1，3，2-二氧磷杂环己烷衍生物的合成和阻燃性能的研究
|
摘要
高分子材料的应用领域日益扩大，已遍及国民经济的各个领域和人民生活的各个方面，由其可燃性所带来的火灾危险已受到各国政府和人民的密切关注，也是有关人类和环境的重大社会问题。因此，推广使用阻燃材料，对易燃和可燃材料进行阻燃处理，制订合理的阻燃法规和阻燃标准，以提高全社会防止火灾的能力，尽量减少火灾损失，具有重大的现实意义。
由于对材料的抑烟、减毒要求日益严格，使当今许多传统的阻燃剂面临困境，而膨胀型阻燃剂低烟、低毒的特点正给它的发展提供了良好的机遇，成为20世纪90年代以来阻燃剂最为活跃的研究领域之一，也被认为是实现阻燃无卤化的很有希望的途径之一。
因此，我们设计并合成了集酸源、炭源、气源于一体的三个系列二十四个未见文献报导的化合物：①N，N′-双(5，5-二甲基-4-芳基-2-氧(硫)代-1，3，2-二氧磷杂环己基-2-)哌嗪；②N，N′-双(5，5-二甲基-4-芳基-2-氧(硫)代-1，3，2-二氧磷杂环己基-2-)乙(丙、己)二胺；③N，N′-双(5，5-二甲基-4-芳基-2-氧(硫)代-1，3，2-二氧磷杂环己基-2-)脲(硫脲、胍)。我们对反应条件和后处理过程进行了探索和改进。采用IR、~1HNMR、~(31)PNMR、MS和元素分析等方法对目标化合物进行了结构表征，并对其波谱性质进行了系统分析，结果表明合成化合物的结构和预期目标化合物结构一致。
对部分具有代表性的化合物进行了热重(TG)和差示扫描量热(DSC)分析，这些化合物多数在220℃以上开始分解，具有一定的热稳定性，在220～400℃降解迅速，与大部分高分子材料的热氧降解温区重叠，具有较好的阻燃配伍性能；600℃时，残炭量较高，具有较好的成炭作用。前两个系列的化合物在相应失重温区内都出现了吸热峰，这对阻燃体系是非常有利的。
将这三个系列化合物分别应用于醇酸清漆、环氧树脂(E-44)中进行初步阻燃性能测试。其中用于环氧树脂(E-44)的水平燃烧试验(GB2408-80)是标准实验方法。结果表明，题称化合物具有较好的阻燃效果。阻燃醇酸清漆时，添加量为1％可以达到1～2秒钟内的自熄效果；当添加量为10％时，环氧树脂样条燃烧长度在10～20mm左右，均能达到自熄效果。前两个系列的化合物在
环氧树脂（E－44）中的阻燃效果明显优于第三系列。燃烧过程中有发泡膨胀现
象，样品离火后迅速炭化自熄，无熔融、滴落现象，发烟量小，是一类较好的
膨胀型阻燃剂。本论文阐述了膨胀型阻燃剂的阻燃机理，依据阻燃效果的不同，
初步探讨了磷、硫、芳构型碳含量对阻燃性能的影响。
通过热分析和初步阻燃实验结果表明，我们所合成的目标化合物都具有较
好的阻燃性能，与高分子材料具有较好的配伍性，是一类具有应用开发价值的
膨胀型阻燃剂。
With the development of science technology, the application of polymeric materials has been on the rise and has involved almost every aspect of people's daily life. Accordingly, the fire disasters caused by then- combustion, which is a social problem that concerns all human beings and then- environment, have attracted more and more attention from people all over the world. Thus, it is of great significance to carry research on the treatment of inflammable materials with flame retardants, and to lay out reasonable flame retardant regulation and standard so as to improve people capability of preventing fire disasters and to reduce the loss caused by those disasters.
Many traditional flame retardants are in a dilemma due to the more and more strict requirement of less smoke and less poisonous, which, however, offers a good opportunity for the development of the inrumescent flame retardant(IFR) owing to its low smoke and low poison characteristics,and IFR has becoming one of the most active research fields and one of the most promising approach to realizing the accomplishment of research on non-halogen flame retardant.
