WO2017166916A1 - 四(4-羟基苯胺甲基)硫酸膦及其合成方法 - Google Patents

四(4-羟基苯胺甲基)硫酸膦及其合成方法 Download PDF

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WO2017166916A1
WO2017166916A1 PCT/CN2017/072322 CN2017072322W WO2017166916A1 WO 2017166916 A1 WO2017166916 A1 WO 2017166916A1 CN 2017072322 W CN2017072322 W CN 2017072322W WO 2017166916 A1 WO2017166916 A1 WO 2017166916A1
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tetrakis
hydroxyanilinomethyl
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sulfate according
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戴李宗
柳超
黄佳美
陈国荣
袁丛辉
罗伟昂
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen

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  • the invention relates to a flame retardant, in particular to a phosphorus-nitrogen flame retardant and a synthesis method thereof.
  • Polymer materials are widely used in all aspects of daily life because of their light weight, excellent mechanical strength, corrosion resistance, and design, which are different from traditional materials.
  • polymer materials are flammable in the air and release a large amount of toxic gases when burned.
  • Traditional flame retardants such as halogen flame retardants, have been widely used because of their high flame retardant efficiency and reasonable price.
  • the application of such flame retardants is greatly limited because it releases hydrogen halide when it burns, and itself becomes a source of pollution. Therefore, the development of new halogen-free flame retardants with high flame retardant efficiency has become one of the major issues in the development of polymer materials.
  • Phosphorus-containing flame retardants are used in a wide variety of polymer materials and do not cause environmental pollution. Therefore, they have become a good substitute for halogen-based flame retardants.
  • flame retardants containing phosphorus and other flame retardant elements have become a research hotspot in the field of flame retardant because of their synergistic flame retardant effects.
  • Wang Yuzhong et al. Ind. Eng. Chem. Res., 2012, 51 (29), pp 9769–9776), etc., in which 2-carboxyethylbenzene phosphate was dissolved in water, and melamine was added thereto to synthesize 2-carboxyethylbenzene.
  • Melamine phosphate (CMA) Melamine phosphate
  • the polyurethane soft foam can pass the Cal T.B.117A-I standard flame retardant test, and the LOI can be increased from 18.2% to 24.1% without reducing the mechanical properties of the polyurethane soft foam.
  • Liufeng Cheng et al. (Ind. Eng. Chem. Res., 2015, 54(32), pp7777–7786) synthesized TMT with N-hydroxyphenylmaleimide and cyanuric chloride, and then reacted with DOPO to obtain DOPO-TMT, which is incorporated into epoxy resin, is found to have a flame retardant effect in both the gas phase and the solid phase.
  • the invention uses tetrakis-hydroxymethylphosphine sulfate (THPS) and p-aminophenol as raw materials to synthesize a phosphine sulfate salt by the Mannich reaction of tetramethylolsulfate phosphine and p-aminophenol, ie tetrakis(4-hydroxyaniline) Phosphate, its structural formula is as follows:
  • the phosphonium sulfate salt of the invention is prepared by reacting tetrakishydroxymethylphosphine sulfate (THPS) and p-aminophenol as raw materials in an organic solvent to obtain a crude product, and then suction filtration, washing the filter residue with an organic solvent, dispersing with distilled water, and centrifuging. The lower layer of the precipitate was taken, organic solvent was added, the water was washed away, and finally dried under vacuum.
  • THPS tetrakishydroxymethylphosphine sulfate
  • the raw materials used are tetramethylolsulfate (THPS) and p-aminophenol; the reaction solvent includes anhydrous ethanol and acetone; and the washing solvent includes anhydrous ethanol, acetone, and distilled water.
  • THPS tetramethylolsulfate
  • p-aminophenol purchased from Aladdin Reagent Company, and anhydrous ethanol and acetone were purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the p-aminophenol is added to a certain amount of an organic solvent, stirred under a nitrogen atmosphere and raised in temperature, and after complete dissolution, tetrakishydroxymethylphosphine sulfate (THPS) is added dropwise, and after the completion of the dropwise addition, the reaction is kept for 0.5 to 3 hours.
  • the ratio of the amount of tetramethylolsulfate (THPS) and p-aminophenol is 1:4-1:10
  • the reaction solvent is anhydrous ethanol or acetone
  • the amount of the reaction solvent is 20-30 of the mass of p-aminophenol.
  • the reaction temperature is 30 ° C - 80 ° C.
  • the reaction system was suction-filtered under reduced pressure to obtain a residue, which was washed one to three times with a solvent.
  • a certain amount of distilled water was completely dispersed, ultrasonically dispersed, and then centrifuged, and washed repeatedly with distilled water once or twice.
  • the lower layer precipitate after centrifugation is taken, a certain amount of the reaction solvent is added, ultrasonically dispersed, and then the precipitate is centrifuged, and the washing is repeated one to three times with the reaction solvent. Finally, it is vacuum dried.
  • the ratio of the mass of the distilled water to the mass of the reaction solvent is 1:2-1:6, and the ratio of the mass of the reaction solvent added to the mass of the distilled water to be added at the time of washing is 0.5:1 to 2:1.
  • Figure 1 is a nuclear magnetic resonance spectrum of tetrakis(4-hydroxyanilinomethyl)phosphine sulfate.
  • Figure 2 is a nuclear magnetic resonance phosphorus spectrum of tetrakis(4-hydroxyanilinomethyl)phosphine sulfate.
  • Figure 3 is an infrared spectrum of tetrakis(4-hydroxyanilinomethyl)phosphine sulfate.
  • p-aminophenol 2.18 g was weighed into a three-necked flask equipped with a reflux condenser of 100 mL, and then 50 mL of acetone was added thereto, and the temperature was raised to 60 ° C under a nitrogen atmosphere. After the aminophenol was dissolved, 2.7 g of tetramethylolsulfate (THPS) was added dropwise with a constant pressure dropping funnel, and the reaction was kept for 2 hours after the completion of the dropwise addition. After completion of the reaction, the mixture was filtered under reduced pressure and the residue was washed twice with 20 mL of anhydrous ethanol.
  • THPS tetramethylolsulfate
  • p-aminophenol 2.18 g was weighed into a three-necked flask equipped with a reflux condenser of 100 mL, 60 mL of acetone was further added, and the temperature was raised to 60 ° C under a nitrogen atmosphere. After the aminophenol was dissolved, 2.7 g of tetramethylolsulfate (THPS) was added dropwise with a constant pressure dropping funnel, and the reaction was kept for 1 hour after the completion of the dropwise addition. After completion of the reaction, the mixture was filtered under reduced pressure and the residue was washed twice with 20 mL of anhydrous ethanol.
  • THPS tetramethylolsulfate

