壬基苯甲醚系列磺酸盐的合成与构效关系研究
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摘要
本论文旨在合成一种新型Gemini阴离子型表面活性剂——甲基偶联双(壬基苯甲醚磺酸钠)(MBSMN),对其相转移催化O-甲基化反应的催化剂、磺化反应条件进行优化实验,并对产物Gemini表面活性剂的性能等进行研究。
以“绿色试剂”碳酸二甲酯(DMC)为原料,通过相转移催化,对甲基偶联双壬基酚(MDN)实施O-甲基化反应,合成得到中间体甲基偶联双(壬基苯甲醚)(MBMN);再经氯磺酸磺化、氢氧化钠溶液中和,制得终产物甲基偶联双(壬基苯甲醚磺酸钠)(MBSMN)。为了考察壬基苯甲醚磺酸盐的构效关系,本研究还合成了另外两种壬基苯甲醚磺酸盐型表面活性剂:壬基苯甲醚磺酸钠(SMN)和甲基偶联双(壬基苯甲醚)磺酸钠(SMBMN)。测定了中间体和各终产物的红外光谱(IR)、质谱(MS)及核磁共振氢谱(1H-NMR)。通过单因素实验对O-甲基化反应的催化剂及相转移催化剂进行筛选,最终确定为碱性催化剂K2CO3、相转移催化剂四正丁基溴化铵(TBAB),通过HPLC测得O-甲基化反应产物转化率可以达92 %以上。通过正交试验对磺化反应条件进行优化,实验结果表明磺化反应合成MBSMN的最优条件为,n(MBMN) : n(氯磺酸) = 1 : 4,反应温度为30℃,反应时间为9 h。经两相滴定测得MBSMN与海明1622的滴定终点的摩尔量比为1 : 1.72。可指导今后此类磺化反应的进行,及判断反应的进行程度。
性能测定结果表明,本研究合成的三种表面活性剂的Krafft点均低于0℃。故在25±0.1℃下利用OCA40动态接触角测量仪对合成的各表面活性剂的表面张力进行了测定,由实验结果可见,Gemini型阴离子表面活性剂MBSMN的临界胶束浓度cmc为0.407×10~(-3) mol·L~（-1）,γcmc为30.4 mN·m~（-1）,与传统阴离子表面活性剂直链烷基苯磺酸钠(LAS)相比,cmc降低约一个数量级左右,γcmc也有所降低。钙皂分散力和钙离子稳定性测定结果表明,MBSMN的钙皂分散指数(LSDP)可以达到33 %,优于LAS的41 %;MBSMN的钙离子稳定性可以达到749.4 ppm,这也优于LAS的497.2 ppm。耐酸、耐碱及耐盐的实验结果表明,MBSMN可以在4 %的无机盐溶液或0.5 mol·L~（-1）的碱溶液中保持稳定状态,这要优于LAS(可以在2 %的无机盐或0.4 mol·L~（-1）的碱溶液中保持稳定)。通过以上这些性能以及乳化力和泡沫性能测定结果表明,本文合成的新型Gemini阴离子表面活性剂MBSMN具有优良的表化性能,优于单尾壬基苯甲醚磺酸盐(SMN)和双尾壬基苯甲醚磺酸盐(SMBMN),显示了其在相关工业领域具有良好的应用前景。说明对酚羟基进行O-甲基化反应,对其性能具有一定的积极影响。
A novel anionic gemini surfactant methylene bis(sodium sulfonated O-methyl- nonylphenol) (MBSMN) was synthesized in this thesis. The catalyst of phase transfer catalyzed O-methylation, technics conditions of sulofnation and the surface properties of products were investigated.