Therefore, we design and synthesize 24 novel compounds that have never been Reported in any literature:(1)N,N-bis(5,5-dimethyl-4-aiyl-2-oxo(sul)-l,3,2-dioxaph osphacyclohexyl-2-)piperazine;(2)N,N'-bis(5,5-dunethyl-4-aryl-2-oxo(sul)-1,3,2-di oxaphosphacyclohexyl-2-)ethylene(promethylene,hexmethylene)diamine;(3)N,N'-bis(5,5-dimethyl-4-aryl-2-oxo(sul)-l,3,2-dioxaphosphacyclohexyl-2-)urea(thiourea ,imino-urea).The reaction conditions and after-treatment process are studied and improved. The structure of the target compounds are confirmed by IR, 1HNMR, 31NMR, MS and elementary analysis. The spectroscopy properties are analyzed systematically. Result shows that the structures of the synthesized compounds are identical with the expected ones.
TG and DSC analysis of some of the typical compounds are discussed. Most of the compounds begin to decompose at 220℃ and have certain thermal stability.
They decompose rapidly during 220-400℃ and overlap many high polymer materials decomposition temperature range and show good fireproofing performance with materials.The high carbon residues at 600℃, which shows that the compounds have good carbonization function.
We apply the compounds to alkyd resin varnish, epoxy resin(E-44) to test their flame resistanc. Among the methods the level combustion method (GB2408-80) used in epoxy resin are standard methods. Result indicates that the title compounds have better flame resistance capability. The compounds I have the effect of self-extinguish within Is or 2s with 1% addition in alkyd resin varnish. All title compounds have the effect of self-extinguish with 10% addition in epoxy resin(E-44), and the combustion length is about 10~20mm in the level combustion test. Compounds I and II have better flame retardance than compounds III in epoxy resin(E-44). The samples foam and expand during the combustion process, and they carbonize and extinguish right after being deviated from fire, without melting and dropping and with low smoking. The thesis also gives a brief description of flame-retarding mechanisms and discusses the influence of the factor, such as P%,S% and the existence of aromatization carbon on flame retardance.
The above thermal analysis and initial fireproofing test show that the target compounds do have better flame retardance and are promising m flame retardants.
由于对材料的抑烟、减毒要求日益严格，使当今许多传统的阻燃剂面临困境，而膨胀型阻燃剂低烟、低毒的特点正给它的发展提供了良好的机遇，成为20世纪90年代以来阻燃剂最为活跃的研究领域之一，也被认为是实现阻燃无卤化的很有希望的途径之一。
因此，我们设计并合成了集酸源、炭源、气源于一体的三个系列二十四个未见文献报导的化合物：①N，N′-双(5，5-二甲基-4-芳基-2-氧(硫)代-1，3，2-二氧磷杂环己基-2-)哌嗪；②N，N′-双(5，5-二甲基-4-芳基-2-氧(硫)代-1，3，2-二氧磷杂环己基-2-)乙(丙、己)二胺；③N，N′-双(5，5-二甲基-4-芳基-2-氧(硫)代-1，3，2-二氧磷杂环己基-2-)脲(硫脲、胍)。我们对反应条件和后处理过程进行了探索和改进。采用IR、~1HNMR、~(31)PNMR、MS和元素分析等方法对目标化合物进行了结构表征，并对其波谱性质进行了系统分析，结果表明合成化合物的结构和预期目标化合物结构一致。
对部分具有代表性的化合物进行了热重(TG)和差示扫描量热(DSC)分析，这些化合物多数在220℃以上开始分解，具有一定的热稳定性，在220～400℃降解迅速，与大部分高分子材料的热氧降解温区重叠，具有较好的阻燃配伍性能；600℃时，残炭量较高，具有较好的成炭作用。前两个系列的化合物在相应失重温区内都出现了吸热峰，这对阻燃体系是非常有利的。
将这三个系列化合物分别应用于醇酸清漆、环氧树脂(E-44)中进行初步阻燃性能测试。其中用于环氧树脂(E-44)的水平燃烧试验(GB2408-80)是标准实验方法。结果表明，题称化合物具有较好的阻燃效果。阻燃醇酸清漆时，添加量为1％可以达到1～2秒钟内的自熄效果；当添加量为10％时，环氧树脂样条燃烧长度在10～20mm左右，均能达到自熄效果。前两个系列的化合物在
环氧树脂（E－44）中的阻燃效果明显优于第三系列。燃烧过程中有发泡膨胀现
象，样品离火后迅速炭化自熄，无熔融、滴落现象，发烟量小，是一类较好的
膨胀型阻燃剂。本论文阐述了膨胀型阻燃剂的阻燃机理，依据阻燃效果的不同，
初步探讨了磷、硫、芳构型碳含量对阻燃性能的影响。
通过热分析和初步阻燃实验结果表明，我们所合成的目标化合物都具有较
好的阻燃性能，与高分子材料具有较好的配伍性，是一类具有应用开发价值的
膨胀型阻燃剂。
With the development of science technology, the application of polymeric materials has been on the rise and has involved almost every aspect of people's daily life. Accordingly, the fire disasters caused by then- combustion, which is a social problem that concerns all human beings and then- environment, have attracted more and more attention from people all over the world. Thus, it is of great significance to carry research on the treatment of inflammable materials with flame retardants, and to lay out reasonable flame retardant regulation and standard so as to improve people capability of preventing fire disasters and to reduce the loss caused by those disasters.
