磷腈阻燃环氧树脂的制备及热分解动力学研究
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摘要
以六氯环三磷腈(HCCP)和对羟基苯甲醛为原料,一步法合成了六(4-醛基苯氧基)环三磷腈(HAPCP)。然后以HAPCP为阻燃剂,将其添加到环氧树脂(EP)中制备阻燃环氧树脂(FR/EP)。最后,通过热重法(TG)和微商热重法(DTG),研究了EP和FR/EP在氮气气氛下的热分解动力学行为,运用Flynn-WallOzawa(FWO)法和Kissinger法求出EP和FR/EP的热分解反应的活化能E和指前因子A,采用Coast-Redfern法确定了热分解动力学机理函数g(α)和反应级数n。实验结果表明,相同升温速率下,FR/EP的热分解反应的活化能比EP的低,其活化能和指前因子分别为Ek(FR/EP)=1.34×105 J/mol,EO(FR/EP)=1.38×105 J/mol,A(FR-EP)=1.4×1010 min-1,FR/EP的热分解动力学方程为g(α)=1-(1-α)3,反应级数n=3。
Hexakis(4-formacylphenoxy)cyclotriphosphazene(HAPCP)was synthesized by one-step synthesis using hexachlorocyclotriphosphazene(HCCP)and 4-hydroxybenzaldehyde as raw materials.Then HAPCP was used in epoxy resins as flame retardant in certain proportion.The thermal decomposition kinetics of EP and FR/EP in the atmosphere of nitrogen were studied by TG-DTG.The thermal decomposition kinetic parameters,including pre-exponential factor A and activation energy E,the thermal decomposition kinetic mechanism function and reaction order of the thermal decomposition reaction of EP and FR/EP were calculated by Kissinger,Flynn-Wall-Ozawa(FWO)and Coast-Redfern equation.The results show that the activation energy Eof FR/EP is lower than that of EP with the same heating rate.The thermal decomposition activation energy of FR/EP are1.34×105 J/mol(Ek)and 1.38×105 J/mol(EO)and its pre-exponential factor Ais 1.4×1010 min-1.The thermal decomposition kinetic equation of FR/EP can be expressed as g(α)=1-(1-α)3,while the reaction order n=3.
Hexakis(4-formacylphenoxy)cyclotriphosphazene(HAPCP)was synthesized by one-step synthesis using hexachlorocyclotriphosphazene(HCCP)and 4-hydroxybenzaldehyde as raw materials.Then HAPCP was used in epoxy resins as flame retardant in certain proportion.The thermal decomposition kinetics of EP and FR/EP in the atmosphere of nitrogen were studied by TG-DTG.The thermal decomposition kinetic parameters,including pre-exponential factor A and activation energy E,the thermal decomposition kinetic mechanism function and reaction order of the thermal decomposition reaction of EP and FR/EP were calculated by Kissinger,Flynn-Wall-Ozawa(FWO)and Coast-Redfern equation.The results show that the activation energy Eof FR/EP is lower than that of EP with the same heating rate.The thermal decomposition activation energy of FR/EP are1.34×105 J/mol(Ek)and 1.38×105 J/mol(EO)and its pre-exponential factor Ais 1.4×1010 min-1.The thermal decomposition kinetic equation of FR/EP can be expressed as g(α)=1-(1-α)3,while the reaction order n=3.
引文
[1] Schafer A,Seibold S,Walter O,et al.Novel high Tg flame retardancy approach for epoxy resins[J].Polymer Degradation and Stability,2008,93(2):557-560.
[2] Kandola B K,Biswas B,Price D,et al.Studies on the effect of different levels of toughener and flame retardants on thermal stability of epoxy resin[J].Polymer Degradation and Stability,2010,95(2):144-152.
[3] Shieh J Y,Wang C S.Synthesis of novel flame retardant epoxy harderers and properties of cured products[J].Polymer,2001,42:7617-7625.
[4] Levchik S,Piotrowski A,Weil E,et al.New developments iname retardancy of epoxy resins[J].Polymer Degradation and Stability,2005,88:57-62.
[5] Choi S W,Ohba S,Brunovska Z,et al.Synthesis,characterization and thermal degradation of functionalbenzoxazine monomers and polymers containing phenylphosphine oxide[J].Polymer Degradation and Stability,2006,91(5):1166-1178.
[6] Zima V,Svoboda J,Benes L,et al.Synthesis and characterization of new strontium 4-carboxyphenylphosphonates[J].Journal of Solid State Chemistry,2007,180(3):929-939.
