双（对—羧苯基）苯基氧化膦的合成及其工艺优化
摘要
由于双(对-羧苯基)苯基氧化膦(BCPPO)分子结构中含有两个羧基和阻燃元素磷,因此可用作聚酯、聚酰胺、棉纤维等多种聚合物的反应型阻燃剂或阻燃单体以制得阻燃聚合物材料,它可同时赋予聚合物较好的阻燃性、抗静电性和染色性,较高的热稳定性和氧化稳定性以及较高的玻璃化转变温度等性能,具有广阔的应用前景。
本论文通过优化BCPPO的各步合成工艺条件,缩短实验周期,减少贵重溶剂的用量,以降低成本,为其工业化生产提供依据,主要工作及创造性研究有以下几个方面:
(1)苯基二氯化膦的合成(DCPP)
合成中间体苯基二氯化膦,确定原料最佳的摩尔比及苯的投料方式,探索最佳的工艺条件。
(2)双(对-甲苯基)苯基硫化膦(BMPPS)的合成
优化BMPPS的合成工艺,确定各种原料的最佳配比并缩短反应时间,提高BMPPS的收率。
(3)不同配比的水-吡啶混合液中BMPPS的溶解度的测定
研究了同一配比的吡啶-水溶液中,BMPPS的溶解度与温度的关系;以及相同温度下,BMPPS的溶解度随着吡啶-水溶液中吡啶摩尔数的增加的变化趋势。
(4)BCPPO的合成
选择了合适的高锰酸钾的加料温度及反应氧化温度,在保证BCPPO较高收率的前提下,用廉价的水替代部分吡啶,降低昂贵溶剂吡啶的用量,得出最佳的吡啶和水的配比,缩短反应周期,降低生产成本。
(5)产物的表征
通过显微熔点测定仪,IR,UV,DSC,1H-NMR对制得的中间物BMPPS和目标物BCPPO进行结构表征及定量分析。
Because two carboxyl group and flame retardant element phosphorus exist in the molecular structure, Bis(4-carboxyphenyl) phenyl phosphine oxide(BCPPO) was applied as the reactive-type flame retardant for plastics of many polymers such as polyester , polyamide , cotton fiber and so on, or as flame retardant monomer to obtain flame retardant polymer material. Polymers had the properties of flame retardance, antistatic electricity, dyeability, thermal stability, oxidation stability and high glass transition temperature because of BCPPO, so it had a broad application prospect.
This topic provided the basis of industrialization, according to optimizing every process condition, decreasing the production cycle and the consumption of expensive solvent to reduce production costs. The work and the study were as follows:
(1) The synthesis of phenylphosphorus dichloride (DCPP)
DCPP was synthesized, the feeding style of C6H6 and the appropriate mol ratio of all kinds of raw materials was determined.
(2) The synthesis of bis(4-methylphenyl)phenyl Phosphine Sulfid (BMPPS)
Process conditions of BMPPS were optimized. The appropriate mol ratio of all kinds of raw materials was determined, the reaction time was shortened, and rate of production of BMPPS was improved at the same time.
(3) The measurement of the solubility of BMPPS in water and pyridine solution
How the solubility of BMPPS would change was studied when the temperature elevated in the same solution and when mole fraction of pyridine increased at the same temperature.
(4) The synthesis of product
The appropriate feeding temperature and reaction temperature were chosen. Some pyridine was replaced by low-cost water to cut down the consumption of expensive pyridine, the reaction time was shortened and the mole ratio of pyridine and water was determined, when the yield of BCPPO was high. So production costs were cut down.
(5) The characterization of product
The ultimate product and intermediate product were inspected and synthesized by micro-melting point inspector, IR, UV, DSC, 1H-NMR technology.
本论文通过优化BCPPO的各步合成工艺条件,缩短实验周期,减少贵重溶剂的用量,以降低成本,为其工业化生产提供依据,主要工作及创造性研究有以下几个方面:
(1)苯基二氯化膦的合成(DCPP)
合成中间体苯基二氯化膦,确定原料最佳的摩尔比及苯的投料方式,探索最佳的工艺条件。
(2)双(对-甲苯基)苯基硫化膦(BMPPS)的合成
优化BMPPS的合成工艺,确定各种原料的最佳配比并缩短反应时间,提高BMPPS的收率。
(3)不同配比的水-吡啶混合液中BMPPS的溶解度的测定
研究了同一配比的吡啶-水溶液中,BMPPS的溶解度与温度的关系;以及相同温度下,BMPPS的溶解度随着吡啶-水溶液中吡啶摩尔数的增加的变化趋势。
(4)BCPPO的合成
选择了合适的高锰酸钾的加料温度及反应氧化温度,在保证BCPPO较高收率的前提下,用廉价的水替代部分吡啶,降低昂贵溶剂吡啶的用量,得出最佳的吡啶和水的配比,缩短反应周期,降低生产成本。
(5)产物的表征
通过显微熔点测定仪,IR,UV,DSC,1H-NMR对制得的中间物BMPPS和目标物BCPPO进行结构表征及定量分析。
Because two carboxyl group and flame retardant element phosphorus exist in the molecular structure, Bis(4-carboxyphenyl) phenyl phosphine oxide(BCPPO) was applied as the reactive-type flame retardant for plastics of many polymers such as polyester , polyamide , cotton fiber and so on, or as flame retardant monomer to obtain flame retardant polymer material. Polymers had the properties of flame retardance, antistatic electricity, dyeability, thermal stability, oxidation stability and high glass transition temperature because of BCPPO, so it had a broad application prospect.