Many traditional flame retardants are in a dilemma due to the more and more strict requirement of less smoke and less poisonous, which, however, offers a good opportunity for the development of the inrumescent flame retardant(IFR) owing to its low smoke and low poison characteristics,and IFR has becoming one of the most active research fields and one of the most promising approach to realizing the accomplishment of research on non-halogen flame retardant.
Therefore, we design and synthesize 24 novel compounds that have never been Reported in any literature:(1)N,N-bis(5,5-dimethyl-4-aiyl-2-oxo(sul)-l,3,2-dioxaph osphacyclohexyl-2-)piperazine;(2)N,N'-bis(5,5-dunethyl-4-aryl-2-oxo(sul)-1,3,2-di oxaphosphacyclohexyl-2-)ethylene(promethylene,hexmethylene)diamine;(3)N,N'-bis(5,5-dimethyl-4-aryl-2-oxo(sul)-l,3,2-dioxaphosphacyclohexyl-2-)urea(thiourea ,imino-urea).The reaction conditions and after-treatment process are studied and improved. The structure of the target compounds are confirmed by IR, 1HNMR, 31NMR, MS and elementary analysis. The spectroscopy properties are analyzed systematically. Result shows that the structures of the synthesized compounds are identical with the expected ones.
TG and DSC analysis of some of the typical compounds are discussed. Most of the compounds begin to decompose at 220℃ and have certain thermal stability.
They decompose rapidly during 220-400℃ and overlap many high polymer materials decomposition temperature range and show good fireproofing performance with materials.The high carbon residues at 600℃, which shows that the compounds have good carbonization function.
We apply the compounds to alkyd resin varnish, epoxy resin(E-44) to test their flame resistanc. Among the methods the level combustion method (GB2408-80) used in epoxy resin are standard methods. Result indicates that the title compounds have better flame resistance capability. The compounds I have the effect of self-extinguish within Is or 2s with 1% addition in alkyd resin varnish. All title compounds have the effect of self-extinguish with 10% addition in epoxy resin(E-44), and the combustion length is about 10~20mm in the level combustion test. Compounds I and II have better flame retardance than compounds III in epoxy resin(E-44). The samples foam and expand during the combustion process, and they carbonize and extinguish right after being deviated from fire, without melting and dropping and with low smoking. The thesis also gives a brief description of flame-retarding mechanisms and discusses the influence of the factor, such as P%,S% and the existence of aromatization carbon on flame retardance.
The above thermal analysis and initial fireproofing test show that the target compounds do have better flame retardance and are promising m flame retardants.
