环三磷腈类阻燃剂的合成及应用研究进展

doi:10.3724/SP.J.1095.2014.30536

摘要/Abstract

摘要： 简要介绍了制备环三磷腈类阻燃剂所需起始原料六氯环三磷腈的合成方法、合成及取代反应机理；介绍了环三磷腈阻燃剂的阻燃机理；着重阐述了近20年间反应型的羟基/氨基环三磷腈、环氧基环三磷腈、含不饱和双键的环三磷腈、羧基环三磷腈阻燃剂，以及添加型烷氧基环三磷腈、芳氧基环三磷腈的合成及阻燃应用，同时综述了其应用材料的热稳定性能和阻燃性能，并对其发展趋势作了总结和展望。

关键词: 有机磷阻燃剂, 六氯环三磷腈, 阻燃机理, 反应型, 添加型

Abstract: In this paper, the synthesis and reaction mechanism of hexachlorocyclotriphosphazene were briefly introduced. The flame-retardant mechanism of cyclotriphosphazene-based flame retardants was also summarized. The reactive-type hydroxyl, amino, epoxy, alkenyl, and carboxyl, cyclotriphosphazene and the additive-type alkoxy and aryloxy cyclotriphosphazene flame retardants were elaborated on their synthesis and application. The thermal stability and flame retardant properties of cyclotriphosphazene-based flame retardant materials were summarized. The development trend of cyclotriphosphazenebased flame retardants was also summarized and prospected.

Key words: organophosphate flame retardants, hexachlorocyclotriphosphazene, flame-retardant mechanism, reactive-type, additive-type

中图分类号:

游歌云, 程之泉, 彭浩, 贺红武. 环三磷腈类阻燃剂的合成及应用研究进展[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30536.

YOU Geyun, CHENG Zhiquan, HAO Peng, HE Hongwu*. Research Progress on Synthesis and Application of Cyclotriphosphazene-based Flame Retardants[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30536.

参考文献

[1] Simonsen F A,Moller L M,Madsen T,et al. Brominated Flame Retardants:Toxicity and Ecotoxicity[D]. Danmark:Danish Environmental Protection Agency,2000.

[2] D′silva K,Fernandes A,Rose M. Brominated Organic Micropollutants-Igniting the Flame Retardant Issue[J]. Crit Rev Environ Sci Tech,2004,34(2):141-207.

[3] Lu S Y,Hamerton I. Recent Developments in the Chemistry of Halogen-free Flame Retardant Polymers[J]. Prog Polym Sci,2002,27(8):1661-1712.

[4] OU Yuxiang. Developments of Organic Phosphorus Flame Retardant Industry in China[J]. Chinese Chem Ind Eng Prog,2011,30(1):210-215(in Chinese).

欧育湘. 我国有机磷阻燃剂产业的分析与展望[J]. 化工进展,2011,30(1):210-215.

[5] Schlabach M. Brominated Flame Retardants(BFR) in the Nordic Environment[M]. Copenhagen:Nordic Council of Ministers,2011:67-68.

[6] OU Yuxiang,LI Jianjun. Flame Retardants:Properties, Manufacture and Application[M]. Beijing:Chemical Industry Press,2006:162-233(in Chinese).

欧育湘,李建军. 阻燃剂: 性能、制造及应用[M]. 北京:化学工业出版社,2006:162-233.

[7] ZHU Lijun,CHEN Jinfang. Literature Metrology Analysis of Organic Phosphorus Flame Retardant[J]. J Wuhan Inst Tech,2012,34(7):75-78(in Chinese).

朱丽君,陈金芳. 有机磷系阻燃剂文献计量学分析[J]. 武汉工程大学学报,2012,34(7):75-78.

[8] Allen,C W D. Hernandez-Rubio, Phosphazenes:A Worldwide Insight: Chapter 20:The Use of Phosphazenes as Flame Retardants[M]. New York:Nova Science Publishers,Inc.,2004:485-503.

[9] YIN Zhigang. Organic Phosphorus Compounds[M]. Beijing:Chemical Industry Press,2011:144-152(in Chinese).

尹志刚. 有机磷化合物[M]. 北京:化学工业出版社,2011,144-152.

[10] ZHANG Heng. Research Progress on Synthesis and Application of Hexachlorotriphosphazene in China[J]. Plast Addit,2012,92(2):11-17(in Chinese).

张亨. 我国六氯环三磷腈的合成和应用研究进展[J]. 塑料助剂,2012,92(2):11-17.

[11] YAN Hongxia,NING Rongchang,MA Xiaoyan. Catalytic Synthesis of n-Butyl Lactate by Polyvinyl Chloride Ferric Chloride Resin[J]. Shaanxi Chem Ind,1999,28(3):5-6(in Chinese).

