六氯环三磷腈及其苯氧基衍生物的合成与表征
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摘要
合成了六氯环三磷腈及其含苯氧基衍生物，通过优化实验选择了最佳反应条件，并用IR，NMR，DSC等谱学手段对合成产物进行了表征。研究发现，采用缚酸剂体系合成六氯环三磷腈的合成方法简单，反应时间短，但是反应过程中会放出大量热量，较适合小试规模的研究生产；复式催化剂／氮气体系装置较复杂，反应时间较长，但是反应过程稳定，较适于大规模工业生产。采用KOH／甲苯体系成功合成了含苯氧基的衍生物——六(苯氧基)环三磷腈、六(对氯苯氧基)环三磷腈和六(4-硝基苯氧基)环三磷腈，并利用K_2CO_3／丙酮体系改进了实验过程，发现这种体系对六(4-硝基苯氧)环三磷腈的合成非常有效。
Hexachlorocyclotriphosphazene and its relative derivatives containing phenoxy group were synthesized and the best reaction conditions were selected. The products were characterized by IR, NMR and DSC. The results show that in the acid-captor system the method to synthesize hexachlorocyclotriphosphazene was simple and the reaction time was also short, but this method generally was suitable for the lab scale because of the heat given out in this system; In the duplex catalyst/nitrogen system the method was complicated and the reaction time was long, but the process was comparatively steady, so it was suitable for the industry scale. Besides that ,the derivatives containing phenoxy group were synthesized successfully by potassium hydroxide/ toluene system, such as hexakis(phenoxy)cyclotriphosphazene hexakis(p-chlorophenoxy)cyclotriphosphazenehexakis(4-nitrophenoxy)cyclotriphos-phazene. This process was also improved by the potassium carbonate/ acetone system which was found to be very effective for the synthesi
s of hexakis(4-nitrophenoxy)cyclotriphosphazene.
Hexachlorocyclotriphosphazene and its relative derivatives containing phenoxy group were synthesized and the best reaction conditions were selected. The products were characterized by IR, NMR and DSC. The results show that in the acid-captor system the method to synthesize hexachlorocyclotriphosphazene was simple and the reaction time was also short, but this method generally was suitable for the lab scale because of the heat given out in this system; In the duplex catalyst/nitrogen system the method was complicated and the reaction time was long, but the process was comparatively steady, so it was suitable for the industry scale. Besides that ,the derivatives containing phenoxy group were synthesized successfully by potassium hydroxide/ toluene system, such as hexakis(phenoxy)cyclotriphosphazene hexakis(p-chlorophenoxy)cyclotriphosphazenehexakis(4-nitrophenoxy)cyclotriphos-phazene. This process was also improved by the potassium carbonate/ acetone system which was found to be very effective for the synthesi
s of hexakis(4-nitrophenoxy)cyclotriphosphazene.
引文
[1] 赵玉芬，赵国辉编著．元素有机化学．北京：清华大学出版社，1998：82～83
[2] W. Sulkowski, A. Sulkowska, et al. Synthesis and spectroscopic studies of cyclo-and polyphosphazenes[J]. European Polymer Journal.2000,36:1519～1524
[3] 赵玉芬，赵国辉编著．元素有机化学．北京：清华大学出版社，1998：139～142
[4] De Jaeger R, Gleria M. Poly(organophosphazene)s and related compounds: synthesis properties and applications[J]. Prog Polym Sci. 1998,23(2): 179-276
[5] 袁淳，夏和平，胡理国．氯化磷腈的合成．化工时刊．1999，6：33～35
[6] 郑福安，王志强，林志宏等．环状氯化磷腈的合成．吉林大学自然科学学报．1992，2：119～120
[7] Shui-Yu Lu,Ian.Hamerton. Recent developments in the chemistry of halogen-free flame retardant polymers[J]. Prog. Polym. Sci.2002,27:1661～1712
[8] 侯锐峰，李顺香，马爱丽．磷腈系列磷——氮系阻燃剂．山西化工．1998，4：30～31
[9] Chang J Y, Ji H J，Han MJ, Rhee S B,Cheong S, Yoon M. Preparation of star-branched polymers with cyclophosphazenecores[J]. Macromolecules.1994,27(6):1376～80
[10] Allcock H R.Inorganic-organic polymers[J].Adv Mater.1994,6(2):106～15
[11] Dewar M J S,Lucken E A C,Whitehead M A．The Structure of the phosphanitrilic halides[J]. J Chem Soc.1960,2423～2429
[12] 陈茹玉，李玉桂编著．有机磷化学．北京：高等教育出版社，1987：360～375
[13] Elvira Pelaez-Arango,Francisco J.Garcia-Alonso,Gabino Carriedo, et al.~(15)N NMR Spectroscopy of Cyclotriphosphazenes and Polyphosphazenes Based on ~(31)P,~(15)N HMQC Correlations[J].Journal of Magnetic Resonance, Series A. 1996,121:154～159
[14] Potin P, De Jaeger R. Polyphosphazenes: synthesis structures properties applications[J]. Eur Polym J. 1991,27(4-5):341～8
[15] Victor Luana, A.Martin Pendas,Aurora Costales.Topological Analysis of Chemical Bonding in Cyclophosphazenes[J].J.Phys.Chem.A.2001,105:5280～5291
[16] Allcock H R. The synthesis of functional polyphosphazenes and their surfaces[J]. Appl
Organomet Chem. 1998,12(11-12): 659～66.
