磷酸酯表面活性剂的合成及性能研究
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摘要
磷酸酯表面活性剂作为一类重要的阴离子表面活性剂,它具有优良的溶解性、乳化性、润湿性以及低的表面张力等而被广泛应用到各个领域中,本文以P205和POC13为磷化剂合成了系列的磷酸酯表面活性剂,并对其应用和性能进行了研究。本课题主要包括以下几点内容：
1、本文中制备了系列的普通磷酸酯表面活性剂,并通过单因素实验探讨了反应温度、反应时间以及反应物投料比对酯化率的影响。对酚醚磷酸酯来说,投料比n(OP-10)/n(P2O5)=2时单酯收率较高,随其摩尔比的增加单酯收率逐渐降低,双酯收率逐渐增加,而当n(OP-10)/n(P2O5)=3时,总酯化率最高,较佳酯化温度为75℃,酯化时间为4h；对醇醚磷酸酯来说,投料比n(AEo-9)/n(P2O5)=2时总酯化率最高,较佳酯化温度为80℃,酯化时间为3h。
2、将制备的普通磷酸酯表面活性剂与其他非离子表面活性剂复配,得到乳化性能良好的复配乳化剂,并通过单因素实验探讨了乳化剂的选择、用量及乳化时间对乳液稳定性的影响,将乳化性能最好的配方应用到甲基硅油的乳化中,制得稳定性较好的硅油乳液。
3、本课题以三氯氧磷、二元醇(酚)、正十二醇以及正十六醇等为原料经磷化、酯化、水解及成盐反应合成了五种磷酸酯类双子表面活性剂,在磷化和酯化两步反应过程中设计了正交试验,确定了最佳的磷化条件为：n(POCl3)/n(二醇)=1:1,反应时间为5h,反应温度为10℃。得出较佳酯化条件为：n(POCl3)/n正十二醇=1:1,反应时间6h,酯化温度为30℃。
4、通过用重结晶的方法对合成的中间产物进行提纯,并采用FT-IR,1HNMR以及MS对中间产物进行了结构表征,最后对最终产品的表面张力、临界胶束浓度、乳化性、润湿性和泡沫性能进行了测试,并探讨了疏水链长度与连接基的长短及刚柔性对其性能的影响,本课题的实验工作这对今后磷酸酯双子表面活性剂的实际生产及应用具有重要的指导意义。
Phosphate surfactant is an important type of anionic surfactant, it has been widely applied to various fields for which has good solubility, emulsifying, wetting and low surface tension. In this paper a series of ordinary phosphate and gemini phosphate surfactants were synthesized with phosphating agent P2O5 and POCl3, the applications and the properties of the phosphate surfactants were studied. This research include the following sections:
1. Four kinds of ordinary phosphate surfactants were prepared. The influences of the ratio of reactants, the reaction temperature and the reaction time on the yield of the esterification rate have been studied by the single-factor experiment. The conclusions are as followed: when the ratio of reactants n(phenol ether or alcohol ether)/n(P2O5)=2,the yield of the mono-ester is higher than the di-ester,with the increase of the molar ratio the yield of the mono-ester decreased, while the n(phenol ether or alcohol ether)/n(P2O5)=3, we get the highest total esterification rate, the better esterification temperature is 75℃,and the reaction time is 4h for the phenol ether phosphate; when n(AEO-9)/n(P2O5)=2, the esterification rate is very good, and the better esterification temperature is 80℃, and the reaction time is 3h for alcohol ether phosphate.
2. A kind of mixed emulsifier which has good emulsifying properties was prepared by ordinary phosphate mix with other non-ionic surfactants at a certain ratio. The effects of the selection and dosages of the emulsifier and emulsifying time on the stability of emulsion has been studied by single factor experiments. And the emulsifier was used to emulsified the methyl silicone oil, and the stability of the obtained emulsion is very good.
3. A series of phosphate gemini surfactants have been synthesized by phosphorylation, esterification, hydrolysis and neutralization reaction between diols or hydroquinone, 1-dodecanol,1-hexadecanol and phosphating agent phosphorus oxychloride in this topic. In order to optimize the reaction conditions the orthogonal experiments have been designed in the process of phosphorylation and esterification. The optimum conditions during phosphorylation are as follows:n(phosphoms oxychloride/n(diols)=1:1,the reaction time is 5h and the reaction temperature is 10℃, the optimum conditions during esterification:n (phosphorus oxychloride) /n(1-dodecanol/1-hexadecanol)=1:1, the reaction time is 6h and the reaction temperature is 30℃.
4. The synthesised intermediates were purified by recrystallization. The structures of the purified intermediates were characterized by FT-IR,1H-NMR and MS. The critical micelle concentration, surface tension, emulsification, wetting and foaming properties of the final products have been tested, and the influences of the length of the hydrophobic, the spacer chain and it's flexible of the synthesised gemini phosphate surfactants on the various properties.The experimental work of this subject has important significance for the actual production and the application of the phosphate gemini surfactants.