引文
[1] 欧育湘．阻燃剂—制造、性能及应用．北京：兵器工业出版社，1997
[2] 欧育湘，陈宇，王筱梅．阻燃高分子材料．北京：国防工业出版社，2001
[3] 朱艳秋．聚烯烃阻燃剂的发展动态．石化技术，2003，4
[4] 贺峥杰，陈文彬，唐除痴．有机磷阻燃剂研究进展．化学工业与工程，1997,14(3)：43～49
[5] 欧育湘．有机阻燃剂最新进展．现代化工，1997,4：9～12
[6] 贡长生．磷系阻燃剂的现状和发展．第四届全国磷化学学术讨论会论文摘要集，青岛，1997，212～213
[7] 梁诚．我国阻燃剂生产现状与发展趋势．化工新型材料，2001，29(8)：5～7
[8] 秦华军，张立新．阻燃剂的现状与展望．华北工学院学报，2001，22(2)：112～115
[9] 赵小平．阻燃科学．使我们的工作生活更安全．安徽消防，2003，09：34～35
[10] 时虎，梁红林，赵华伟，胡源．世贸大楼的倒塌与钢结构防火．消防技术与产品信息，2002，10：3～7
[11] Y Halpem,M Mott,R H Niswander.Fire retardancy of thermoplastic materialsbyintumescence.Ind.Eng.Chem.Prod.Res.Dev, 1984,23(2):233～238
[12] 彭治汉，欧育湘．含溴笼状磷酸酯的合成和热重分析研究．化学通报，1998，8：39～42
[13] A Kettrup,K H Ohrbach,G Matuschek,A Joachim.Thermal analysis-mass spectrometry and thermogravimetric adsorption on fire retardants. Thermochin.Acta, 1990,166:41～52
[14] Saito Toranosuke,Oishi Hiroyuki.Phosphorus-Containing diimide.Jp 60 174,794[85174,794]09 Sep,1985 6pp
[15] Shinlki Mitsuharu, Matsumoto Testuo.Fireproofing Polyester film laminates. Jp62,297,146[87,297,146]24 Dec, 1987
[16] Delobel Rene.Intumescent fire resistant compositions for use on polymer.Eur Pat Appl.Ep,555,136,11 Aug,1993.16pp
[17] K H Sivrier, V Kaleva, G Borisov, L Zabski,Z Jedlinski.Rigid Polyurethane foams with reduced flammability modified with phosphorus and nitrogen-containing polyolobtained from tetrakis(hydroxymethyl) phosphonium chloride.Eur.Poly.J, 1998,24(4):365～370
[18] Hewel Manfred,et al.Fire proofing agents for polyamides.Eur pat Appl.Ep 659,836,28 Jun, 1995,8pp
[19] AmdtVwe,BlockHansdieter, Schulz-Schlittle,WolfgangHans.Preparation of Phosphoromethylmelamines as flame retardants and crosslinking agents.Ger
often DE 3,933,546;11 Apr,1991.4pp
[20] 单玉华，王旭，徐美英．新型阻燃剂乙二胺四甲撑四[双(2-羟基-3-氯丙基)]膦酸酯的合成及应用效果评价．精细化工，1998,15(3)：35～38
[21] Okia Shigeru, et al.Polyphosphonamides as fireproofing agents for ther moplastic resin.Jp 07 41,598 [95 41,598] 10 Feb, 1995,9pp
[22] 李伟，叶大铿．聚丙烯的膨胀阻燃剂．化学通报，1995(10)：30～34
[23] Sugii Naoyuke,Yamauchi Toshuki,Yano Toshihiro.Preparation of flameresisting nitilotris(methylene phosphonate).Jp 05 04,997[93 04,997] 1993
[24] Giroldini william,Rinaldi Antonio,Landoni Gianluigi,Neri Carlo. Poly(pentaery thrityl diphosphonate) and its use in self extinguishing thermoplastic compositions.EP 684250,1995
[25] 贡长生．积极开发磷—氮系阻燃剂．现代化工，1996,(2)：14～17
[26] Chun Shan Wang,Jeng Yueh Shieh,Yih Min Sun.Synthesis and properties of phosphorus containing PET and PEN(1).J.Appl.Poly.Sci,1998,70:1958～1964
