【作者】 郭春伟；

【导师】 殷福珊； 刘俊康；

【作者基本信息】 江南大学 ， 应用化学， 2005， 硕士

【摘要】 本文对烷基磷酸酯系列表面活性剂的合成及性能进行了研究。首先,对烷基磷酸酯的分析方法进行了系统的研究,归纳出一次性即可分析出单、双烷基磷酸酯含量、磷酸含量,并计算出脂肪醇含量的一体化电位滴定分析法,经气相色谱验证了分析结果的可靠性。该方法简捷、准确、重现行好,适合于工厂生产单烷基磷酸酯产品的快速分析测试。接着,以聚磷酸和月桂醇为原料合成单十二烷基磷酸酯,采用双参数正交设计的方法找出了反应时间、反应温度、聚磷酸浓度以及聚磷酸与月桂醇投料比例对产品组分的影响。以MAP比例为指标时,最佳合成条件为:115%PPA、醇酸摩尔比0.9:1、90℃、5h,酯化后60℃下水解30min,得到MAP比例为95.8%、醇转化率81.1%的磷酸酯;以月桂醇转化率为指标时,最佳合成条件为:120%PPA,其他条件同上,得到醇转化率95.9%、MAP比例为88.0%的无色或浅色磷酸酯,实验结果达到了美国5554781号专利水平。并由红外光谱、质谱对合成的单十二醇磷酸酯进行结构表征。对磷酸酯产品的分离纯化进行了研究,发现减压至25kPa、122℃尚无法蒸出月桂醇,通过水洗磷酸酯的乙醚溶液,3次水洗后磷酸被水洗除去效率达99.8%。在研究单十二醇烷基磷酸酯的基础上,对脂肪醇醚与聚磷酸反应合成单醇醚磷酸酯进行了研究,发现聚磷酸浓度及投料比依然是影响单醇醚磷酸酯含量的重要因素,但整体影响趋势比十二醇更复杂。在聚磷酸与醇醚投料比为2:1、75℃、2h、PPA浓度115%进行酯化,再在80℃下水解2h的磷酸酯产品中MAP/(MAP+DAP)达95.3%,醇醚转化率达95.8%的白色或浅色醇醚磷酸酯产品。实验还对合成双十二烷基磷酸酯进行探索,研究了以三氯氧磷与月桂醇反应制取双十二烷基磷酸酯中反应时间、反应温度、投料比对结果的影响。在50℃、6h、1:2.1时得到双十二烷基磷酸酯含量为84.9%,DAP/(MAP+DAP)为93.3%的白色双十二烷基磷酸酯产品。最后,对合成的单、双十二烷基磷酸酯进行复配,研究了磷酸酯的表面张力、泡沫性和乳化性,发现单十二烷基磷酸酯的泡沫性和乳化能力优于双十二烷基磷酸酯,但双酯表面活性更强,单双酯无复配增效作用。更多还原

【Abstract】 This research was mainly focused on the synthesis of a series of Alkyl phosphate ester andon their properties.Firstly, the analytical method of mono-lauryl phosphate ester was studied carefully. It wasfound that the method of potentiometric titration can determine the contents of mono-alkylphosphate ester (MAP), di-alkyl phosphate ester (DAP) and phosphorus acid (PA)simultaneously, and the content of fatty alcohol unreacted can be calculated. Abovepotentiometric titration analysis was confirmed further by gas chromatography. There for, asimple, rapid and more precise method was provided. It is suitable for industrial application.In preparation of MAP, PPA and dodecanol were as raw material. An orthogonalexperimental design with two objective functions was used to optimise the process parameters.The parameters investigated were as follow: temperature, time, PPA density, PPA anddodecanol`s mole ratio. To enhance the ratio of MAP, the best combination of parameters was115% PPA,90℃,0.9:1(mole ratio of dodecanol to PPA),5h, and the product obtained afterhydrolysis (60℃,30min) has the ratio of MAP to 95.8% while the conversion of dodecanol at81.1%. To enhance the conversion of dodecanol, the concentration of PPA was up to 120% andthe other parameters were the same. Then, the conversion of dodecanol reached 95.9% whilethe ratio of MAP down to 88.0%. The product is colorless or light color. Above experimentalresults are comparable with the US patent 5554781. The MAP was characterized by IR and MS.To enhance the content of MAP in products, the methods of purification were tried. It wasfound that the dodecanol residue in product was hard to be removed by vacuumdistillation(25kPa, 122℃). However, by triple washing the ether solution of crude phosphateester with water, 99.8% PA could be removed.The further investigation used ethoxylated fatty alcohol and PPA as raw materials. Thesame factors were investigated even the same result was obtained. The optimal condition was115% PPA,75℃,2h, 2:1(mole ratio of PPA to ethoxylated fatty alcohol) followed by a 2hhydrolysis at 80℃, and the mono-ester ratio arrived at 95.3% while the conversion ofethoxylated fatty alcohol got 95.8%. The product is colorless or light color.We also have exploded the synthesis of DAP with POCl3 and dodecanol as raw materials.The process parameters use the same as above.The optimum condition was 50℃,1:2.1(moleratio of POCl3 to dodecanol),6h esterfization followed by a washing and drying process.Theresearch shows that the yield of DAP was 84.9% while the ratio of DAP was 93.3%.Theproduct is colorless.At last, the phosphate ester was mixed based on MAP and DAP. The properties of surfacetension, foaming and emulsifying ability were measured. DAP has stronger surfactive thanMAP, but MAP and DAP have not synergistic effect. The foaming and emulsifying ability ofMAP is better than DAP.更多还原