颜红侠,宁荣昌,马晓燕. 六氯环三磷腈的合成进展[J]. 陕西化工,1999,28(3):5-6.

[12] MOU Li,SUN De. Synthesis of Hexachlorocy-clophosphazene Trimer[J]. J Changchun Univ,2006,16(3):55-57(in Chinese).

牟莉,孙德. 六氯环三磷腈的合成与分离[J]. 长春大学学报,2006,16(3):55-57.

[13] WU Yong,ZHU Jing,ZHAO Lei,et al. Study of Synthesis of Hexachlorocyclotriphosphazeneby Orthogonal Test[J]. Chinese Chem Res,2011,22(1):32-36(in Chinese).

吴勇,朱靖,赵磊,等. 正交法研究六氯环三磷腈的合成[J]. 化学研究,2011,22(1):32-36.

[14] BAO Dongmei,LIU Jiping. Research on Synthesis and Purification of Hexachlorocyclotriphosphazene[J]. J Funct Mater,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.

[15] CHEN Haiqun,WAN Libing,MENG Xinjing,et al. Synthesis of Hexachlorocyclotriphosphazene by an Improved Method[J]. Chinese Chem. World,2008,49(1):34-37(in Chinese).

陈海群,万利兵,孟新静,等. 一种改进的方法合成六氯环三磷腈[J]. 化学世界,2008,49(1):34-37.

[16] Allcock H R. Polyphosphazenes:New Polymers with Inorganic Backbone Atoms[J]. Science,1976,193(4259):1214-1219.

[17] Allcock H R. Polyphosphazenes[J]. J Inorg Organomet Polym,1992,2(2):197-211.

[18] Allcock H R,Connolly M S,Sisko J T,et al. Effects of Organic Side Group Structures on the Properties of Poly(organophosphazenes)[J]. Macromolecules,1988,21(2):323-334.

[19] CHEN Sheng,ZHENG Qingkang. Progress in the Research on Cyclotriphosphazene-based Flame Retardants[J]. China Text Leader,2004,5:92-96(in Chinese).

陈胜,郑庆康. 环状磷腈阻燃剂的研究进展[J]. 纺织导报,2004,5:92-96.

[20] SHAO Zonglong,LIANG Jun,SHI Hu,et al. Studies on Heat Decomposition and Combustion of Polyethylene Modified by Flame Retardants[J]. Fire Safety Sci,1998,7(1):39-43(in Chinese).

邵宗龙,梁军,时虎,等. 阻燃聚乙烯热解燃烧特性的研究[J]. 火灾科学,1998,7(1):39-43.

[21] SHI Hu,HU Yuan,Zhao Huawei. The Synthesis of Cyclotriphosphazene-based Flame Retardants and Its Application in PP[J]. Fire Tech Prod Inform,2001,9:25-28(in Chinese).

时虎,胡源,赵华伟. 磷腈阻燃剂的合成及在聚乙烯阻燃中的应用[J]. 消防技术与产品信息,2001,9:25-28.

[22] Kumar D,Khullar M,Gupta A D. Synthesis and Characterization of Novel Cyclotriphosphazene-containing Poly(ether imide)s[J]. Polymer,1993,34(14):3025-3029.

[23] Buckingham M R,Lindsay A J,Stevenson D E,et al. Synthesis and Formulation of Novel Phosphorylated Flame Retardant Curatives for Thermoset Resins[J]. Polym Degrad Stab,1996,54(2):311-315.

[24] HU Yuan,SHAO Zonglong. Synthesis of 2,2,4,4-Tetra(4′-hydroxymethylphenoxy)-6,6-diphenylcyclotriphosphazene[J]. Chinese J Appl Chem,1998,15(1):22-24(in Chinese).

胡源,邵宗龙. 2,2,4,4-四对羟甲基酚氧基-6,6-二苯基三聚磷腈的合成[J]. 应用化学,1998,15(1):22-24.

[25] MA Qin,JIANG Yuemei,HU Minqi,et al. Study on Synthesis of Hexakis [4-(hydroxymethyl) phenoxyl]cyclotriphosphazene[J]. Guangzhou Chem Ind,2011,39(5):69-71(in Chinese).

马琴,姜月梅,胡敏奇,等. 六(4-羟甲基苯氧基)环三膦腈的合成研究[J]. 广州化工,2011,39(5):69-71.

[26] XIAO Xiao,GAN Xiaoxian,GE Zhongxue,et al. Synthesis of Hex(4-hydroxyl ethoxyl)cyclotriphosphazene:CN,201210286374.5[P],2012-11-07(in Chinese).