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本发明合成了四(4-羟基苯胺甲基)硫酸膦，并详述了其合成方法。其结构式为(I)。原料为四羟甲基硫酸膦(THPS)、对氨基苯酚、有机溶剂和蒸馏水。合成方法为四羟甲基硫酸膦(THPS)和对氨基苯酚在有机溶剂中反应，并经过减压抽滤，洗涤提纯，最后脱去溶剂后得到该种硫酸膦盐。

Description

四(4-羟基苯胺甲基)硫酸膦及其合成方法 技术领域
本发明涉及一种阻燃剂，尤其是一种磷氮阻燃剂及其合成方法。
背景技术
高分子材料因其具有质轻、优异的机械强度、耐腐蚀以及可设计等不同于传统材料的优点而广泛应用于日常生活的方方面面。但高分子材料在空气中易燃，且燃烧时释放出大量有毒气体。传统的阻燃剂，如卤系阻燃剂，因为阻燃效率高、价格合适等优点曾得到广泛应用。但该类阻燃剂的应用因其燃烧时会释放出卤化氢，并且本身会成为污染源而受到极大限制。因此，开发阻燃效率高的新型无卤阻燃剂已经成为高分子材料发展的重大课题之一。
含磷阻燃剂种类繁多，能适用于多种高分子材料，并且不会造成环境污染，因此，其已成为卤系阻燃剂的良好替代品。尤其，含有磷元素和其它阻燃元素的阻燃剂因其具有协同阻燃作用已成为阻燃领域的研究热点。王玉忠等(Ind.Eng.Chem.Res.，2012，51(29)，pp 9769–9776)等将2-羧乙基苯磷酸溶于水，向其中加入三聚氰胺，合成了2-羧乙基苯磷酸三聚氰胺盐(CMA)。他们发现仅添加质量分数为12％的CMA，聚氨酯软泡可以通过Cal T.B.117A-I标准阻燃测试，LOI可从18.2％提高到24.1％，同时不降低聚氨酯软泡的机械性能。Liufeng Cheng等(Ind.Eng.Chem.Res.，2015，54(32)，pp7777–7786)用N-羟基苯基马来酰亚胺和三聚氯氰合成了TMT，再与DOPO反应，得到DOPO-TMT，掺到环氧树脂中发现其在气相和固相均可发挥阻燃作用。
发明内容
本发明以四羟甲基硫酸膦(THPS)和对氨基苯酚为原料，通过四羟甲基硫酸膦和对氨基苯酚发生曼尼希反应合成一种硫酸膦盐，即四(4-羟基苯胺甲基)硫酸膦，其结构式如下：
Figure PCTCN2017072322-appb-000001
本发明所述的硫酸膦盐以四羟甲基硫酸膦(THPS)和对氨基苯酚为原料，在有机溶剂中反应得到粗产物，然后抽滤，并用有机溶剂洗涤滤渣，用蒸馏水分散，离心，取下层沉淀物，加入有机溶剂，洗去水分，最后真空干燥。
所用原料为四羟甲基硫酸膦(THPS)和对氨基苯酚；反应溶剂包括无水乙醇、丙酮；洗涤溶剂包括无水乙醇、丙酮、蒸馏水。四羟甲基硫酸膦(THPS)和对氨基苯酚购自阿拉丁试剂公司，无水乙醇、丙酮购自国药集团化学试剂有限公司。
四(4-羟基苯胺甲基)硫酸膦的合成工艺如下：
将对氨基苯酚加入到一定量的有机溶剂中，在氮气氛围下搅拌并升高温度，待完全溶解后逐滴加入四羟甲基硫酸膦(THPS)，滴完后保温反应0.5-3小时。四羟甲基硫酸膦(THPS)和对氨基苯酚的物质的量之比为1:4-1:10，反应溶剂为无水乙醇或丙酮，反应溶剂的用量为对氨基苯酚质量的20-30倍，反应温度为30℃-80℃。
