摘 要

1-烯丙氧基-3-脂肪醇-2-羟丙聚氧乙烯基硫酸铵盐乳化剂是一种性能优良的反应型乳化剂，在丙烯酸散体中应用广泛。本文以烯丙基缩水甘油醚（以下简称AGE）和十二-十四醇为原料，通过开环反应合成了1-烯丙氧基-3-十二-十四醇-2-羟基丙烷；后在碱性条件下合成了1-烯丙氧基-3-十二-十四醇-2-羟丙聚氧乙烯醚（EO=10）；最后采用1-烯丙氧基-3-十二-十四醇-2-羟丙聚氧乙烯醚（EO=10）和氨基磺酸为原料，通过硫酸化反应合成了1-烯丙氧基-3-十二-十四醇-2-羟丙聚氧乙烯醚硫酸铵盐(EO=10)。并对产品的性能进行了检测。

本文研究了反应温度、反应时间等对开环反应的影响，并用正交试验进一步优化，得到最佳工艺条件：反应物摩尔比为n(C_12~14-OH):n(AGE)=1:1.15、反应温度为100 ℃、反应时间为3.5 h、催化剂用量（以反应物总质量计）为0.9%，此时烯丙基缩水甘油醚的转化率为100%。采用红外光谱对开环产物进行表征。

探讨了反应温度等对硫酸化反应的影响，并用正交试验进一步优化，得到最佳工艺条件：硫酸化反应的反应温度为105 ℃、反应时间为4 h、反应物摩尔比n(C_12~14•OH-10EO):n(NH2SO3H)=1:1.06、催化剂用量（以反应物总质量计）为0.5%，此时硫酸化率为100%。采用红外光谱和核磁氢谱对硫酸化产物进行表征。

对比了1-烯丙氧基-3-十二-十四醇-2-羟丙聚氧乙烯醚（EO=10）和1-烯丙氧基-3-十二-十四醇-2-羟丙聚氧乙烯基硫酸铵（EO=10）的乳化性能、泡沫性能，得到硫酸化产物的性能较好，它的乳化性能为270 s，泡沫性能开始时为68 mL，稳定后为26.5 mL。同时探索了硫酸化产物的表面张力，得到当浓度为1×10^-4 g/L到达它的临界胶束浓度，此时溶液的表面张力为33.03 g/L。

关键词：阴-非离子乳化剂；硫酸化率；开环反应；乳液应用

Preparation and application of 1-allyloxy-3-fatty alcohol-2-hydroxypropane polyoxyethylene ammonium sulfate

ABSTRACT

1-Allyloxy-3-fatty alcohol-2-hydroxypropane polyoxyethylene ammonium sulfate emulsifier is a reactive emulsifier with excellent performance and is widely used in acrylic dispersion. In this paper, allyl glycidyl ether (hereinafter referred to as AGE) and Twelve-tetradecanol were used as raw materials to synthesize 1-allyloxy-3-fatty alcohol-2-hydroxypropane by ring-opening reaction; 1-Allyloxy-3-fatty alcohol-2-hydroxypropoxyethylene ether (EO=10) was synthesized under the conditions; finally, 1-allyloxy-3-fatty alcohol-2-hydroxypropane polyoxyl was used. A vinyl ether (EO=10) and sulfamic acid were used as raw materials to synthesize 1-allyloxy-3-aliphatic-2-hydroxypropoxypolyvinyl sulfate ammonium salt by sulfation reaction. The performance of the product was tested.

In this paper, the effects of reaction temperature and reaction time on the ring-opening reaction were studied and further optimized by orthogonal test. The optimum process conditions were as follows: n(C_12~14-OH): n(AGE)=1:1.11, reaction temperature It was 100 °C; the reaction time was 4.5 h; the amount of the catalyst was 0.9%, and the conversion of allyl glycidyl ether was 100%. The ring-opening product was characterized by infrared spectroscopy.

The effects of reaction temperature on the sulfation reaction were studied and further optimized by orthogonal test. The optimum conditions were as follows: the reaction temperature was 105 °C, the reaction time was 3 h, and the molar ratio of the reactants was n(C_12~14·OH-10EO):n(NH ₂SO₃H)=1:1.11, at which time the sulfation rate was 100%. The sulfated product was characterized by infrared spectroscopy and nuclear magnetic resonance spectroscopy.

Comparison of 1-allyloxy-3-fatty alcohol-2-hydroxypropoxyethylene ether (EO=10) and 1-allyloxy-3-fatty alcohol-2-hydroxypropane polyoxyethylene ammonium sulfate The emulsification performance and foam performance of (EO=10) gave better performance of the sulfated product, and its emulsifying property was 270 s, the foaming property was 68 mL at the beginning, and it was 26.5 mL after the stabilization. At the same time, the surface tension of the sulfated product was explored, and the critical micelle concentration reached at a concentration of 10^-4 g/L was obtained. At this time, the surface tension of the solution was 33.03 g/L.

Key words: anionic nonionic emulsifier; sulfation rate; ring opening reaction; emulsion application目录

1绪论 - 1 -

1.1 反应型乳化剂的分类 - 1 -

1.1.1反应型乳化剂按可聚合的基团分类 - 2 -

1.1.2亲水基团对反应型乳化剂的影响 - 3 -

1.2 1-烯丙氧基-3-脂肪醇-2-羟丙聚氧乙烯基硫酸铵乳化剂的优点 - 4 -

1.3 研究的目的意义及主要内容 - 5 -

2实验部分 - 6 -

2.1 实验原料与仪器 - 6 -

2.1.1实验原料 - 6 -

2.1.2实验仪器和设备 - 6 -

2.2 实验原理及步骤 - 7 -

2.2.1实验原理 - 7 -

2.2.2实验步骤 - 8 -

2.3性能测试与表征 - 9 -

2.3.1环氧值计算转化率的方法 - 9 -

2.3.2硫酸化率的测定 - 10 -

2.3.3表面活性剂的表面张力（δ）测定方法 - 11 -

2.3.4表面活性剂的临界胶束浓度（CMC）测定方法 - 11 -

2.3.5产物的红外光谱分析 - 12 -

2.3.6产物的核磁氢谱分析 - 12 -

2.3.6表面活性剂的乳化性能（EP）测定方法 - 12 -

2.3.7表面活性剂的泡沫性能（FP）测定方法 - 12 -

2.4 本章小结 - 12 -

3 实验结果与讨论 - 14 -

3.1 开环单因素实验结果分析 - 14 -

3.1.1反应物摩尔比对1-烯丙氧基-3-脂肪醇-2-羟基丙烷合成反应的影响 - 14 -

3.1.2反应温度对1-烯丙氧基-3-脂肪醇-2-羟基丙烷合成反应的影响 - 15 -

3.1.3反应时间对1-烯丙氧基-3-脂肪醇-2-羟基丙烷合成反应的影响 - 16 -

3.1.4催化剂用量对1-烯丙氧基-3-脂肪醇-2-羟基丙烷合成反应的影响 - 17 -

3.2 开环正交试验设计及结果 - 17 -

3.3 开环正交实验结果分析 - 18 -

3.3.1反应物摩尔比对转化率的影响 - 19 -

3.3.2反应温度对转化率的影响 - 19 -

3.3.3反应时间对转化率的影响 - 20 -

3.3.4催化剂的量对转化率的影响 - 21 -

3.4 开环反应重现性实验 - 22 -