新型磷系阻燃剂双（对-羧苯基）苯基氧化膦的合成研究
摘要
双(对-羧苯基)苯基氧化膦(BCPPO)是一种适用于PET纤维阻燃改性的新型有机磷阻燃剂，本文主要研究了其合成工艺，整个合成路线分为三步，通过Friedel-Crafts烷基化反应制备了苯基二氯化膦(DCPP)，进而通过Friedel-Crafts酰基化反应合成了双(对-甲苯基)苯基氧化瞵(BMPPO)，经氧气、高锰酸钾氧化得到了产品BCPPO。
通过一一考察各种因素对产品收率的影响，改进和优化了工艺路线；产品经过元素分析、热分析、质谱分析、气相色谱、红外光谱、酸值等分析方法进行了表征；测定了中间体的物性参数，为实验及工业化设计提供了依据。
本论文合成方案与文献报道相比，有如下改进：第一，在DCPP产物分离过程中，采用细颗粒氯化钠作为络合剂，与文献中采用的吡啶和三氯氧磷相比，络合效果好，反应比较平缓，易于控制，减少了对环境的污染，降低了生产成本；第二，氧化剂用廉价的双氧水和氧气代替部分高锰酸钾，降低了生产成本；第三，在双氧水和氧气氧化过程中采用醋酸作为反应溶剂，与采用甲苯和吡啶相比，减少了环境污染，降低了生产成本。
The main work of the article was to synthesize a suitable monomer, bis(4-carboxyphenyl)phenyl phosphine oxide (BCPPO), as the retardant for poly(ethylene terephthalate) (PET) fibre. The procedures were divided into three steps: dichloride phenyl phosphine oxide (DCPP) was synthesized and bis(4-methyl phenyl)phosphate oxide(BMPPO) was prepared from DCPP by Friedel-Crafts reaction. BCPPO was produced by two steps of oxidizing BMPPO with KMnO4 and O2.
The procedures were improved and optimized by reviewing different factors effects. The product was identified by elements analysis, DSC analysis, MS analysis, GAS chromatogram, infrared chromatogram, acid number and so on. The physical constants of products were measured, which provided evidences for experiment and industrialization plan.
Some improvements were made in this synthesis method. First, sodium chloride was adopted as the separation reagent in the process of DCPP synthesis, which had approving effect and the reaction is easy to control. The environment pollution was decreased and production cost was reduced. Second, the H2O2 and 67 were substituted for KMnO4 as oxidant in the oxidation process. Third, acetic acid was adopted as solvent, which made environment pollution reduced and production cost decreased, too.
通过一一考察各种因素对产品收率的影响，改进和优化了工艺路线；产品经过元素分析、热分析、质谱分析、气相色谱、红外光谱、酸值等分析方法进行了表征；测定了中间体的物性参数，为实验及工业化设计提供了依据。
本论文合成方案与文献报道相比，有如下改进：第一，在DCPP产物分离过程中，采用细颗粒氯化钠作为络合剂，与文献中采用的吡啶和三氯氧磷相比，络合效果好，反应比较平缓，易于控制，减少了对环境的污染，降低了生产成本；第二，氧化剂用廉价的双氧水和氧气代替部分高锰酸钾，降低了生产成本；第三，在双氧水和氧气氧化过程中采用醋酸作为反应溶剂，与采用甲苯和吡啶相比，减少了环境污染，降低了生产成本。
The main work of the article was to synthesize a suitable monomer, bis(4-carboxyphenyl)phenyl phosphine oxide (BCPPO), as the retardant for poly(ethylene terephthalate) (PET) fibre. The procedures were divided into three steps: dichloride phenyl phosphine oxide (DCPP) was synthesized and bis(4-methyl phenyl)phosphate oxide(BMPPO) was prepared from DCPP by Friedel-Crafts reaction. BCPPO was produced by two steps of oxidizing BMPPO with KMnO4 and O2.
The procedures were improved and optimized by reviewing different factors effects. The product was identified by elements analysis, DSC analysis, MS analysis, GAS chromatogram, infrared chromatogram, acid number and so on. The physical constants of products were measured, which provided evidences for experiment and industrialization plan.
Some improvements were made in this synthesis method. First, sodium chloride was adopted as the separation reagent in the process of DCPP synthesis, which had approving effect and the reaction is easy to control. The environment pollution was decreased and production cost was reduced. Second, the H2O2 and 67 were substituted for KMnO4 as oxidant in the oxidation process. Third, acetic acid was adopted as solvent, which made environment pollution reduced and production cost decreased, too.