[17] 胡源，胡进良，范维澄等．含羟基环三磷腈衍生物的合成及其对聚氨酯的阻燃改性．火灾科学．1996，5(2)：12～16
[18] Allen C W, Hayes R F, Myer C N, Freund A S, Kearney M E. New organofunctional cyclophosphazene derivatives[J]. Phosphorus Sulfur Silicon Relat Elem. 1996,110(1-4):79～82
[19] Bosscher G, Meetsma A, Van De Grampel JC. Novel organo-substituted cyclophosphazenes via reaction of a monohydrocyclophosphazene and acetyl chloride[J]. Inorg Chem.1996,35(23):6646～50
[20] 朱宇军，袁福龙，赵经贵等．六氯环三磷腈的合成．黑龙江大学自然科学学报．1998，15(4)：102～104
[21] 颜红侠，宁荣昌，马晓艳．六氯环三磷腈的合成进展．陕西化工．1999，28(3)：5～6
[22] Roger De Jaeger, Mario Gleria. Poly(Organphosphazene)s Related Compounds:Synthesis, Properties and Applications[J].Prog.Polym.Sci. 1998,23:179～276
[23] 颜红侠，杨青芳，魏斌．催化合成六氯环三磷腈．氯碱工业．2000，8(8)：27～28
[24] Hiroshi Tanino,Tetsuhiko Okamoto,Shinichiro Ueyama.Process for the preparation of phosphonitrile chloride oligomer[P].GB 2154567,1985
[25] Allcock H R, et al. Pyridine phosphonitrilic halide trimer process[P]. US:4656 017,1987
[26] Kinoshita Itaru,Ugata Yuzuru, Suzue Masayoshi.Phosphorus nitride chloride oligomer[P].US 4256715,1979
[27] Fekete, et al. Continuous process for the production of phosphonitrilic chlorides[P].US:4046 857,1977
[28] Hesub M. Li,Baton Rouge La, Selective oligomer production[P].US 4537755,1985
[29] Fiedlhouse,John William.Purification of crude chlorophosphazene compounds by treatment with water[P].EP 4878,1979
[30] Tanino, et al. Process for purifying phosphonitrile chlorides[P].US 4522689
[31] 赵玉芬，赵国辉编著．元素有机化学．北京：清华大学出版社，1998：141～143
[32] Fantin G, Medici A, Fogagnolo M, Pedrini P, Gleria M, Bertani R, Facchin G
Functionalization of poly(organophosphazene)Ⅲ. Synthesis of phosphazene materials containing carbon-carbon double bonds and epoxide groups[J].Eur Polym J.1993,29(12):1571～9.