[27] Koyong hoon,Cheong Seon kyeng.Flame retardant wholly aromatic polyester and method of its preparation.US 5,677,416,1996
[28] 肖新颜，万彩霞，陈国栋．双氯螺磷及膨胀型阻燃剂(IFR)的合成研究．化学工业与工程，2000,17(5)：274～277
[29] E D Weil,Zhu Weiming,N Patel,et al.[J].Polym Degrad Stab,1996, 54(2):125～126
[30] 高复业，欧育湘．新型磷—氮阻燃剂三(5，5-二甲基-1，3-氧-2-磷杂环己烷-2-氧甲基)胺的合成及应用．精细化工，1998,15(2)：35～37
[31] 李昕，欧育湘，张蕴宏．三(1-氧代-1-磷杂-2，6，7-三氧杂双环[2．2．2]辛烷-4-亚甲基)磷酸酯的合成、晶体结构及热性能．高等化学学报，2002，23(4)：695～699
[32] 徐旭荣，陈关喜，胡耿源．磷杂螺环化合物的合成及表征．精细化工，1997，14(5)：35～38
[33] 彭治汉，欧育湘，连旦军．一种笼状磷酸酯三聚氰胺盐的合成新工艺．现代化工，1998(10)：20～22
[34] 高复业，欧育湘，田雨晴．磷—氮系膨胀型阻燃剂1，2-(2-氧代-5．5-二甲-1，3-二氧-2-磷杂环己基-2-亚氨基)乙烷及其同系物的合成．化学世界，1999，(7)：353～356
[35] 李巧玲，欧育湘．一种含P-N键的双环磷酸酯化合物的合成及晶体结构．结构化学，2001，20(2)：128～130
[36] 彭治汉，欧育湘．1，4-二(5，5-二甲基-1，3-二氧要己内磷酰亚胺基)苯的合
成．精细化工，1999，16(1)：20～23
[37] 李巧玲，欧育湘．新型磷-氮阻燃剂N，N~′-双(2-氧-5，5-二甲基-1，3，2-二氧磷杂环己烷)-2，2~′-间苯二胺的合成研究．化学世界，1999，(5)：239～241
[38] Mc Euen, Beltz, Kumar.Flame retardant polycarbonate-ABS polymer compositons.Eur Pat Appl.Ep 1,067,153 A1 10,01,2001
[39] 赵文革，马志领，刘志广．螺环磷酸酯酰胺阻燃剂的合成及其在醇酸清漆中的应用．河北大学学报(自然科学版)，1996,16(2)：20～23
[40] 宦双燕．含1，3．2-二氧磷杂环己烷结构的磷-氮系膨胀型阻燃剂的合成和阻燃性能研究．华中师范大学硕士学位论文．2001
[41] 杨华铮，王建武，和慕如等．α-氨基磷(次膦)酸类衍生物的合成及其性质．高等学校化学学报，1989,V10(3)：254～259
[42] K Kim.Phosphorus-containing polymers: I.low temperature polycondensation of phenylphosphonic dichloride with bisphenols. J Appl Polym Sci,1983,28:1119～1123
[43] Almeria Natansohn.Synthesis and Characterization of Some Aromatic Polyphosphonates.J Appl Polym Sci, 1986,32:2961～2968
[44] K S Annakutty, K Kishore. Flame retardant polyphosphate esters: 1.condensation polymers of bisphenol with aryl phosphorodichloridates: synthesis,characterization and thermal studies. Polymer, 1988,29(4):756～761
[45] K S Annakutty, K Kishore.A novel approach, to structure-flammability correlation in polyphosphate esters.Polymer, 1988;29(7): 1273～1276
[46] K Kishore, P Kannan.Synthesis of novel flame retardant polyamidophosphate esters from aromatic diols and N-arylphosphoramidic dichlorides.Polymer Bulletin, 1990,24,481～486
[47] D J Liaw, W C Shen.Synthesis of aromatic polyphosphonate: low temperature solution polycondensation of 4,4~'-sulphonyldiphenol with phenoxy dichlorophosphate.Polymer, 1993,34(6): 1336～1338
[48] 王玉忠，郑长义，杨科柯等．聚苯基膦酸二苯砜酯的合成与表征．高分子材料科学与工程，1999,15(1)：53～56