引文
[1] 周享近．阻燃技术的现状和发展．国外塑料，1995，13(1)：9～17
[2] 王玉钟．聚酯纤维阻燃化设计．成都：四川科学技术出版社，1994．12～17
[3] 王玉钟．阻燃PET纤维的制备、结构和性能．合成纤维工业，1993，16(3)：22～25
[4] 沈发治，梁波涛．磷-溴双元素阻燃涤纶的研制．合成纤维工业，1996，19(3)：13～16
[5] Koch P J, Pearce E M, Lapham J A, et al. Flam-retardant poly(ethylene terephthalate). J Appl Polym Sci, 1979, 19:227～234
[6] Van Krevelen D M. Flame Resistance of Chemical Fibers. J Appl polym Sci, 1977, 31: 269～292
[7] Ou Y X, ed. Proceedings of the International Symposium on Flame Retardants, Bcijing: International Academic Pulisher, 1989. 548～553
[8] Bollert U, Lohmar E Ohorodnik A. Process for the manufacture of flame retarding linear polyesters. US Pat, C08G, 4033 936. 1977-05-05
[9] Lewin M M. Flame retardant Polymetic Material. New York : Plenum, 1975 (3): 193～196
[10] Herlinger H．合成纤维发展趋势．合成纤维工业，1981(1)：55～60
[11] 欧育湘．有机阻燃剂最新进展．现代化工，1997(4)：9～12
[12] Kidder R C. Fire safety issues in the United States in 1994. In The British P1 a stics Federation, ed. Flame Retardants'94 London: Elsevier Applied Science, 1990, 114～125
[13] Chaplin D, Brown S C. Flamtard, A new range of flame and smoke retardants. In: the British Plastics Federation, ed. FlameRetadants'90. London Elsevier Applied Science, 1990, 21～31
[14] Cusack P A. Flame-retardant inorganic in additive which suppress smoke and carb on monoxide emisson from burning polymers. In: The British Plastics Federation, ed.
FlameRetadants'90． London Elsevier Applied Science, 1990, 176-190
[15] Mount R A. Flame-retardant Non-halogen themoplastics. In: The Fire Retardant Chemicals Association, USA, ed. Fire Retardant Technology and Marketing. New York: Wiley Interscience, 1994． 253-259
[16] Cicchetti O, Bertelli G, Bevilacqua A et al. Advances in intumescent flame retardants'94 London: Elsevier Applied Science, 1994:129-142
[17] Cullis C F, Hirshler M M. The Combudtion of Organic Polymers.Oxford: Clarendon Press, 1981:241-254
[18] Pagliari A, Cicchetti O, Bevilacqua A, et al. Intumescent flame retardants: new evidence of their higher fire safety, In: The British Plastics Federation, ed. Flame Retardants'92． London: Elsevier Applied Science, 1992:41-52
[19] Deshpande A B, Pearce E M, Yoon H S, et al. Some structure-property relationships in polymer flammability: Studies on poly(ethylene terephthalate). J Appl Polyrn Sci, 1977(31) :257-268
[20] Banks M, Ebdon J R, Johnson M. Influence of covalently bound phosphorus-comtaining groups on the fanmmability of some common addition homo-and polymers,In: The British plastics Federation, ed. Flame Retardants'94． London: Elsevier Applied Science, 1994:183-192
[21] Barker R H. Fire Safety Research. Gaithersburg: National Bureau of Standars Special Publication, 1973:37-42
[22] Endo S, kashihara T, Osako A, et al,. Phosphorus-containing compounds. US Pat, C07F 4 127 590． 1978-11-28
[23] Van Krevelen D M. Flame resistande of chemical fibers. J Appl Polym Sci, 1977(31) : 269-292