[33] Medici A, Fantin G, Pedrini P, Gleria M, Minto F. Functionalisation of phosphazenes. 1. Synthesis of phosphazene materials containing hydroxyl groups[J]. Macromolecules. 1992,25(10):2569～74
[34] Dez I, De Jaeger R. Synthesis and radical polymerization of methacrylate monomers containing cyclotriphosphazene.Thin-layer grafts of their polymers on a poly(vinyl alcohol) surface[J]. Macromolecules. 1997,30(26):8262～9
[35] Brown D E, RamachandraK, Carter K R, Allen C W. Poly[(vinyloxy) cyclophosphazene[J]. Macromolecules.2001,34(9):2870～5
[36] Bosscher G, Van De Grampel JC. Synthesis and polymerisation of gem-methyl(vinylbenzyl) tetrachlorocyclotriphosphazene[J]. J Inorg Organomet Polym. 1995,5(3):209～16
[37] 时虎．聚磷腈化合物的应用研究．化工科技市场．2002，5：29～32
[38] 刘安华．由SiO_2非碳热法直接合成硅有机化合物及其结构表征．华南理工大学．1999，66
[39] 王九，董浚修，陈波水．磷偶氮的研究现状及发展趋势．润滑与密封．2000，2：9～12
[40] 时虎，胡源．聚磷腈．精细与专用化学品．2002，12：17～18
[41] Kenzo Inoue and Tomoyuki Itaya.Synthesisi and Functionality of Cyclophosphazene-Based Polymers[J].Bull.Chem.Soc.Jpn..2001,74:1～10
[42] Raith, et al. Polymerizable phosphazene derivatives: a process for preparing them and their uses [P]. US 5912321
[43] Chandrasekhar V, Thomas KRJ. Coordination and organometallic chemistry of cyclophosphazenes and polyphosphazenes[J]. Appl Organomet Chem. 1993,7(1): 1-31
[44] 张亚峰，刘安华，龚克成．聚磷腈合成的研究进展．合成橡胶工业．2001，24(4)：240～243
[45] Allcock H R, Kwon S,Pucher S R.Bioerodible polymers with a phosphorus-nitrogen backbone[J]. Polym Prepr. 1990,31(2): 180～186
[46] Allcock H R, Robert W A,John P B.Synthesis of platinum derivatives of polymeric and cyclic phosphazenes[J]. J Am Chem Soc. 1977,99:3984～3987
[47] Allcock H R.Rational design and synthesis of new polymeric materials[J].Science. 1992,255:1106～1112
[48] Marco P D,Giro G, Lora S,et al.Photoconductive properties of some polyorganophosphazenes doped with trinitrofluorenone[J].Mol Cryst Lliq Cryst. 1985,118:439～442
[49] Yang Y W C,Hwang J J,Chang F H.Polyphosphazene electrolytes:1.Preparation and conductivities of nem polymer electrolytes based on poly[bis(amino)phosphazene] and lithium perchlorate[J].Macromolecules. 1997,30:3825～3831
[50] Allcock H R.A.A.Dembek, C.Kim, et al.Second-order nonlinear optical polyorganophosphazenes:Synthesis and nonlinear optical characterization[J]. Macromolecules. 1991,24:1000～1100
[51] Selvaraj I I,Chaklanobis S,Chandrasekhar V.New lipophilic cyclo-and poly-phosphazenes containing surfactant substituents[J].Polym Intern. 1998,46:111～116
[52] Allcock H R.Poly(organophosphazenes)-unusual new high polymers[J].Angew Chem Int Ed Engl.1977,16:147～156
[53] 徐寿昌编著．有机化学．北京：高等教育出版社，1993：254～255
[54] Meredith, Philip Lacy. Flame retardant polymeric compositions containing halogen substituted hexakis-(substituted phenoxy)cyclotriphosphazene [P]. US 4029634
[55] 吴祥雯，房昌水，王民等．一种改进方法合成六(4-硝基酚氧)环三磷腈．化学学报．2002，60(5)：955～956
[2] W. Sulkowski, A. Sulkowska, et al. Synthesis and spectroscopic studies of cyclo-and polyphosphazenes[J]. European Polymer Journal.2000,36:1519～1524
[3] 赵玉芬，赵国辉编著．元素有机化学．北京：清华大学出版社，1998：139～142
[4] De Jaeger R, Gleria M. Poly(organophosphazene)s and related compounds: synthesis properties and applications[J]. Prog Polym Sci. 1998,23(2): 179-276