反应体系减压抽滤得到滤渣，滤渣用反应溶剂洗涤一到三次。洗涤完全后一定量的蒸馏水，超声分散，然后离心沉淀，用蒸馏水重复洗涤一到两次。取离心后的下层沉淀物，加入一定量的反应溶剂，超声分散，然后离心沉淀，用反应溶剂重复洗涤一到三次。最后真空干燥。加入的蒸馏水的质量与反应溶剂质量的比为1:2-1:6，洗涤时加入的反应溶剂的质量与加入的蒸馏水的质量的比为0.5:1-2:1。
附图说明
附图1为四(4-羟基苯胺甲基)硫酸膦的核磁共振氢谱图。
附图2为四(4-羟基苯胺甲基)硫酸膦的核磁共振磷谱图。
附图3为四(4-羟基苯胺甲基)硫酸膦的红外谱图。
具体实施方式
下面通过实施实例对本发明做具体说明。
实施例1
称取2.18g对氨基苯酚加入到装有回流冷凝管100mL的三口烧瓶中，再加入50mL无水乙醇，在氮气氛围下升温到60℃。待对氨基苯酚溶解后用恒压滴液漏斗逐滴加入1.35g四羟甲基硫酸膦(THPS)，滴完后保温反应2小时。反应结束后减压抽滤，滤渣用20mL无水乙醇洗涤两次。向滤渣中加入20mL蒸馏水，超声使其均匀分散，然后离心沉淀，用蒸馏水重复洗涤一次。再向经洗涤过的粗产物中加入20mL无水乙醇，离心沉淀，用无水乙醇重复洗涤两次。将最后得到的产物真空干燥，即得目标产物。
实施例2
称取2.18g对氨基苯酚加入到装有回流冷凝管100mL的三口烧瓶中，再加入50mL丙酮，在氮气氛围下升温到60℃。待对氨基苯酚溶解后用恒压滴液漏斗逐滴加入2.7g四羟甲基硫酸膦(THPS)，滴完后保温反应2小时。反应结束后减压抽滤，滤渣用20mL无水乙醇洗涤两次。向滤渣中加入20mL蒸馏水，超声使其均匀分散，然后离心沉淀，用蒸馏水重复洗涤一次。再向经洗涤过的粗产物中加入20mL无水乙醇，离心沉淀，用无水乙醇重复洗涤两次。将最后得到的产物真空干燥，即得目标产物。
实施例3
称取2.18g对氨基苯酚加入到装有回流冷凝管100mL的三口烧瓶中，再加入50mL丙酮，在氮气氛围下升温到65℃。待对氨基苯酚溶解后用恒压滴液漏斗逐滴加入1.35g四羟甲基硫酸膦(THPS)，滴完后保温反应2小时。反应结束后减压抽滤，滤渣用20mL无水乙醇洗涤两次。向滤渣中加入20mL蒸馏水，超声使其均匀分散，然后离心沉淀，用蒸馏水重复洗涤一次。再向经洗涤过的粗产物中加入20mL无水乙醇，离心沉淀，用无水乙醇重复洗涤两次。将最后得到的产物真空干燥，即得目标产物。
实施例4
称取2.18g对氨基苯酚加入到装有回流冷凝管100mL的三口烧瓶中，再加入60mL丙酮，在氮气氛围下升温到60℃。待对氨基苯酚溶解后用恒压滴液漏斗逐滴加入2.7g四羟甲基硫酸膦(THPS)，滴完后保温反应1小时。反应结束后减压抽滤，滤渣用20mL无水乙醇洗涤两次。向滤渣中加入20mL蒸馏水，超声使其均匀分散，然后离心沉淀，用蒸馏水重复洗涤一次。再向经洗涤过的粗产物中加入20mL无水乙醇，离心沉淀，用无水乙醇重复洗涤两次。将最后得到的产物真空干燥，即得目标产物。