肖啸,甘笑贤,葛忠学,等. 六(4-羟基乙氧基)环三磷腈的合成方法:中国,201210286374.5[P],2012-11-07.

[27] LI Shizhen,XU Weijian,HUANG Yuanju. Synthesis of Hexakis(4-aminophenoxy)cyclotriphosphazene[J]. Inner Mongolia Sci Tech Econ,2006,19:124-125(in Chinese).

李时珍,徐伟箭,黄远驹. 六(氨基苯氧)环三磷腈的合成[J]. 内蒙古科技与经济,2006,19:124-125.

[28] ZHANG Xuan,WU Qian,MAO Zhiping. Preparation of Hexakis(4-aminophenoxy) Cyclotriphosphazene by Hydrazine Hydrate Reduction Method[J]. Chem Reag,2012,34(11):1025-1026.

张璇,吴茜,毛志平. 水合肼还原制备六(4-氨基苯氧基)环三磷腈[J]. 化学试剂,2012,34(11):1025-1026.

[29] Levchik G F,Grigoriev Y V,Balabanovich A I,et al. Phosphorus Nitrogen Containing Fire Retardants for Poly(butylene terephthalate)[J]. Polym Int,2000,49(10):1095-1100.

[30] Qian L J,Ye L J,Xu G Z,et al. The Non-halogen Flame Retardant Epoxy Resin Based on a Novel Compound with Phosphaphenanthrene and Cyclotriphosphazene Double Functional Groups[J]. Polym Degrad Stab,2011,96(6):1118-1124.

[31] Qian L J,Ye L J,Qiu Y,et al. Thermal Degradation Behavior of the Compound Containing Phosphaphenanthrene and Phosphazene Groups and Its Flame Retardant Mechanism on Epoxy Resin[J]. Polymer,2011,52(24):5486-5493.

[32] Yuan W Z,Zhu L,Huang X B,et al. Synthesis, Characterization and Degradation of Hexa-armed Star-shaped Poly(l-lactide)s and Poly(d,l-lactide)s Initiated with Hydroxyl-terminated Cyclotriphosphazene[J]. Polym Degrad Stab,2005,87(3):503-509.

[33] Huang W K,Yeh J T,Chen K J,et al. Flame Retardation Improvement of Aqueous-based Polyurethane with Aziridinyl Phosphazene Curing System[J]. J Appl Polym Sci,2001,79(4):662-673.

[34] Kawahara T,Yuuki A,Hashimoto K,et al. Immobilization of Flame-retardant onto Silica Nanoparticle Surface and Properties of Epoxy Resin Filled with the Flame-retardant-immobilized silica(2)[J]. React Funct Polym,2013,73(3):613-618.

[35] El Gouri M,El Bachiri A,Hegazi S E,et al. Thermal Degradation of a Reactive Flame Retardant Based on Cyclotriphosphazene and Its Blend with DGEBA Epoxy Resin[J]. Polym Degrad Stab,2009,94(11):2101-2106.

[36] Chen-Yang Y W,Lee H F,Yuan C Y. A Flame-retardant Phosphate and Cyclotriphosphazene-containing Epoxy Resin:Synthesis and Properties[J]. J Polym Sci A Polym Chem,2000,38(6):972-981.

[37] Chen-Yang Y W,Yuan C Y,Li C H,et al. Preparation and Characterization of Novel Flame Retardant(aliphatic phosphate) Cyclotriphosphazene-containing Polyurethanes[J]. J Appl Polym Sci,2003,90(5):1357-1364.

[38] Yuan C Y,Chen S Y,Tsai C H,et al. Thermally Stable and Flame-retardant Aromatic Phosphate and Cyclotriphosphazene-containing Polyurethanes:Synthesis and Properties[J]. Polym Adv Technol,2005,16(5):393-399.

[39] Liu H,Wang X D,Wu D Z. Novel Cyclotriphosphazene-based Epoxy Compound and Its Application in Halogen-free Epoxy Thermosetting Systems:Synthesis, Curing Behaviors, and Flame Retardancy[J]. Polym Degrad Stab,2014,103:96-112.

[40] Bai Y W,Wang X D,Wu D Z. Novel Cyclolinear Cyclotriphosphazene-Linked Epoxy Resin for Halogen-Free Fire Resistance:Synthesis, Characterization, and Flammability Characteristics[J]. Ind Eng Chem Res,2012,51(46):15064-15074.

[41] Sun J,Wang X D,Wu D Z. Novel Spirocyclic Phosphazene-Based Epoxy Resin for Halogen-Free Fire Resistance:Synthesis, Curing Behaviors, and Flammability Characteristics[J]. Appl Mater Interfaces,2012,4(8):4047-4061.