[49] 马少君．阻燃剂聚对二苯砜苯基磷酸酯的制备．辽阳石油化工高等专科学校学报，2000，16(2)：26～28
[50] Wolter ten Hoeve,Hans Wynberg.The design of resolving agents.Chiral cyclic phosphoric acid.J.Org.Chem, 1985,50:4508～4514
[51] 陈宇，高富业，欧育湘．新型磷—卤协效阻燃剂的合成与应用．精细化工，1998，15(、3)：32～34
[52] Maier Ludwing.Organic Phosphorous Compouds 69:Synthesis and properties
of cyclic phosphonate and thiophosphonate ester.Synth.React.Inorg.Met-Org.Chem,1976,6(2):133～155
[53] 邵瑞链，杨敏华，职承信．不对称环磷化合物的合成及立体化学(Ⅰ)—环磷酰氯和3—羟基异唑的反应及其立体化学．高等学校化学学报，1994，15(10)：1473～1476
[54] R L Shao,G F Yang,W S Miao,M H Yang.Chinese Chem lett.1 997,8(4):269～271
[55] 杨光富，韩传荣．N-(2-硫代-1，3，2-氧磷杂环己烷-2-基)-~′-芳基(烷基)硫脲的合成、杀菌活性及构效关系．华中师范大学学报(自然科学版)，1998,32(4)：434～438
[56] 张友杰，李念平主编．《有机波谱学教程》．武汉：华中师范大学出版社，1990
[57] 王芹珠，邓友节，于文徐，杨增家．0，0-二烷基磷酰胍及衍生物的合成．化学试剂，1997，19(4)：230～232
[58] 王悠梅，杨平，刘长欣．新型粉体溴代缩聚磷酸芳香酯的合成及其应用．化工进展，1998,(4)：54～55
[59] 赵文元，王亦军．功能高分子材料化学．北京：化学工业出版社，1996：289
[60] 王筱梅，杨平等．芳香族聚磷酸酯的聚合度与阻燃性质的研究．高分子材料科学与工程．1999，15(4)：81～83
[61] 徐应麟等．高聚物材料的实用阻燃技术．化学工业出版社，1987
[62] Wang Tsui-Shuang,Shau Min-Da.Properties of Epon 828 resin cured by cyclic phosphine oxida tetra acid.J.Appl.Poly.Sci. 1998,70:1877～1885
[63] 马志领，赵文革等．溴代磷酸酯酰胺阻燃剂的合成及其在醇酸清漆中的应用试验．精细化工，1996,13(2)：26～28
[64] 周少林．新型磷氮系阻燃剂的合成及其阻燃性能的研究．华中师范大学硕士学位论文．2003
[2] 欧育湘，陈宇，王筱梅．阻燃高分子材料．北京：国防工业出版社，2001
[3] 朱艳秋．聚烯烃阻燃剂的发展动态．石化技术，2003，4
[4] 贺峥杰，陈文彬，唐除痴．有机磷阻燃剂研究进展．化学工业与工程，1997,14(3)：43～49
[5] 欧育湘．有机阻燃剂最新进展．现代化工，1997,4：9～12
[6] 贡长生．磷系阻燃剂的现状和发展．第四届全国磷化学学术讨论会论文摘要集，青岛，1997，212～213
[7] 梁诚．我国阻燃剂生产现状与发展趋势．化工新型材料，2001，29(8)：5～7
[8] 秦华军，张立新．阻燃剂的现状与展望．华北工学院学报，2001，22(2)：112～115
[9] 赵小平．阻燃科学．使我们的工作生活更安全．安徽消防，2003，09：34～35
[10] 时虎，梁红林，赵华伟，胡源．世贸大楼的倒塌与钢结构防火．消防技术与产品信息，2002，10：3～7
[11] Y Halpem,M Mott,R H Niswander.Fire retardancy of thermoplastic materialsbyintumescence.Ind.Eng.Chem.Prod.Res.Dev, 1984,23(2):233～238
[12] 彭治汉，欧育湘．含溴笼状磷酸酯的合成和热重分析研究．化学通报，1998，8：39～42
[13] A Kettrup,K H Ohrbach,G Matuschek,A Joachim.Thermal analysis-mass spectrometry and thermogravimetric adsorption on fire retardants. Thermochin.Acta, 1990,166:41～52
[14] Saito Toranosuke,Oishi Hiroyuki.Phosphorus-Containing diimide.Jp 60 174,794[85174,794]09 Sep,1985 6pp
[15] Shinlki Mitsuharu, Matsumoto Testuo.Fireproofing Polyester film laminates. Jp62,297,146[87,297,146]24 Dec, 1987
[16] Delobel Rene.Intumescent fire resistant compositions for use on polymer.Eur Pat Appl.Ep,555,136,11 Aug,1993.16pp