[24] Morgan P W. Herr B C. Some dicarboxylic acids and esters containing me phosphine
oxide group, J Amer Chem Soc, 1952,74:4526～4529
[25] Wan I Y, Kashiwagi T, Me Grath J E. Synthesis, characterization and flame retardancy behavior of triaryl phosphine oxide containing nylon 6, 6copolymer. Polymeric Materials Science and Engineering Preprint, 1994,71:233～234
[26] Morgan P W, Kenmore N Y. Synthetics linear consideration polymers containing phosporus. US Pat, C1260-75, 2 646 420. 1953-07-21
[27] Shciemenz G P, Siebeneick H U. Phosphine mit mehreren elektronenak zeptordubstituenten. Chem Ber, 1969, 102:1883～1891
[28] Deshpande A B, Pearce E M, Yoon H S, et al. some sructure-property relationships in polymer flammability: Studies on poly(ethylene terephthalate). J Appl Polym Sci,1997, 31: 257～268
[29] Monagle J J, Mengenhauser J V, Jones D A, Jr. Nucleophilic activity of the phosphoryl group: resonance of the phosphoryl group with aromatic systems. J Org Chem, 1967, 32: 2477～2481
[30] Wan I Y, Kashiwagi T, Mc Grath J E. Synthesis, characterization and flame retardancy behavior of triaryl phosphine oxide containing nylon 6, 6copolymer. Polymeric Materials Science and Engineering Preprint, 1994,71:233～234
[31] Jensen W L. Organophosphorus Monomers and Polymers. Oxford: Pergamon, 1962
[32] 胡文祥，恽留红等．有机磷化物及其规律研究．军事医学科学院院刊，1993，17(3)
[33] 魏文德主编，有机化工原料大全．北京：化学工业出版社，1994，440
[34] 刑其毅。有机化学(上册)．北京：高等教育出版社，1992
[35] 常明勤．芳烃侧链氧化在有机合成中的应用进展．锦州师范学院学报(自然科学版)，1998(1)：37-44
[36] 邢其毅．有机化学(上册)．北京：高等教育出版社，1992
[37] 黄金印．PET阻燃剂的合成；(学位论文)．北京：北京理工大学化工与化学学院，1998
[38]Thiesing N, Feld W A. The synthesis of a polybenzoxazole containing phosphine oxide and hexafluoroisopropylidene linkages. Polym Prepr, 1995.36(2): 271
[39]岳阳化工总厂研究院有机合成二室．以醋酸锆为共催化剂的对二甲苯液相空气钴催化氧化制对苯二甲酸．合成纤维工业，1980．(1)：11～21
[40]崔玉民，邵思常．对硝基苯甲酸新工艺的研究．石油化工，1999，28(11)：742～744
[41]王树良，戴桂元，史达清．卤索取代甲苯的合成及其在Co(OAC)_2-Mn(OAC)_2-NaBr催化下的液相氧化反应．应用化学，1996，13(2)：41～44
[42]张永华．氧气液相氧化蒽制取蒽醌的研究．现代化工，1999，19(11)：29～31
[43]张祥富，时效天．甲苯常压催化氧化制苯甲酸及其它芳烃的氧化反应的研究．合成化学，1998，6(4)：433～437
[44]Res Dev. Trans Mechanism. Ind. Eng Trans 1973, 12(2):16～18
[45]D.A.S.Revens. Trans,Faraday Soc., 1959(55):1768
[46]M.G.Evans, N.S.Hush, and N.Uri.:Quart. Rev. J Amer chem Soc 1952(6):186
[47]阿莫科化学品公司．迪凯特4号厂氧化装置操作手册，1979
[48]Kyugo Tanaka. Adipic acid in one step. Chomtech September, 1974, 555～559
[49]曹鸿林．合成纤维单体工艺学．北京：纺织工业出版社，1981
[50]王忠元，阎丽梅，季景华，王坤．液相空气氧化制均苯三酸的研究．天津化工，1998(1)：2～5
[51]都国华，骆晓玲．邻二甲苯空气氧化制取邻甲基苯甲酸．石油化工，1998(27)：82～84
[52]姜恒，马学良，宫红．过渡金属盐及络合物在乙苯液相氧化中的催化作用．石油化工，1998，27(12)：877～879
[53]武现春，单希林，张坤斌，王宁．钴—溴催化氧化邻二甲苯制邻甲基苯甲酸．大庆石油学院学报，1999，23(2)：33～35
[54]罗澄源．物理化学实验．北京：高等教育出版社，1983
[55]姚允斌，解涛，高英敏．物理化学手册．上海：上海科学技术出版社，1985
[56]丁丽娟．数值计算方法．北京：北京理工大学出版社，1997
[57]Perry R H, Gree D W, Maloney J O. Perry's Chemical Engineer's Handbook. 6th edition, McGraw-Hill Book Company, 1984
[58]川田裕郎著．陈惠钊译．粘度．北京：计量出版社，1981
[59]Pal M, Glenn Hefter. Viscosities and Densities of highly concentrated aqueous MOH solutionsat 25.0℃. J. Chem, Eng. Data 2000, (45):613-617
