醇钠法合成磷酸三异辛酯
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摘要
以异辛醇和固体氢氧化钠为原料,采用共沸带水法合成异辛醇钠,再以异辛醇钠与三氯氧磷反应合成了磷酸三异辛酯,通过单因素实验考察了两步合成过程中共沸剂的种类和用量、异辛醇钠与三氯氧磷的摩尔比、三氯氧磷的滴加温度及保持时间等因素对反应的影响。实验结果表明,使用甲苯为共沸剂,可快速有效地脱除异辛醇钠制备过程中生成的水,当加入量占总溶剂25%(w)时,异辛醇钠含量为19.45%(w)。在n(异辛醇钠)∶n(三氯氧磷)=3.1∶1.0,滴加三氯氧磷温度30℃,保温温度110℃,保温时间30 min条件下,磷酸三异辛酯的收率达94.1%,纯度为99.5%(w)。所采用的合成方法不抽真空、反应速率快、收率高,有一定的实用价值。
Triisooctyl phosphate was synthesized from phosphorus oxychloride and sodium isooctanoxide which was prepared from isooctyl alcohol and solid sodium hydroxide via azeotropic distillation. The influences of azeotropic agents,the mole ratio of the reactants,dropping temperature of phosphorus oxychloride and reaction time on the synthesis were investigated by single-factor experiments. The experimental results indicated that using toluene as the azeotropic agent could quickly and effectively remove the water produced in the preparation process of sodium isooctanoxide. Under the conditions of toluene dosage 25%(w)(based on the total solvent mass,sodium isooctanoxide 19.45%(w),mole ratio of sodium isooctanoxide to phosphorus oxychloride 3.1 ∶ 1.0,dropping temperature of phosphorus oxychloride 30 ℃,holding temperature 110 ℃ and holding time 30 min,the yield and purity of triisooctyl phosphate reached 94.1% and 99.5%(w),respectively. The synthetic method has certain practical value with the advantages of no vacuum,fast reaction rate and high product yield.
Triisooctyl phosphate was synthesized from phosphorus oxychloride and sodium isooctanoxide which was prepared from isooctyl alcohol and solid sodium hydroxide via azeotropic distillation. The influences of azeotropic agents,the mole ratio of the reactants,dropping temperature of phosphorus oxychloride and reaction time on the synthesis were investigated by single-factor experiments. The experimental results indicated that using toluene as the azeotropic agent could quickly and effectively remove the water produced in the preparation process of sodium isooctanoxide. Under the conditions of toluene dosage 25%(w)(based on the total solvent mass,sodium isooctanoxide 19.45%(w),mole ratio of sodium isooctanoxide to phosphorus oxychloride 3.1 ∶ 1.0,dropping temperature of phosphorus oxychloride 30 ℃,holding temperature 110 ℃ and holding time 30 min,the yield and purity of triisooctyl phosphate reached 94.1% and 99.5%(w),respectively. The synthetic method has certain practical value with the advantages of no vacuum,fast reaction rate and high product yield.
引文
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[3]Shim E G,Nam T H,Kim J G,et al.Effects of trioctylphosphate and cresyl diphenyl phosphate as fl ame-retarding additives for Li-ion battery electrolytes[J].Met Mater Int,2009,15(4):615-621.
[4]张雪,张园,叶斐斐,等.磷系阻燃剂的发展及应用研究[J].工程塑料应用,2015,43(11):112-117.
[5]Anitha M,Kotekar M K,Singh D K,et al.Solvent extraction studies on rare earths from chloride medium with organophosphorous extractant dinonyl phenyl phosphoric acid[J].Hydrometallurgy,2014,146(3):128-132.
[6]Akzo Nobel NV.Process for the production of hydroge peroxide and composition for use therein:EP1292533 B1[P].2009-12-30.
[7]乔迎超,万双华.蒽醌法生产双氧水的传统工艺和全酸性工艺对比[J].当代化工,2016,45(1):185-188.
[8]刘航,方向晨,贾立明,等.蒽醌法生产H2O2工作液的改进[J].石油学报,2015,31(1):73-77.
[9]FMC Corporation.Pregeneration of tetra hydro anthra quinones in a make-up solution to be added to a hydrogen peroxide working solution:US4514376[P].1985-04-30.
[10]韩秀山,磷酸三辛酯的合成[J].沈阳化工,1998,27(4):4-7.
[11]天津市联瑞阻燃材料有限公司.一种磷酸三辛酯的合成方法:103224516 A[P].2013-07-31.
[12]青岛旺裕橡胶制品有限公司.磷酸三辛酯的制备方法:14592294 A[P].2015-05-06.
[13]FMC Corporation.Continuous phosphorylation process:US8404045 A[P].1984-8-30.
[14]陈筱京,王国华,吴静.磷酸三辛酯的研制[J].江苏化工,1991(4):27-28.
[15]杭州潜阳科技有限公司.一种磷酸三辛酯的生产方法:103435642 B[P].2014-07-23.
[16]吕文学.用异辛醇合成磷酸酯[J].辽宁化工,2008,37(7):440-441.
[17]Dynamit Nobel AG.Verfahren zur herstellung von phosphor enthaltenden verbindungen:DE1905095 A[P],1969-01-30.
[18]岳阳市中顺化工有限责任公司.一种磷酸三辛酯工业生产方法:103304595 A[P].2013-09-18.
[19]高清伟,李效军.金属氯化物催化磷酸三丁酯的合成研究[J].精细石油化工,2015,32(1):23-25.