[42] Liu R,Wang X. Synthesis, Characterization, Thermal Properties and Flame Retardancy of a Novel Nonflammable Phosphazene-based Epoxy Resin[J]. Polym Degrad Stab,2009,94(4):617-624.

[43] Gu X,Huang X,Wei H,et al. Synthesis of Novel Epoxy-group Modified Phosphazene-containing Nanotube[J]. Eur Polym J,2011,47(5):903-910.

[44] You G Y,Cai Z,Peng H,et al. A Well-defined Cyclotriphosphazene-based Epoxy Monomer and Its Application as a Novel Epoxy Resin:Synthesis, Curing Behaviors, and Flame Retardancy[J]. Phosphorus Sulfur Silicon Relat Eleme,2013,189(4):541-550.

[45] Kuan J F,Lin K F. Synthesis of Hexa-Allylamino-Cyclotriphosphazene as a Reactive Fire Retardant for Unsaturated Polyesters[J]. J Appl Polym Sci,2004,91(2):697-702.

[46] Guo Y N,Zhao C,Liu S Z,et al. Synthesis and Properties of the Optical Resin Composed of Cyclotriphosphazenes[J]. Polym Bull,2009,62(4):421-431.

[47] Herrera-Gonzlez A M,García-Serrano J,Pelaez-Cid A A,et al. Efficient Method for Polymerization of Diallycarbonate and Hexa(allylcarbonate) Monomers and Their Thermal Properties[C]. In Third Congress on Materials Science and Engineering. Mexico,2013:1-4.

[48] BING Baichun,LI Bin,HE Jia,et al. Synthesis and Thermal Properties of Hexa[p-(carboxyl) phenoxy] Cyclotriphosphazene[J]. Chinese J Appl Chem,2009,26(7):753-756(in Chinese).

邴柏春,李斌,贺贾,等. 六对羧基苯氧基环三磷腈的合成及其热性能[J]. 应用化学,2009,26(7):753-756.

[49] Tao K,Li J,Xu L,et al. A Novel Phosphazene Cyclomatrix Network Polymer:Design, Synthesis and Application in Flame Retardant Polylactide[J]. Polym Degrad Stabil,2011,96(7):1248-1254.

[50] Muraki T,Ueta M,Ihara E,et al. Enhancement of Thermal Stability of Polystyrene and Poly(methyl methacrylate) by Cyclotriphosphazene Derivatives[J]. Polym Degrad Stab,2004,84(1):87-93.

[51] Shin Y J,Ham Y R,Kim S H,et al. Application of Cyclophosphazene Derivatives as Flame Retardants for ABS[J]. Ind Eng Chem,2010,16(3):364-367.

[52] Zhang X,Zhong Y,Mao Z P. The Flame Retardancy and Thermal Stability Properties of Poly(ethylene terephthalate)/hexakis(4-nitrophenoxy) Cyclotriphosphazene Systems[J]. Polym Degrad Stabil,2012,97(8):1504-1510.

[53] Zhang X,Zhang L P,Wu Q,et al. The Influence of Synergistic Effects of Hexakis(4-nitrophenoxy) Cyclotriphosphazene and POE-g-MA on Anti-dripping and Flame Retardancy of PET[J]. J Ind Eng Chem,2013,19(3):993-999.

[54] Kumar D,Gupta A D. Aromatic Cyclolinear Phosphazene Polyimides Based on a Novel Bis-spiro-substituted Cyclotriphosphazene Diamine[J]. Macromolecules,1995,28(18):6323-6329.

[55] Mathew D,Nair C P R,Ninan K N. Phosphazene Triazine Cyclomatrix Network Polymers:Some Aspects of Synthesis, Thermal- and Flame-retardant Characteristics[J]. Polym Int,2000,49(1):48-56.

[56] Zhang T,Cai Q,Wu D Z,et al. Phosphazene Cyclomatrix Network Polymers:Some Aspects of the Synthesis, Characterization, and Flame-retardant Mechanisms of Polymer[J]. J Appl Polym Sci,2005,95(4):880-889.

[57] Wu X,Zhou Y,Liu S Z,et al. Highly Branched Benzoxazine Monomer Based on Cyclotriphosphazene:Synthesis and Properties of the Monomer and Polybenzoxazines[J]. Polymer,2011,52(4):1004-1012.

[58] Wu X,Liu S Z,Tian D T,et al. Well-defined Organic Inorganic Hybrid Benzoxazine Monomers Based on Cyclotriphosphazene:Synthesis, Properties of the Monomers and Polybenzoxazines[J]. Polymer,2011,52(19):4235-4245.