[17] K H Sivrier, V Kaleva, G Borisov, L Zabski,Z Jedlinski.Rigid Polyurethane foams with reduced flammability modified with phosphorus and nitrogen-containing polyolobtained from tetrakis(hydroxymethyl) phosphonium chloride.Eur.Poly.J, 1998,24(4):365～370
[18] Hewel Manfred,et al.Fire proofing agents for polyamides.Eur pat Appl.Ep 659,836,28 Jun, 1995,8pp
[19] AmdtVwe,BlockHansdieter, Schulz-Schlittle,WolfgangHans.Preparation of Phosphoromethylmelamines as flame retardants and crosslinking agents.Ger
often DE 3,933,546;11 Apr,1991.4pp
[20] 单玉华，王旭，徐美英．新型阻燃剂乙二胺四甲撑四[双(2-羟基-3-氯丙基)]膦酸酯的合成及应用效果评价．精细化工，1998,15(3)：35～38
[21] Okia Shigeru, et al.Polyphosphonamides as fireproofing agents for ther moplastic resin.Jp 07 41,598 [95 41,598] 10 Feb, 1995,9pp
[22] 李伟，叶大铿．聚丙烯的膨胀阻燃剂．化学通报，1995(10)：30～34
[23] Sugii Naoyuke,Yamauchi Toshuki,Yano Toshihiro.Preparation of flameresisting nitilotris(methylene phosphonate).Jp 05 04,997[93 04,997] 1993
[24] Giroldini william,Rinaldi Antonio,Landoni Gianluigi,Neri Carlo. Poly(pentaery thrityl diphosphonate) and its use in self extinguishing thermoplastic compositions.EP 684250,1995
[25] 贡长生．积极开发磷—氮系阻燃剂．现代化工，1996,(2)：14～17
[26] Chun Shan Wang,Jeng Yueh Shieh,Yih Min Sun.Synthesis and properties of phosphorus containing PET and PEN(1).J.Appl.Poly.Sci,1998,70:1958～1964
[27] Koyong hoon,Cheong Seon kyeng.Flame retardant wholly aromatic polyester and method of its preparation.US 5,677,416,1996
[28] 肖新颜，万彩霞，陈国栋．双氯螺磷及膨胀型阻燃剂(IFR)的合成研究．化学工业与工程，2000,17(5)：274～277
[29] E D Weil,Zhu Weiming,N Patel,et al.[J].Polym Degrad Stab,1996, 54(2):125～126
[30] 高复业，欧育湘．新型磷—氮阻燃剂三(5，5-二甲基-1，3-氧-2-磷杂环己烷-2-氧甲基)胺的合成及应用．精细化工，1998,15(2)：35～37
[31] 李昕，欧育湘，张蕴宏．三(1-氧代-1-磷杂-2，6，7-三氧杂双环[2．2．2]辛烷-4-亚甲基)磷酸酯的合成、晶体结构及热性能．高等化学学报，2002，23(4)：695～699
[32] 徐旭荣，陈关喜，胡耿源．磷杂螺环化合物的合成及表征．精细化工，1997，14(5)：35～38
[33] 彭治汉，欧育湘，连旦军．一种笼状磷酸酯三聚氰胺盐的合成新工艺．现代化工，1998(10)：20～22
[34] 高复业，欧育湘，田雨晴．磷—氮系膨胀型阻燃剂1，2-(2-氧代-5．5-二甲-1，3-二氧-2-磷杂环己基-2-亚氨基)乙烷及其同系物的合成．化学世界，1999，(7)：353～356
[35] 李巧玲，欧育湘．一种含P-N键的双环磷酸酯化合物的合成及晶体结构．结构化学，2001，20(2)：128～130
[36] 彭治汉，欧育湘．1，4-二(5，5-二甲基-1，3-二氧要己内磷酰亚胺基)苯的合
成．精细化工，1999，16(1)：20～23
[37] 李巧玲，欧育湘．新型磷-氮阻燃剂N，N~′-双(2-氧-5，5-二甲基-1，3，2-二氧磷杂环己烷)-2，2~′-间苯二胺的合成研究．化学世界，1999，(5)：239～241
[38] Mc Euen, Beltz, Kumar.Flame retardant polycarbonate-ABS polymer compositons.Eur Pat Appl.Ep 1,067,153 A1 10,01,2001
[39] 赵文革，马志领，刘志广．螺环磷酸酯酰胺阻燃剂的合成及其在醇酸清漆中的应用．河北大学学报(自然科学版)，1996,16(2)：20～23
[40] 宦双燕．含1，3．2-二氧磷杂环己烷结构的磷-氮系膨胀型阻燃剂的合成和阻燃性能研究．华中师范大学硕士学位论文．2001
