壬基酚聚氧乙烯醚双子表面活性剂的合成

Synthesis of Gemini Nonylphenol Polyethoxylate Surfactant

以壬基酚、多聚甲醛和环氧乙烷为原料,经3步反应合成了壬基酚聚氧乙烯醚双子表面活性剂(GNP-10),对比了不同固体超强酸催化剂对第二步反应的催化性能。考察了反应条件对2-羟甲基-4-壬基苯酚(化合物Ⅰ)和二-(2-羟基-5-壬基苯基)-甲烷(化合物Ⅱ)的转化率和收率的影响,并对化合物Ⅰ、化合物Ⅱ及 GNP-10的结构进行了表征。实验结果表明,合成GNP-10的适宜条件为:第一步,以氢氧化钠为催化剂、n(壬基酚):n(多聚甲醛)=1:1、反应温度40℃、反应时间12 h、pH 为9,此时壬基酚的转化率为63.1%,化合物Ⅰ的收率为40.2%;第二步,以 SO_4^(2-)/TiO_2固体超强酸为催化剂、n(化合物Ⅰ):n(壬基酚)=1:1、反应温度110℃、反应时间6 h,此时化合物Ⅰ的转化率和化合物Ⅱ的收率分别为73.7%和69.8%;第三步,n(化合物Ⅱ):n(环氧乙烷)=1:20,120～150℃,氢氧化钠催化下反应2 h,GNP-10的收率为98.0%。3步反应的总收率为27.5%。

A novel surfactant of Gemini nonylphenol polyethoxylate （GNP-10） was synthesized from nonylphenol, paraformaldehyde and ethylene oxide by a three-step process. Effects of different catalysts, starting material ratio, reaction temperature and time on synthesis of 2-hydroxymethyl-4- nonylphenol （ intermediate compound Ⅰ ）, bis-（ 2-hydroxy-5-nonylphenyl ）-methane （ intermediate compound Ⅱ ） and end product GNP-10 were investigated. The chemical structures of intermediates and GNP-10 were characterized by means of ^1H NMR and PTIR. Under optimal conditions for preparation of compound Ⅰ ：NaOH as catalyst, n（nonylphenol） ： n（paraformaldehyde） = 1 ： 1, pH 9, reaction time 12 h and reaction temperature 40 ℃, conversion of nonylphenol is 63.1% and yield to compound Ⅰ is 40. 2%; for second-step compound Ⅱ：SO4^2-/TiO2 solid superacid as catalyst, n（compound Ⅰ ）：n（nonylphenol）= 1 ： 1, reaction time 6 h and reaction temperature 110 ℃, conversion of compound Ⅰ is 73.7% and yield to compound 11 is 69.8% ; as for end product： NaOH as catalyst, n （ compound Ⅱ ） ： n （ ethylene oxide） = 1 ： 20, reaction time 2 h and reaction temperature 120 - 150 ℃, end product yield is 98.0%. Total yield of GNP-10 prepared by the three-step process is 27.5%.