1、本文中制备了系列的普通磷酸酯表面活性剂,并通过单因素实验探讨了反应温度、反应时间以及反应物投料比对酯化率的影响。对酚醚磷酸酯来说,投料比n(OP-10)/n(P2O5)=2时单酯收率较高,随其摩尔比的增加单酯收率逐渐降低,双酯收率逐渐增加,而当n(OP-10)/n(P2O5)=3时,总酯化率最高,较佳酯化温度为75℃,酯化时间为4h；对醇醚磷酸酯来说,投料比n(AEo-9)/n(P2O5)=2时总酯化率最高,较佳酯化温度为80℃,酯化时间为3h。
2、将制备的普通磷酸酯表面活性剂与其他非离子表面活性剂复配,得到乳化性能良好的复配乳化剂,并通过单因素实验探讨了乳化剂的选择、用量及乳化时间对乳液稳定性的影响,将乳化性能最好的配方应用到甲基硅油的乳化中,制得稳定性较好的硅油乳液。
3、本课题以三氯氧磷、二元醇(酚)、正十二醇以及正十六醇等为原料经磷化、酯化、水解及成盐反应合成了五种磷酸酯类双子表面活性剂,在磷化和酯化两步反应过程中设计了正交试验,确定了最佳的磷化条件为：n(POCl3)/n(二醇)=1:1,反应时间为5h,反应温度为10℃。得出较佳酯化条件为：n(POCl3)/n正十二醇=1:1,反应时间6h,酯化温度为30℃。
4、通过用重结晶的方法对合成的中间产物进行提纯,并采用FT-IR,1HNMR以及MS对中间产物进行了结构表征,最后对最终产品的表面张力、临界胶束浓度、乳化性、润湿性和泡沫性能进行了测试,并探讨了疏水链长度与连接基的长短及刚柔性对其性能的影响,本课题的实验工作这对今后磷酸酯双子表面活性剂的实际生产及应用具有重要的指导意义。
Phosphate surfactant is an important type of anionic surfactant, it has been widely applied to various fields for which has good solubility, emulsifying, wetting and low surface tension. In this paper a series of ordinary phosphate and gemini phosphate surfactants were synthesized with phosphating agent P2O5 and POCl3, the applications and the properties of the phosphate surfactants were studied. This research include the following sections:
1. Four kinds of ordinary phosphate surfactants were prepared. The influences of the ratio of reactants, the reaction temperature and the reaction time on the yield of the esterification rate have been studied by the single-factor experiment. The conclusions are as followed: when the ratio of reactants n(phenol ether or alcohol ether)/n(P2O5)=2,the yield of the mono-ester is higher than the di-ester,with the increase of the molar ratio the yield of the mono-ester decreased, while the n(phenol ether or alcohol ether)/n(P2O5)=3, we get the highest total esterification rate, the better esterification temperature is 75℃,and the reaction time is 4h for the phenol ether phosphate; when n(AEO-9)/n(P2O5)=2, the esterification rate is very good, and the better esterification temperature is 80℃, and the reaction time is 3h for alcohol ether phosphate.
2. A kind of mixed emulsifier which has good emulsifying properties was prepared by ordinary phosphate mix with other non-ionic surfactants at a certain ratio. The effects of the selection and dosages of the emulsifier and emulsifying time on the stability of emulsion has been studied by single factor experiments. And the emulsifier was used to emulsified the methyl silicone oil, and the stability of the obtained emulsion is very good.
3. A series of phosphate gemini surfactants have been synthesized by phosphorylation, esterification, hydrolysis and neutralization reaction between diols or hydroquinone, 1-dodecanol,1-hexadecanol and phosphating agent phosphorus oxychloride in this topic. In order to optimize the reaction conditions the orthogonal experiments have been designed in the process of phosphorylation and esterification. The optimum conditions during phosphorylation are as follows:n(phosphoms oxychloride/n(diols)=1:1,the reaction time is 5h and the reaction temperature is 10℃, the optimum conditions during esterification:n (phosphorus oxychloride) /n(1-dodecanol/1-hexadecanol)=1:1, the reaction time is 6h and the reaction temperature is 30℃.
4. The synthesised intermediates were purified by recrystallization. The structures of the purified intermediates were characterized by FT-IR,1H-NMR and MS. The critical micelle concentration, surface tension, emulsification, wetting and foaming properties of the final products have been tested, and the influences of the length of the hydrophobic, the spacer chain and it's flexible of the synthesised gemini phosphate surfactants on the various properties.The experimental work of this subject has important significance for the actual production and the application of the phosphate gemini surfactants.
引文
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