[2] 王玉钟．聚酯纤维阻燃化设计．成都：四川科学技术出版社，1994．12～17
[3] 王玉钟．阻燃PET纤维的制备、结构和性能．合成纤维工业，1993，16(3)：22～25
[4] 沈发治，梁波涛．磷-溴双元素阻燃涤纶的研制．合成纤维工业，1996，19(3)：13～16
[5] Koch P J, Pearce E M, Lapham J A, et al. Flam-retardant poly(ethylene terephthalate). J Appl Polym Sci, 1979, 19:227～234
[6] Van Krevelen D M. Flame Resistance of Chemical Fibers. J Appl polym Sci, 1977, 31: 269～292
[7] Ou Y X, ed. Proceedings of the International Symposium on Flame Retardants, Bcijing: International Academic Pulisher, 1989. 548～553
[8] Bollert U, Lohmar E Ohorodnik A. Process for the manufacture of flame retarding linear polyesters. US Pat, C08G, 4033 936. 1977-05-05
[9] Lewin M M. Flame retardant Polymetic Material. New York : Plenum, 1975 (3): 193～196
[10] Herlinger H．合成纤维发展趋势．合成纤维工业，1981(1)：55～60
[11] 欧育湘．有机阻燃剂最新进展．现代化工，1997(4)：9～12
[12] Kidder R C. Fire safety issues in the United States in 1994. In The British P1 a stics Federation, ed. Flame Retardants'94 London: Elsevier Applied Science, 1990, 114～125
[13] Chaplin D, Brown S C. Flamtard, A new range of flame and smoke retardants. In: the British Plastics Federation, ed. FlameRetadants'90. London Elsevier Applied Science, 1990, 21～31
[14] Cusack P A. Flame-retardant inorganic in additive which suppress smoke and carb on monoxide emisson from burning polymers. In: The British Plastics Federation, ed.
FlameRetadants'90． London Elsevier Applied Science, 1990, 176-190
[15] Mount R A. Flame-retardant Non-halogen themoplastics. In: The Fire Retardant Chemicals Association, USA, ed. Fire Retardant Technology and Marketing. New York: Wiley Interscience, 1994． 253-259
[16] Cicchetti O, Bertelli G, Bevilacqua A et al. Advances in intumescent flame retardants'94 London: Elsevier Applied Science, 1994:129-142
[17] Cullis C F, Hirshler M M. The Combudtion of Organic Polymers.Oxford: Clarendon Press, 1981:241-254
[18] Pagliari A, Cicchetti O, Bevilacqua A, et al. Intumescent flame retardants: new evidence of their higher fire safety, In: The British Plastics Federation, ed. Flame Retardants'92． London: Elsevier Applied Science, 1992:41-52
[19] Deshpande A B, Pearce E M, Yoon H S, et al. Some structure-property relationships in polymer flammability: Studies on poly(ethylene terephthalate). J Appl Polyrn Sci, 1977(31) :257-268
[20] Banks M, Ebdon J R, Johnson M. Influence of covalently bound phosphorus-comtaining groups on the fanmmability of some common addition homo-and polymers,In: The British plastics Federation, ed. Flame Retardants'94． London: Elsevier Applied Science, 1994:183-192
[21] Barker R H. Fire Safety Research. Gaithersburg: National Bureau of Standars Special Publication, 1973:37-42
[22] Endo S, kashihara T, Osako A, et al,. Phosphorus-containing compounds. US Pat, C07F 4 127 590． 1978-11-28
[23] Van Krevelen D M. Flame resistande of chemical fibers. J Appl Polym Sci, 1977(31) : 269-292
[24] Morgan P W. Herr B C. Some dicarboxylic acids and esters containing me phosphine