Claims (10)

  1. 四(4—羟基苯胺甲基)硫酸膦，其结构式如下：
    Figure PCTCN2017072322-appb-100001
  2. 如权利要求1所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于其具体步骤如下：
    将对氨基苯酚加入到有机溶剂中，在氮气氛围下搅拌，溶解后加入四羟甲基硫酸膦，反应后减压抽滤，得滤渣，滤渣洗涤后超声分散，离心沉淀，再用蒸馏水洗涤，取离心后的下层沉淀物加入有机溶剂超声分散，然后再离心沉淀，再次洗涤，干燥后即得四(4-羟基苯胺甲基)硫酸膦。
  3. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述四羟甲基硫酸膦和对氨基苯酚的质量比为1∶(4～10)。
  4. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述反应的温度为30～80℃，反应的时间为0.5～3h。
  5. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述有机溶剂采用无水乙醇或丙酮。
  6. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述有机溶剂的用量按质量比为对氨基苯酚的20～30倍。
  7. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述滤渣洗涤采用无水乙醇洗涤1～3次。
  8. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述用蒸馏水洗涤1～2次，加入的蒸馏水与有机溶剂的质量比为1∶(2～6)。
  9. 如权利要求2所述四(4-羟基苯胺甲基)硫酸膦的合成方法，其特征在于所述再次洗涤用有机溶剂重复洗涤1～3次，再次洗涤时加入的有机溶剂与加入的蒸馏水的质量比为(0.5～2)∶1。
  10. 如权利要求1所述四(4-羟基苯胺甲基)硫酸膦在制备阻燃材料中的应用。
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CN121155222A (zh) * 2025-08-27 2025-12-19 安徽中电环保材料股份有限公司 一种高炉煤气过滤材料

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CN106905510B (zh) * 2017-03-13 2019-06-25 厦门大学 一种含多官能团的反应型阻燃剂及其合成方法和应用
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