy of epoxy resins[J].Journal of Thermal Analysis and Calorimetry.2015,123(2):1343-1350.
[3]Salmeia K A,Gaan S.An overview of some recent advances in DOPO-derivatives:Chemistry and flame retardant applications[J].Polym.Degrad.Stab.2015,113:119-134.
[4]Wang J,Qian L,Huang Z,et al.Synergistic flame-retardant behavior and mechanisms of aluminum poly-hexamethylenephosphinate and phosphaphenanthrene in epoxy resin[J].Polym.Degrad.Stab.2016,130:173-181.
[5]Min Y,Li P,Yin X,et al.Synthesis and characterization of an novel flame retardant based on phosphaphenanthrene for epoxy resin[J].Polym.Bull.2017,74(1):1-10.
[6]Artner J,Ciesielski M,Walter O,et al.A Novel DOPO-Based Diamine as Hardener and Flame Retardant for Epoxy Resin Systems[J].Macromolecular Materials and Engineering Macromol.Mater.Eng.2008,293(6):503-514.
[7]Schartel B,Braun U,Balabanovich A I,et al.Pyrolysis and fire behaviour of epoxy systems containing a novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-(DOPO)-based diamino hardener[J].European Polymer Journal.2008,44(3):704-715.
[8]Shree Meenakshi K,Pradeep Jaya Sudhan E,Ananda Kumar S,et al.Development and characterization of novel DOPO based phosphorus tetraglycidyl epoxy nanocomposites for aerospace applications[J].Prog.Org.Coat.2011,72(3):402-409.
[9]Perret B,Schartel B,St??K,et al.Novel DOPO-based flame retardants in high-performance carbon fibre epoxy composites for aviation[J].Eur.Polym.J.2011,47(5):1081-1089.
[10]Qian L,Qiu Y,Sun N,et al.Pyrolysis route of a novel flame retardant constructed by phosphaphenanthrene and triazine-trione groups and its flame-retardant effect on epoxy resin[J].Polym.Degrad.Stab.2014,107:98-105.
[11]Weng Z,Senthil T,Zhuo D,et al.Flame retardancy and thermal properties of organoclay and phosphorous compound synergistically modified epoxy resin[J].J.Appl.Polym.Sci.2016,133(18):1-11.
[12]Yang S,Wang J,Huo S,et al.Synthesis of a Phosphorus/Nitrogen-Containing Additive with Multifunctional Groups and Its Flame-Retardant Effect in Epoxy Resin[J].Ind.Eng.Chem.Res.2015,54(32):7777-7786.
[2]Zhang L,Wang Y,Liu Q,et al.Synergistic effects between silicon-containing flame retardant and DOPO on flame retardancy of epoxy resins[J].Journal of Thermal Analysis and Calorimetry.2015,123(2):1343-1350.
[3]Salmeia K A,Gaan S.An overview of some recent advances in DOPO-derivatives:Chemistry and flame retardant applications[J].Polym.Degrad.Stab.2015,113:119-134.
[4]Wang J,Qian L,Huang Z,et al.Synergistic flame-retardant behavior and mechanisms of aluminum poly-hexamethylenephosphinate and phosphaphenanthrene in epoxy resin[J].Polym.Degrad.Stab.2016,130:173-181.
[5]Min Y,Li P,Yin X,et al.Synthesis and characterization of an novel flame retardant based on phosphaphenanthrene for epoxy resin[J].Polym.Bull.2017,74(1):1-10.
[6]Artner J,Ciesielski M,Walter O,et al.A Novel DOPO-Based Diamine as Hardener and Flame Retardant for Epoxy Resin Systems[J].Macromolecular Materials and Engineering Macromol.Mater.Eng.2008,293(6):503-514.
[7]Schartel B,Braun U,Balabanovich A I,et al.Pyrolysis and fire behaviour of epoxy systems containing a novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-(DOPO)-based diamino hardener[J].European Polymer Journal.2008,44(3):704-715.
[8]Shree Meenakshi K,Pradeep Jaya Sudhan E,Ananda Kumar S,et al.Development and characterization of novel DOPO based phosphorus tetraglycidyl epoxy nanocomposites for aerospace applications[J].Prog.Org.Coat.2011,72(3):402-409.
[9]Perret B,Schartel B,St??K,et al.Novel DOPO-based flame retardants in high-performance carbon fibre epoxy composites for aviation[J].Eur.Polym.J.2011,47(5):1081-1089.
[10]Qian L,Qiu Y,Sun N,et al.Pyrolysis route of a novel flame retardant constructed by phosphaphenanthrene and triazine-trione groups and its flame-retardant effect on epoxy resin[J].Polym.Degrad.Stab.2014,107:98-105.
[11]Weng Z,Senthil T,Zhuo D,et al.Flame retardancy and thermal properties of organoclay and phosphorous compound synergistically modified epoxy resin[J].J.Appl.Polym.Sci.2016,133(18):1-11.
[12]Yang S,Wang J,Huo S,et al.Synthesis of a Phosphorus/Nitrogen-Containing Additive with Multifunctional Groups and Its Flame-Retardant Effect in Epoxy Resin[J].Ind.Eng.Chem.Res.2015,54(32):7777-7786.