This topic provided the basis of industrialization, according to optimizing every process condition, decreasing the production cycle and the consumption of expensive solvent to reduce production costs. The work and the study were as follows:
(1) The synthesis of phenylphosphorus dichloride (DCPP)
DCPP was synthesized, the feeding style of C6H6 and the appropriate mol ratio of all kinds of raw materials was determined.
(2) The synthesis of bis(4-methylphenyl)phenyl Phosphine Sulfid (BMPPS)
Process conditions of BMPPS were optimized. The appropriate mol ratio of all kinds of raw materials was determined, the reaction time was shortened, and rate of production of BMPPS was improved at the same time.
(3) The measurement of the solubility of BMPPS in water and pyridine solution
How the solubility of BMPPS would change was studied when the temperature elevated in the same solution and when mole fraction of pyridine increased at the same temperature.
(4) The synthesis of product
The appropriate feeding temperature and reaction temperature were chosen. Some pyridine was replaced by low-cost water to cut down the consumption of expensive pyridine, the reaction time was shortened and the mole ratio of pyridine and water was determined, when the yield of BCPPO was high. So production costs were cut down.
(5) The characterization of product
The ultimate product and intermediate product were inspected and synthesized by micro-melting point inspector, IR, UV, DSC, 1H-NMR technology.
引文
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[5] Howell B A, Uhl F M, Sohnston K J.Flameretardant Phosphonium Salts Containing High Levels of Bromine[J]. Polym Mater Sci Eng,1997, (76): 399~400.
[6] 杨锦飞,丁海嵘.磷系阻燃剂现状与展望[J].江苏化工.1999, 27(6): 1-6.
[7] 袁金颖,左光汉,黄钢.反应型阻燃剂N,N-二羟乙基胺甲基磷酸二乙酯及其阻燃试验[J].精细石油化工.1997, (1): 6-8.
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[9] 欧育湘.实用阻燃技术[M].北京:化学工业出版社.2002, (4) : 168-231.
[10] 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, 3-16.
[11] 欧育湘,陈宇,王筱梅.阻燃高分子材料[M].北京:国防工业出版社.2001: 4-20.
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[13] 欧育湘.国外阻燃剂发展动态及对发展我国阻燃剂工业之浅见[J].精细与专用化学品.2003, (2): 3-6.
[14] 庞晓华.未来几年美国阻燃剂市场将快速增长[J].精细石油化工进展.2005, 6(5): 20.
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[16] 欧育湘.无卤阻燃 PA 最新研究进展[J].高分子材料科学与工程.2005, 21(3): 1-5.
[17] 丁涛,田明等.聚碳酸酯无卤阻燃剂进展[J].现代化工.2004, 24(10): 10-14.
[18] Troitzsch J. The future of flame retarded production in Europe[A].Proceedings of Flame Retardants 2002[C],London: Interscience Communications, 2002, 249-257.
[19] Troitzsch J. The globalization of fire testing and its impact on polymers and flameretardants[J].Polymer degradation and stability,2005, 88: 146-149.
[20] 黄汉生.日本非卤素阻燃剂发展动向[J].现代化工.2002, 22(12): 52-55.
[21] 欧育湘[M]精细与专用化学品.2003, (2): 3-6.
[22] 孙卫青,邱宗玺等.[J]郑州大学学报,2002, 34(4): 60-64.
[23] 王新龙,韩平.有机磷阻燃剂研究进展[J]精细石油化工进展.2002, 3(6): 33-34.
[24] Pagliari A, Cicohetti O, Bevilacqua A et al. Intumescent flame retardants: new evidence of their higher fire safety in the British Plastics Federation, ed[J]. Flame Retardants'92.London: Elsevier Applied Science,1992: 41-52.
[25] 鞠剑峰,胡啸林,苏广均.超细赤磷微胶囊阻燃剂对棉织品的阻燃效果研究[J].印染助剂.2004, 21(1): 48-49.
[26] 程志凌,陈文捷.塑料阻燃剂技术的进展[J].齐鲁石油化工.2002, 30(1): 56-58.
[27] 崔隽,姜洪雷,吴明艳等.阻燃剂的现状与发展趋势[J].山东轻工业学院学报.2003, 17(1): 14-17.
[28] Norio T. Functionalization of inorganic powder surfaceby the grafting of polymers[J].J of Polymer,1996,45(6): 416-421.
[29] 李志娟,李青山,杨德治.走向 21 世纪的新型阻燃剂[J].化学工程师.2001, (4): 34-36.
[30] 谢兴华,冯道全,何石文.阻燃材料的绿色化初探[J].淮南工业学院学报.2002, 22(2): 54-56.
[31] 刘丽君,郭奋,陈建峰.纳米氢氧化铝阻燃剂表面改性及其在聚丙烯中的应用[J].中国塑料.2004, 18(2): 74-77.
[32] 汪存东,王久芬.新型无卤阻燃剂的研究进展[J].应用化工.2003, 32(4): 16-19.
[33] 李永华,曾幸荣,刘波等.有机硅树脂与溴系阻燃剂协同阻燃 ABS 的研究[J].塑料工业.2004, 32(1): 13-16.
[34] Shui Yu Lu, Ian Hamerton.Recent developments in the chemistry of halogen free flame retardant polymers[J]. Prog Polym Sci, 2002, 27: 1661-1712.
[35] 阳范文,赵耀明.阻燃剂研究新进展[J].合成材料老化与应用.2000, (3): 18-21.
[36] 王德禧.阻燃、消烟型 PC/ABS 合金的研制[J].塑料.2003, 32(1): 62-67.
[37] 贾少晋,张志成等.辐射制备阻燃 HDPE/EPDM 电缆材料[J].辐射研究与辐射工艺学报.2002, 20(1): 61-66.
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