oxide group, J Amer Chem Soc, 1952,74:4526～4529
[25] Wan I Y, Kashiwagi T, Me Grath J E. Synthesis, characterization and flame retardancy behavior of triaryl phosphine oxide containing nylon 6, 6copolymer. Polymeric Materials Science and Engineering Preprint, 1994,71:233～234
[26] Morgan P W, Kenmore N Y. Synthetics linear consideration polymers containing phosporus. US Pat, C1260-75, 2 646 420. 1953-07-21
[27] Shciemenz G P, Siebeneick H U. Phosphine mit mehreren elektronenak zeptordubstituenten. Chem Ber, 1969, 102:1883～1891
[28] Deshpande A B, Pearce E M, Yoon H S, et al. some sructure-property relationships in polymer flammability: Studies on poly(ethylene terephthalate). J Appl Polym Sci,1997, 31: 257～268
[29] Monagle J J, Mengenhauser J V, Jones D A, Jr. Nucleophilic activity of the phosphoryl group: resonance of the phosphoryl group with aromatic systems. J Org Chem, 1967, 32: 2477～2481
[30] Wan I Y, Kashiwagi T, Mc Grath J E. Synthesis, characterization and flame retardancy behavior of triaryl phosphine oxide containing nylon 6, 6copolymer. Polymeric Materials Science and Engineering Preprint, 1994,71:233～234
[31] Jensen W L. Organophosphorus Monomers and Polymers. Oxford: Pergamon, 1962
[32] 胡文祥，恽留红等．有机磷化物及其规律研究．军事医学科学院院刊，1993，17(3)
[33] 魏文德主编，有机化工原料大全．北京：化学工业出版社，1994，440
[34] 刑其毅。有机化学(上册)．北京：高等教育出版社，1992
[35] 常明勤．芳烃侧链氧化在有机合成中的应用进展．锦州师范学院学报(自然科学版)，1998(1)：37-44
[36] 邢其毅．有机化学(上册)．北京：高等教育出版社，1992
[37] 黄金印．PET阻燃剂的合成；(学位论文)．北京：北京理工大学化工与化学学院，1998
[38]Thiesing N, Feld W A. The synthesis of a polybenzoxazole containing phosphine oxide and hexafluoroisopropylidene linkages. Polym Prepr, 1995.36(2): 271
[39]岳阳化工总厂研究院有机合成二室．以醋酸锆为共催化剂的对二甲苯液相空气钴催化氧化制对苯二甲酸．合成纤维工业，1980．(1)：11～21
[40]崔玉民，邵思常．对硝基苯甲酸新工艺的研究．石油化工，1999，28(11)：742～744
[41]王树良，戴桂元，史达清．卤索取代甲苯的合成及其在Co(OAC)_2-Mn(OAC)_2-NaBr催化下的液相氧化反应．应用化学，1996，13(2)：41～44
[42]张永华．氧气液相氧化蒽制取蒽醌的研究．现代化工，1999，19(11)：29～31
[43]张祥富，时效天．甲苯常压催化氧化制苯甲酸及其它芳烃的氧化反应的研究．合成化学，1998，6(4)：433～437
[44]Res Dev. Trans Mechanism. Ind. Eng Trans 1973, 12(2):16～18
[45]D.A.S.Revens. Trans,Faraday Soc., 1959(55):1768
[46]M.G.Evans, N.S.Hush, and N.Uri.:Quart. Rev. J Amer chem Soc 1952(6):186
[47]阿莫科化学品公司．迪凯特4号厂氧化装置操作手册，1979
[48]Kyugo Tanaka. Adipic acid in one step. Chomtech September, 1974, 555～559
[49]曹鸿林．合成纤维单体工艺学．北京：纺织工业出版社，1981
[50]王忠元，阎丽梅，季景华，王坤．液相空气氧化制均苯三酸的研究．天津化工，1998(1)：2～5
[51]都国华，骆晓玲．邻二甲苯空气氧化制取邻甲基苯甲酸．石油化工，1998(27)：82～84
[52]姜恒，马学良，宫红．过渡金属盐及络合物在乙苯液相氧化中的催化作用．石油化工，1998，27(12)：877～879
[53]武现春，单希林，张坤斌，王宁．钴—溴催化氧化邻二甲苯制邻甲基苯甲酸．大庆石油学院学报，1999，23(2)：33～35
[54]罗澄源．物理化学实验．北京：高等教育出版社，1983
[55]姚允斌，解涛，高英敏．物理化学手册．上海：上海科学技术出版社，1985
[56]丁丽娟．数值计算方法．北京：北京理工大学出版社，1997
[57]Perry R H, Gree D W, Maloney J O. Perry's Chemical Engineer's Handbook. 6th edition, McGraw-Hill Book Company, 1984
[58]川田裕郎著．陈惠钊译．粘度．北京：计量出版社，1981
[59]Pal M, Glenn Hefter. Viscosities and Densities of highly concentrated aqueous MOH solutionsat 25.0℃. J. Chem, Eng. Data 2000, (45):613-617