The intermediate methylene bis (O-methyl-nonylphenol) (MBMN) was prepared by phase transfer catalyzed O-methylation of methylene dinonylphenol (MDN) using green reagent dimethyl carbonate (DMC) as methylating agent, from which a novel anionic gemini surfactant MBSMN was synthesized by followed sulfonation and neutralization. The other two surfactants, sodium sulfonated O-methyl-nonylphenol (SMN) and sodium sulfonated methylene bis (O-methyl- nonylphenol) (SMBMN) were also synthesized for investigate the structure-activity relationship of O-methyl-nonylphenol sulfonates. The structures of intermediate and three final products were recognized by IR spectrometry, mass spectrometry and 1H-NMR. In the monofactorial experiment, the catalyst of phase transfer catalyzed O-methylation was screened, with K2CO3 as catalyst and tetrabutyl ammonium bromide (TBAB) as phase transfer catalyst, the yield of MBMN can be up to at least 92% by HPLC. Optimum sulofnation conditions were obtained by orthogonal experiment, n(MBMN) : n(HSO3Cl) = 1 : 4, T=30℃and t= 9 h. It is found that the molar rate of purified MBSMN to hyamine 1622 is 1 : 1.72.
The krafft point of SMN, SMBMN and MBSMN were below zero all. Air-Liquid surface tensions of the surfactants were investigated in this thesis at the temperature of 298 K. The surface tension and the critical micelle concentration (cmc) of MBSMN was 30.4 mN·m~（-1）and 0.407×10-3 mol·L~（-1）. The experimental results indicated that the surface tension of MBSMN is lower than the ordinary anionic surfactant linear alkylbenzene sulfonate (LAS), and cmc is about one order of magnitude lower than that. The experimental results of lime soap dispersing power(LSDP) and anti-hard water stability indicate that: LSDP of MBSMN is 33 %, is superior to 41 % of LAS, the anti-hard water stability of MBSMN is 749.4 ppm, is superior to 497.2 ppm of LAS. The experimental results of acid resistance, alkali resistance and salt tolerance indicate that: MBSMN can remain stable in the solution of salinity 4 % or alkalinity 0.5 mol·L~（-1）, it is superior to salinity 2 % or alkalinity 0.4 mol·L~（-1）of LAS. In addition, foaming ability, foam stability and emulsifying capacity were investigated. The experimental results indicate that MBSMN has good surface properties with LAS, SMN and SMBMN. It can be apply in related industries .
以“绿色试剂”碳酸二甲酯(DMC)为原料,通过相转移催化,对甲基偶联双壬基酚(MDN)实施O-甲基化反应,合成得到中间体甲基偶联双(壬基苯甲醚)(MBMN);再经氯磺酸磺化、氢氧化钠溶液中和,制得终产物甲基偶联双(壬基苯甲醚磺酸钠)(MBSMN)。为了考察壬基苯甲醚磺酸盐的构效关系,本研究还合成了另外两种壬基苯甲醚磺酸盐型表面活性剂:壬基苯甲醚磺酸钠(SMN)和甲基偶联双(壬基苯甲醚)磺酸钠(SMBMN)。测定了中间体和各终产物的红外光谱(IR)、质谱(MS)及核磁共振氢谱(1H-NMR)。通过单因素实验对O-甲基化反应的催化剂及相转移催化剂进行筛选,最终确定为碱性催化剂K2CO3、相转移催化剂四正丁基溴化铵(TBAB),通过HPLC测得O-甲基化反应产物转化率可以达92 %以上。通过正交试验对磺化反应条件进行优化,实验结果表明磺化反应合成MBSMN的最优条件为,n(MBMN) : n(氯磺酸) = 1 : 4,反应温度为30℃,反应时间为9 h。经两相滴定测得MBSMN与海明1622的滴定终点的摩尔量比为1 : 1.72。可指导今后此类磺化反应的进行,及判断反应的进行程度。