[5] 袁淳，夏和平，胡理国．氯化磷腈的合成．化工时刊．1999，6：33～35
[6] 郑福安，王志强，林志宏等．环状氯化磷腈的合成．吉林大学自然科学学报．1992，2：119～120
[7] Shui-Yu Lu,Ian.Hamerton. Recent developments in the chemistry of halogen-free flame retardant polymers[J]. Prog. Polym. Sci.2002,27:1661～1712
[8] 侯锐峰，李顺香，马爱丽．磷腈系列磷——氮系阻燃剂．山西化工．1998，4：30～31
[9] Chang J Y, Ji H J，Han MJ, Rhee S B,Cheong S, Yoon M. Preparation of star-branched polymers with cyclophosphazenecores[J]. Macromolecules.1994,27(6):1376～80
[10] Allcock H R.Inorganic-organic polymers[J].Adv Mater.1994,6(2):106～15
[11] Dewar M J S,Lucken E A C,Whitehead M A．The Structure of the phosphanitrilic halides[J]. J Chem Soc.1960,2423～2429
[12] 陈茹玉，李玉桂编著．有机磷化学．北京：高等教育出版社，1987：360～375
[13] Elvira Pelaez-Arango,Francisco J.Garcia-Alonso,Gabino Carriedo, et al.~(15)N NMR Spectroscopy of Cyclotriphosphazenes and Polyphosphazenes Based on ~(31)P,~(15)N HMQC Correlations[J].Journal of Magnetic Resonance, Series A. 1996,121:154～159
[14] Potin P, De Jaeger R. Polyphosphazenes: synthesis structures properties applications[J]. Eur Polym J. 1991,27(4-5):341～8
[15] Victor Luana, A.Martin Pendas,Aurora Costales.Topological Analysis of Chemical Bonding in Cyclophosphazenes[J].J.Phys.Chem.A.2001,105:5280～5291
[16] Allcock H R. The synthesis of functional polyphosphazenes and their surfaces[J]. Appl
Organomet Chem. 1998,12(11-12): 659～66.
[17] 胡源，胡进良，范维澄等．含羟基环三磷腈衍生物的合成及其对聚氨酯的阻燃改性．火灾科学．1996，5(2)：12～16
[18] Allen C W, Hayes R F, Myer C N, Freund A S, Kearney M E. New organofunctional cyclophosphazene derivatives[J]. Phosphorus Sulfur Silicon Relat Elem. 1996,110(1-4):79～82
[19] Bosscher G, Meetsma A, Van De Grampel JC. Novel organo-substituted cyclophosphazenes via reaction of a monohydrocyclophosphazene and acetyl chloride[J]. Inorg Chem.1996,35(23):6646～50
[20] 朱宇军，袁福龙，赵经贵等．六氯环三磷腈的合成．黑龙江大学自然科学学报．1998，15(4)：102～104
[21] 颜红侠，宁荣昌，马晓艳．六氯环三磷腈的合成进展．陕西化工．1999，28(3)：5～6
[22] Roger De Jaeger, Mario Gleria. Poly(Organphosphazene)s Related Compounds:Synthesis, Properties and Applications[J].Prog.Polym.Sci. 1998,23:179～276
[23] 颜红侠，杨青芳，魏斌．催化合成六氯环三磷腈．氯碱工业．2000，8(8)：27～28
[24] Hiroshi Tanino,Tetsuhiko Okamoto,Shinichiro Ueyama.Process for the preparation of phosphonitrile chloride oligomer[P].GB 2154567,1985
[25] Allcock H R, et al. Pyridine phosphonitrilic halide trimer process[P]. US:4656 017,1987
[26] Kinoshita Itaru,Ugata Yuzuru, Suzue Masayoshi.Phosphorus nitride chloride oligomer[P].US 4256715,1979
[27] Fekete, et al. Continuous process for the production of phosphonitrilic chlorides[P].US:4046 857,1977
[28] Hesub M. Li,Baton Rouge La, Selective oligomer production[P].US 4537755,1985
[29] Fiedlhouse,John William.Purification of crude chlorophosphazene compounds by treatment with water[P].EP 4878,1979
[30] Tanino, et al. Process for purifying phosphonitrile chlorides[P].US 4522689
[31] 赵玉芬，赵国辉编著．元素有机化学．北京：清华大学出版社，1998：141～143
[32] Fantin G, Medici A, Fogagnolo M, Pedrini P, Gleria M, Bertani R, Facchin G
Functionalization of poly(organophosphazene)Ⅲ. Synthesis of phosphazene materials containing carbon-carbon double bonds and epoxide groups[J].Eur Polym J.1993,29(12):1571～9.