[7] You Geyun,Cheng Zhiquan,Peng Hao,et al.Research progress on synthesis and application ofcyclotriphosphazene-based flame retardants[J].Chinese journal of applied chemistry,2014,31(9):993(in Chinese).游歌云,程之泉,彭浩,等.环三磷腈类阻燃剂的合成及应用研究进展[J].应用化学,2014,31(9):993.
[8] Ma Shangquan,Kang Huihua,Qian Rui,et al.Application of a new type of phosphonitrile flame retardant to the flame retardancy of epoxy resin[J].Journal of North China Institute of Science and Technology,2018,15(3):60-64.
[9] Ye Longjian,Qian Lijun,Tong Shaopeng,et al.Research progress of halogen-free flame-retardant phosphorus-containing epoxy resins[J].China plastics,2010,24(3):11-16(in Chinese).叶龙健,钱立军,佟芍朋,等.无卤阻燃含磷环氧树脂的研究进展[J].中国塑料,2010,24(3):11-16.
[10] Liu R,Wang X D.Synthesis,characterization,thermal properties and flame retardancy of a novel nonflammable phosphazene-based epoxy resin[J].Polymer Degradation and Stability,2009,94(4):617-624.
[11] Gouri M E,Bachiri A E,Hegazi S E,et al.Thermal degradation of a reactive flame retardant based on cyclotriphosphazene and its blend with DGEBA epoxy resin[J].Polymer Degradation and Stability,2009,94(11):2101-2106.
[12] Lu Lingang,Yang Shousheng,Zhang Yan,et al.Synthesis and Thermal Decomposition Kinetics of Novel Flame Retardant 1,3,5-Tris(5,5-dimethyl-1,3-dioxa-2-oxophosphorinanyl-2-oxy)benzene[J].Acta Chimica Sinica,2009,67(14):1695-1699(in Chinese).卢林刚,杨守生,张燕,等.新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯的合成及热分解动力学研究[J].化学学报,2009,67(14):1695-1699.
[13] Bao Dongmei,Liu Jiping.Research on synthesis and purification of hexachlorocyclotriphosphazene[J].Journal of Functional Materials,2012,43(14):1960-1963(in Chinese).宝冬梅,刘吉平.六氯环三磷腈的合成与精制研究[J].功能材料,2012,43(14):1960-1963.
[14] Bao Dongmei,Liu Jiping.Research on synthesis and thermal properties of hexakis(4-formacylphenoxy)cyclotriphosphazene[J].Journal of Functional Materials,2013,44(3):396-400(in Chinese).宝冬梅,刘吉平.六对醛基苯氧基环三磷腈的合成及其热性能研究[J].功能材料,2013,44(3):396-400.
[15] Lu Lingang,Zhang Qing,Xu Xiaonan,et al.Thermal Degradation Kinetics of Novel IntumescentFlame Retardant Polypropylene[J].China plastics,2009,23(5):53-60(in Chinese).卢林刚,张晴,徐晓楠,等.新型膨胀阻燃聚丙烯的热分解动力学研究[J].中国塑料,2009,23(5):53-60.
[16] Xu Xiaonan.The kinetic study on thermal degradation of brominated epoxy resin in synchronizing antimony trioxide flame-retarded pet[J].Fire science and technology,2010,29(5):416-419(in Chinese).徐晓楠.溴化环氧树脂协同三氧化二锑阻燃PET热分解动力学研究[J].消防科学与技术,2010,29(5):416-419.
[17] Deng Limin,Huang Zhiyu,Zhao Chunxia.Effect of Si-P Containing flame retardant on the thermal degradation behavior of epoxy[J].Materials Review,2014,28(2):92-94(in Chinese).邓利民,黄志宇,赵春霞.Si-P阻燃剂对环氧树脂热降解行为的影响[J].材料导报,2014,28(2):92-94.
[18] Tian Xiujuan,Wang Zhongwei,Yu Qing,et al.Kinetics of thermal decomposition of epoxy resins modified with phosphorus-containing flame retardant[J].CIESC Journal,2014,65(12):5082-5089(in Chinese).田秀娟,王忠卫,于青,等.含磷阻燃剂阻燃环氧树脂热降解动力学[J].化工学报,2014,65(12):5082-5089.
[19] Lu Lingang,Han Zhongkai,Yang Shousheng.Study on thermal decomposition kinetics of novel halogen-free flame retardant from bisphenol S-bis(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy)[J].Journal of Molecular Science,2010,26(4):261-265(in Chinese).卢林刚,韩中凯,杨守生.新型无卤阻燃剂双酚S-二(5,5-二甲基-1,3-二氧杂己内磷酸酯)的热分解动力学研究[J].分子科学学报,2010,26(4):261-265.