性能测定结果表明,本研究合成的三种表面活性剂的Krafft点均低于0℃。故在25±0.1℃下利用OCA40动态接触角测量仪对合成的各表面活性剂的表面张力进行了测定,由实验结果可见,Gemini型阴离子表面活性剂MBSMN的临界胶束浓度cmc为0.407×10~(-3) mol·L~（-1）,γcmc为30.4 mN·m~（-1）,与传统阴离子表面活性剂直链烷基苯磺酸钠(LAS)相比,cmc降低约一个数量级左右,γcmc也有所降低。钙皂分散力和钙离子稳定性测定结果表明,MBSMN的钙皂分散指数(LSDP)可以达到33 %,优于LAS的41 %;MBSMN的钙离子稳定性可以达到749.4 ppm,这也优于LAS的497.2 ppm。耐酸、耐碱及耐盐的实验结果表明,MBSMN可以在4 %的无机盐溶液或0.5 mol·L~（-1）的碱溶液中保持稳定状态,这要优于LAS(可以在2 %的无机盐或0.4 mol·L~（-1）的碱溶液中保持稳定)。通过以上这些性能以及乳化力和泡沫性能测定结果表明,本文合成的新型Gemini阴离子表面活性剂MBSMN具有优良的表化性能,优于单尾壬基苯甲醚磺酸盐(SMN)和双尾壬基苯甲醚磺酸盐(SMBMN),显示了其在相关工业领域具有良好的应用前景。说明对酚羟基进行O-甲基化反应,对其性能具有一定的积极影响。
A novel anionic gemini surfactant methylene bis(sodium sulfonated O-methyl- nonylphenol) (MBSMN) was synthesized in this thesis. The catalyst of phase transfer catalyzed O-methylation, technics conditions of sulofnation and the surface properties of products were investigated.
The intermediate methylene bis (O-methyl-nonylphenol) (MBMN) was prepared by phase transfer catalyzed O-methylation of methylene dinonylphenol (MDN) using green reagent dimethyl carbonate (DMC) as methylating agent, from which a novel anionic gemini surfactant MBSMN was synthesized by followed sulfonation and neutralization. The other two surfactants, sodium sulfonated O-methyl-nonylphenol (SMN) and sodium sulfonated methylene bis (O-methyl- nonylphenol) (SMBMN) were also synthesized for investigate the structure-activity relationship of O-methyl-nonylphenol sulfonates. The structures of intermediate and three final products were recognized by IR spectrometry, mass spectrometry and 1H-NMR. In the monofactorial experiment, the catalyst of phase transfer catalyzed O-methylation was screened, with K2CO3 as catalyst and tetrabutyl ammonium bromide (TBAB) as phase transfer catalyst, the yield of MBMN can be up to at least 92% by HPLC. Optimum sulofnation conditions were obtained by orthogonal experiment, n(MBMN) : n(HSO3Cl) = 1 : 4, T=30℃and t= 9 h. It is found that the molar rate of purified MBSMN to hyamine 1622 is 1 : 1.72.
The krafft point of SMN, SMBMN and MBSMN were below zero all. Air-Liquid surface tensions of the surfactants were investigated in this thesis at the temperature of 298 K. The surface tension and the critical micelle concentration (cmc) of MBSMN was 30.4 mN·m~（-1）and 0.407×10-3 mol·L~（-1）. The experimental results indicated that the surface tension of MBSMN is lower than the ordinary anionic surfactant linear alkylbenzene sulfonate (LAS), and cmc is about one order of magnitude lower than that. The experimental results of lime soap dispersing power(LSDP) and anti-hard water stability indicate that: LSDP of MBSMN is 33 %, is superior to 41 % of LAS, the anti-hard water stability of MBSMN is 749.4 ppm, is superior to 497.2 ppm of LAS. The experimental results of acid resistance, alkali resistance and salt tolerance indicate that: MBSMN can remain stable in the solution of salinity 4 % or alkalinity 0.5 mol·L~（-1）, it is superior to salinity 2 % or alkalinity 0.4 mol·L~（-1）of LAS. In addition, foaming ability, foam stability and emulsifying capacity were investigated. The experimental results indicate that MBSMN has good surface properties with LAS, SMN and SMBMN. It can be apply in related industries .
引文
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