[33] Medici A, Fantin G, Pedrini P, Gleria M, Minto F. Functionalisation of phosphazenes. 1. Synthesis of phosphazene materials containing hydroxyl groups[J]. Macromolecules. 1992,25(10):2569～74
[34] Dez I, De Jaeger R. Synthesis and radical polymerization of methacrylate monomers containing cyclotriphosphazene.Thin-layer grafts of their polymers on a poly(vinyl alcohol) surface[J]. Macromolecules. 1997,30(26):8262～9
[35] Brown D E, RamachandraK, Carter K R, Allen C W. Poly[(vinyloxy) cyclophosphazene[J]. Macromolecules.2001,34(9):2870～5
[36] Bosscher G, Van De Grampel JC. Synthesis and polymerisation of gem-methyl(vinylbenzyl) tetrachlorocyclotriphosphazene[J]. J Inorg Organomet Polym. 1995,5(3):209～16
[37] 时虎．聚磷腈化合物的应用研究．化工科技市场．2002，5：29～32
[38] 刘安华．由SiO_2非碳热法直接合成硅有机化合物及其结构表征．华南理工大学．1999，66
[39] 王九，董浚修，陈波水．磷偶氮的研究现状及发展趋势．润滑与密封．2000，2：9～12
[40] 时虎，胡源．聚磷腈．精细与专用化学品．2002，12：17～18
[41] Kenzo Inoue and Tomoyuki Itaya.Synthesisi and Functionality of Cyclophosphazene-Based Polymers[J].Bull.Chem.Soc.Jpn..2001,74:1～10
[42] Raith, et al. Polymerizable phosphazene derivatives: a process for preparing them and their uses [P]. US 5912321
[43] Chandrasekhar V, Thomas KRJ. Coordination and organometallic chemistry of cyclophosphazenes and polyphosphazenes[J]. Appl Organomet Chem. 1993,7(1): 1-31
[44] 张亚峰，刘安华，龚克成．聚磷腈合成的研究进展．合成橡胶工业．2001，24(4)：240～243
[45] Allcock H R, Kwon S,Pucher S R.Bioerodible polymers with a phosphorus-nitrogen backbone[J]. Polym Prepr. 1990,31(2): 180～186
[46] Allcock H R, Robert W A,John P B.Synthesis of platinum derivatives of polymeric and cyclic phosphazenes[J]. J Am Chem Soc. 1977,99:3984～3987
[47] Allcock H R.Rational design and synthesis of new polymeric materials[J].Science. 1992,255:1106～1112
[48] Marco P D,Giro G, Lora S,et al.Photoconductive properties of some polyorganophosphazenes doped with trinitrofluorenone[J].Mol Cryst Lliq Cryst. 1985,118:439～442
[49] Yang Y W C,Hwang J J,Chang F H.Polyphosphazene electrolytes:1.Preparation and conductivities of nem polymer electrolytes based on poly[bis(amino)phosphazene] and lithium perchlorate[J].Macromolecules. 1997,30:3825～3831
[50] Allcock H R.A.A.Dembek, C.Kim, et al.Second-order nonlinear optical polyorganophosphazenes:Synthesis and nonlinear optical characterization[J]. Macromolecules. 1991,24:1000～1100
[51] Selvaraj I I,Chaklanobis S,Chandrasekhar V.New lipophilic cyclo-and poly-phosphazenes containing surfactant substituents[J].Polym Intern. 1998,46:111～116
[52] Allcock H R.Poly(organophosphazenes)-unusual new high polymers[J].Angew Chem Int Ed Engl.1977,16:147～156
[53] 徐寿昌编著．有机化学．北京：高等教育出版社，1993：254～255
[54] Meredith, Philip Lacy. Flame retardant polymeric compositions containing halogen substituted hexakis-(substituted phenoxy)cyclotriphosphazene [P]. US 4029634
[55] 吴祥雯，房昌水，王民等．一种改进方法合成六(4-硝基酚氧)环三磷腈．化学学报．2002，60(5)：955～956