[20] Ren Yuanlin,Cheng Bowen,Xu Ling,et al.Non-isothermal decomposition kinetics of novel fire retarded polyacrylonitrile copolymer in Air[J].Acta Chimica Sinica,2009,67(18):2127-2132(in Chinese).任元林,程博闻,徐玲,等.新型阻燃聚丙烯腈共聚物在空气中的非等温热分解动力学[J].化学学报,2009,67(18):2127-2132.
[21] Ren Yuanlin,Cheng Bowen,Zhang Jinshu,et al.Study on thermal decomposition kinetics of N,N′-Bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine in Air[J].Acta Chimica Sinica,2008,66(9):1123-1126(in Chinese).任元林,程博闻,张金树,等.N,N′-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺在空气中的热分解动力学研究[J].化学学报,2008,66(9):1123-1126.
[22] Hu Rongzu,Shi Qizhen.Thermal Analysis Kinetics[M].Beijing:Science Press,2001:65.
[23] Xu Xiaonan,Wang Fang,Zhang Qing.Study on thermal decomposition kinetics of PBT flame-retarded by brominated epoxy resin synchronized with antimony trioxide[J].Plastics Science and Technology,2009,37(10):34-39.
[24] Lu Lingang,Zhang Yan,Yang Shousheng,et al.Thermal decomposition kinetics of novel flame retardantfrom1,3,5-tri(5,5-dibromomethyl-1,3,-dioxaphosphorinanyl-2-oxy)benzene[J].Plastics,2009,38(1):43-46.
[2] Kandola B K,Biswas B,Price D,et al.Studies on the effect of different levels of toughener and flame retardants on thermal stability of epoxy resin[J].Polymer Degradation and Stability,2010,95(2):144-152.
[3] Shieh J Y,Wang C S.Synthesis of novel flame retardant epoxy harderers and properties of cured products[J].Polymer,2001,42:7617-7625.
[4] Levchik S,Piotrowski A,Weil E,et al.New developments iname retardancy of epoxy resins[J].Polymer Degradation and Stability,2005,88:57-62.
[5] Choi S W,Ohba S,Brunovska Z,et al.Synthesis,characterization and thermal degradation of functionalbenzoxazine monomers and polymers containing phenylphosphine oxide[J].Polymer Degradation and Stability,2006,91(5):1166-1178.
[6] Zima V,Svoboda J,Benes L,et al.Synthesis and characterization of new strontium 4-carboxyphenylphosphonates[J].Journal of Solid State Chemistry,2007,180(3):929-939.
[7] You Geyun,Cheng Zhiquan,Peng Hao,et al.Research progress on synthesis and application ofcyclotriphosphazene-based flame retardants[J].Chinese journal of applied chemistry,2014,31(9):993(in Chinese).游歌云,程之泉,彭浩,等.环三磷腈类阻燃剂的合成及应用研究进展[J].应用化学,2014,31(9):993.
[8] Ma Shangquan,Kang Huihua,Qian Rui,et al.Application of a new type of phosphonitrile flame retardant to the flame retardancy of epoxy resin[J].Journal of North China Institute of Science and Technology,2018,15(3):60-64.
[9] Ye Longjian,Qian Lijun,Tong Shaopeng,et al.Research progress of halogen-free flame-retardant phosphorus-containing epoxy resins[J].China plastics,2010,24(3):11-16(in Chinese).叶龙健,钱立军,佟芍朋,等.无卤阻燃含磷环氧树脂的研究进展[J].中国塑料,2010,24(3):11-16.
[10] Liu R,Wang X D.Synthesis,characterization,thermal properties and flame retardancy of a novel nonflammable phosphazene-based epoxy resin[J].Polymer Degradation and Stability,2009,94(4):617-624.
[11] Gouri M E,Bachiri A E,Hegazi S E,et al.Thermal degradation of a reactive flame retardant based on cyclotriphosphazene and its blend with DGEBA epoxy resin[J].Polymer Degradation and Stability,2009,94(11):2101-2106.
[12] Lu Lingang,Yang Shousheng,Zhang Yan,et al.Synthesis and Thermal Decomposition Kinetics of Novel Flame Retardant 1,3,5-Tris(5,5-dimethyl-1,3-dioxa-2-oxophosphorinanyl-2-oxy)benzene[J].Acta Chimica Sinica,2009,67(14):1695-1699(in Chinese).卢林刚,杨守生,张燕,等.新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯的合成及热分解动力学研究[J].化学学报,2009,67(14):1695-1699.