[41] 杨华铮，王建武，和慕如等．α-氨基磷(次膦)酸类衍生物的合成及其性质．高等学校化学学报，1989,V10(3)：254～259
[42] K Kim.Phosphorus-containing polymers: I.low temperature polycondensation of phenylphosphonic dichloride with bisphenols. J Appl Polym Sci,1983,28:1119～1123
[43] Almeria Natansohn.Synthesis and Characterization of Some Aromatic Polyphosphonates.J Appl Polym Sci, 1986,32:2961～2968
[44] K S Annakutty, K Kishore. Flame retardant polyphosphate esters: 1.condensation polymers of bisphenol with aryl phosphorodichloridates: synthesis,characterization and thermal studies. Polymer, 1988,29(4):756～761
[45] K S Annakutty, K Kishore.A novel approach, to structure-flammability correlation in polyphosphate esters.Polymer, 1988;29(7): 1273～1276
[46] K Kishore, P Kannan.Synthesis of novel flame retardant polyamidophosphate esters from aromatic diols and N-arylphosphoramidic dichlorides.Polymer Bulletin, 1990,24,481～486
[47] D J Liaw, W C Shen.Synthesis of aromatic polyphosphonate: low temperature solution polycondensation of 4,4~'-sulphonyldiphenol with phenoxy dichlorophosphate.Polymer, 1993,34(6): 1336～1338
[48] 王玉忠，郑长义，杨科柯等．聚苯基膦酸二苯砜酯的合成与表征．高分子材料科学与工程，1999,15(1)：53～56
[49] 马少君．阻燃剂聚对二苯砜苯基磷酸酯的制备．辽阳石油化工高等专科学校学报，2000，16(2)：26～28
[50] Wolter ten Hoeve,Hans Wynberg.The design of resolving agents.Chiral cyclic phosphoric acid.J.Org.Chem, 1985,50:4508～4514
[51] 陈宇，高富业，欧育湘．新型磷—卤协效阻燃剂的合成与应用．精细化工，1998，15(、3)：32～34
[52] Maier Ludwing.Organic Phosphorous Compouds 69:Synthesis and properties
of cyclic phosphonate and thiophosphonate ester.Synth.React.Inorg.Met-Org.Chem,1976,6(2):133～155
[53] 邵瑞链，杨敏华，职承信．不对称环磷化合物的合成及立体化学(Ⅰ)—环磷酰氯和3—羟基异唑的反应及其立体化学．高等学校化学学报，1994，15(10)：1473～1476
[54] R L Shao,G F Yang,W S Miao,M H Yang.Chinese Chem lett.1 997,8(4):269～271
[55] 杨光富，韩传荣．N-(2-硫代-1，3，2-氧磷杂环己烷-2-基)-~′-芳基(烷基)硫脲的合成、杀菌活性及构效关系．华中师范大学学报(自然科学版)，1998,32(4)：434～438
[56] 张友杰，李念平主编．《有机波谱学教程》．武汉：华中师范大学出版社，1990
[57] 王芹珠，邓友节，于文徐，杨增家．0，0-二烷基磷酰胍及衍生物的合成．化学试剂，1997，19(4)：230～232
[58] 王悠梅，杨平，刘长欣．新型粉体溴代缩聚磷酸芳香酯的合成及其应用．化工进展，1998,(4)：54～55
[59] 赵文元，王亦军．功能高分子材料化学．北京：化学工业出版社，1996：289
[60] 王筱梅，杨平等．芳香族聚磷酸酯的聚合度与阻燃性质的研究．高分子材料科学与工程．1999，15(4)：81～83
[61] 徐应麟等．高聚物材料的实用阻燃技术．化学工业出版社，1987
[62] Wang Tsui-Shuang,Shau Min-Da.Properties of Epon 828 resin cured by cyclic phosphine oxida tetra acid.J.Appl.Poly.Sci. 1998,70:1877～1885
[63] 马志领，赵文革等．溴代磷酸酯酰胺阻燃剂的合成及其在醇酸清漆中的应用试验．精细化工，1996,13(2)：26～28
[64] 周少林．新型磷氮系阻燃剂的合成及其阻燃性能的研究．华中师范大学硕士学位论文．2003