[13] Bao Dongmei,Liu Jiping.Research on synthesis and purification of hexachlorocyclotriphosphazene[J].Journal of Functional Materials,2012,43(14):1960-1963(in Chinese).宝冬梅,刘吉平.六氯环三磷腈的合成与精制研究[J].功能材料,2012,43(14):1960-1963.
[14] Bao Dongmei,Liu Jiping.Research on synthesis and thermal properties of hexakis(4-formacylphenoxy)cyclotriphosphazene[J].Journal of Functional Materials,2013,44(3):396-400(in Chinese).宝冬梅,刘吉平.六对醛基苯氧基环三磷腈的合成及其热性能研究[J].功能材料,2013,44(3):396-400.
[15] Lu Lingang,Zhang Qing,Xu Xiaonan,et al.Thermal Degradation Kinetics of Novel IntumescentFlame Retardant Polypropylene[J].China plastics,2009,23(5):53-60(in Chinese).卢林刚,张晴,徐晓楠,等.新型膨胀阻燃聚丙烯的热分解动力学研究[J].中国塑料,2009,23(5):53-60.
[16] Xu Xiaonan.The kinetic study on thermal degradation of brominated epoxy resin in synchronizing antimony trioxide flame-retarded pet[J].Fire science and technology,2010,29(5):416-419(in Chinese).徐晓楠.溴化环氧树脂协同三氧化二锑阻燃PET热分解动力学研究[J].消防科学与技术,2010,29(5):416-419.
[17] Deng Limin,Huang Zhiyu,Zhao Chunxia.Effect of Si-P Containing flame retardant on the thermal degradation behavior of epoxy[J].Materials Review,2014,28(2):92-94(in Chinese).邓利民,黄志宇,赵春霞.Si-P阻燃剂对环氧树脂热降解行为的影响[J].材料导报,2014,28(2):92-94.
[18] Tian Xiujuan,Wang Zhongwei,Yu Qing,et al.Kinetics of thermal decomposition of epoxy resins modified with phosphorus-containing flame retardant[J].CIESC Journal,2014,65(12):5082-5089(in Chinese).田秀娟,王忠卫,于青,等.含磷阻燃剂阻燃环氧树脂热降解动力学[J].化工学报,2014,65(12):5082-5089.
[19] Lu Lingang,Han Zhongkai,Yang Shousheng.Study on thermal decomposition kinetics of novel halogen-free flame retardant from bisphenol S-bis(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy)[J].Journal of Molecular Science,2010,26(4):261-265(in Chinese).卢林刚,韩中凯,杨守生.新型无卤阻燃剂双酚S-二(5,5-二甲基-1,3-二氧杂己内磷酸酯)的热分解动力学研究[J].分子科学学报,2010,26(4):261-265.
[20] Ren Yuanlin,Cheng Bowen,Xu Ling,et al.Non-isothermal decomposition kinetics of novel fire retarded polyacrylonitrile copolymer in Air[J].Acta Chimica Sinica,2009,67(18):2127-2132(in Chinese).任元林,程博闻,徐玲,等.新型阻燃聚丙烯腈共聚物在空气中的非等温热分解动力学[J].化学学报,2009,67(18):2127-2132.
[21] Ren Yuanlin,Cheng Bowen,Zhang Jinshu,et al.Study on thermal decomposition kinetics of N,N′-Bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine in Air[J].Acta Chimica Sinica,2008,66(9):1123-1126(in Chinese).任元林,程博闻,张金树,等.N,N′-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺在空气中的热分解动力学研究[J].化学学报,2008,66(9):1123-1126.
[22] Hu Rongzu,Shi Qizhen.Thermal Analysis Kinetics[M].Beijing:Science Press,2001:65.
[23] Xu Xiaonan,Wang Fang,Zhang Qing.Study on thermal decomposition kinetics of PBT flame-retarded by brominated epoxy resin synchronized with antimony trioxide[J].Plastics Science and Technology,2009,37(10):34-39.
[24] Lu Lingang,Zhang Yan,Yang Shousheng,et al.Thermal decomposition kinetics of novel flame retardantfrom1,3,5-tri(5,5-dibromomethyl-1,3,-dioxaphosphorinanyl-2-oxy)benzene[J].Plastics,2009,38(1):43-46.