摘 要

环氧氯丙烷(ECH)的开环反应使用的催化剂具有明显的缺点，如对反应设备腐蚀严重、不能循环回收等。如何制备出廉价、低消耗、高效率、使用寿命长、对环境污染小的开环催化剂具有重要的理论和现实意义。本论文以蒙脱土(MMT)作为载体，四氯化锡为活性组分，采用离子交换法对MMT进行改性。考察了催化剂的制备条件和开环反应的工艺对ECH开环性能的影响。主要研究内容及结论如下：

1. 为探究了不同锡源、制备温度、负载量等条件下的催化剂的催化活性。以含锡化合物和MMT为原料，蒸馏水或无水乙醇为溶剂，采用离子交换法制备了一系列Sn/MMT催化剂。实验结果得出，催化剂最优的制备条件为：制备温度为室温，负载量在1mmol/g，以SnCl₄•5H₂O活性组分。
2. 探究了催化剂在不同应用工艺条件下的催化活性，分别对催化剂用量、反应温度、反应时间以及重复使用进行实验。以烯丙醇和ECH为原料，Sn/MMT为催化剂，进行开环反应得到β-开环产物。实验结果表明，在反应温度50℃下，催化剂用量(以ECH计)为6%，反应时间1h为最优开环反应条件。实验过程中催化剂重复使用至第6次实验时，其选择性仍然没有降低。
3. 为探究催化剂对其它脂肪醇的催化活性的效果，采用了正丁醇、异辛醇和C_12-14醇分别与ECH进行开环反应。实验结果表明，对于其它脂肪醇催化剂的选择性也在80%以上。

关键词：ECH；烯丙醇；蒙脱土；催化剂；开环反应

Study on the catalysts for ring-opening reaction of epoxy compounds with fatty alcohols

ABSTRACT

Epichlorohydrin (ECH) ring opening reaction catalysts commonly used have obvious shortcomings, such as serious corrosion to reaction equipment, can’t be recycled. How to prepare the low cost, low consumption, high efficiency, long service life and small environmental pollution open ring catalyst has important theoretical and practical significance. MMT was modified by ion exchange method with montmorillonite (MMT) as carrier and tin tetrachloride as active component. The effects of preparation conditions of tin tetrachloride supported by MMT on ECH ring opening were investigated. The main research and conclusions are as follows:Using ion exchange of series of Sn/MMT prepared by catalyst, the experimental results, the optimum preparation conditions of catalysts for: under load temperature 50℃, the load tendency for 1mmol/g, crystallization SnCl₄ as active component.

(1) In order to investigate the catalytic activity of catalysts with different tin source, preparation temperature and load. A series of Sn/MMT catalysts were prepared by ion exchange method using tin compounds and MMT as raw materials, distilled water or anhydrous ethanol as solvent. According to the experimental results, the optimal preparation conditions of the catalyst were as follows: the preparation temperature was room temperature, the load was 1mmol/g, and the active component of SnCl₄•5H₂O was used.

(2) The catalytic activity of the catalyst under different application conditions was explored, and the catalyst dosage, reaction temperature, reaction time and repeated use were tested respectively. Using allyl alcohol and ECH as raw materials and Sn/MMT as catalyst, the ring-opening product was obtained by the ring-opening reaction. The experimental results showed that at the reaction temperature of 50℃, the amount of catalyst (measured by ECH) was 6%, and the reaction time of 1h was the optimal ring-opening reaction condition. During the experiment, the selectivity of the catalyst did not decrease after the sixth experiment.

(3) In order to investigate the catalytic activity of the catalyst on other fatty alcohols, n-butanol, iso-octanol and c12-14 alcohol were used for ring-opening reaction with ECH respectively. The results show that the selectivity of other fatty alcohol catalyst is more than 80%.

Key words：ECH; Allyl alcohol; Montmorillonite; Catalytic; Ring-opening reaction

目 录

1 绪论 - 1 -

1.1 环氧氯丙烷开环反应催化剂的概述 - 1 -

1.1.1 相转移催化剂 - 1 -

1.1.2 醇钠 - 3 -

1.1.3 Lewis酸 - 3 -

1.1.4 质子酸 - 4 -

1.1.5 其它 - 4 -

1.2 蒙脱土概述 - 5 -

1.3 研究目的与意义及研究内容 - 5 -

1.3.1 研究目的与意义 - 5 -

1.3.2 研究内容 - 6 -

2 实验原理 - 7 -

2.1 催化剂制备原理 - 7 -

2.1.1 催化剂的制备方法 - 7 -

2.1.2 蒙脱土的无机改性 - 8 -

2.2 开环反应原理 - 8 -

3 实验部分 - 10 -

3.1 实验试剂 - 10 -

3.2 实验设备 - 10 -

3.3 实验装置 - 11 -

3.4 实验步骤 - 11 -

3.4.1 催化剂制备实验步骤 - 11 -

3.4.2 开环反应实验步骤 - 11 -

3.5 气相色谱分析 - 11 -

3.6 红外分析 - 12 -

4 结果与讨论 - 13 -

4.1 催化剂制备工艺研究 - 13 -

4.1.1 不同锡源对催化活性的影响 - 13 -

4.1.2 催化剂制备温度对催化活性的影响 - 13 -

4.1.3 催化剂负载量对催化活性的影响 - 14 -

4.2 催化反应工艺条件优化 - 15 -

4.2.1 催化剂用量对催化活性的影响 - 15 -

4.2.2 反应温度对催化活性的影响 - 16 -

4.2.3 反应时间对催化活性的影响 - 16 -

4.2.4 催化剂重复使用测试 - 17 -

4.3 类似物的制备 - 18 -

5 结论 - 19 -

参考文献 - 21 -

1 绪论

1.1 环氧氯丙烷开环反应催化剂的概述

烯丙基缩水甘油醚(1-烯丙氧基-2，3-环氧丙烷，AGE)属于小分子化合物，是一种含不饱和双键和环氧基团的活泼单体，是一种关键的有机合成中间体，在精细化工的许多领域被广泛的应用，另外也是合成各种表面活性剂及涂层反应的重要中间体。目前在日用精细化工中广泛应用的有机硅表面活性剂，其良好的水溶性和表面活性就是通过烯丙基缩水甘油醚接枝在氢硅键上制得^[1]。因为烯丙基缩水甘油醚本身具有良好的反应性和活泼性，通过加成、水解反应生成的各种试剂可被用于油漆和涂料工业以及粘合剂和化学纤维、塑料和橡胶、环氧树脂的制备等；在生产中还广泛用作添加剂、溶剂、催化剂、交联剂及链转移剂。通过对烯丙基缩水甘油醚的一些性位点进行反应，制得的衍生物具有很多功能性，其衍生物在有机交联剂、印染、有机硅以及功能材料等各行业的应用非常广泛。

烯丙基缩水甘油醚同时含有两个活泼基团，是其成较为困难的主要原因。目前的文献探究烯丙基缩水甘油醚的制备方法的并不多，较为普遍的是合成脂肪族缩水甘油醚^[2~5]。制备烯丙基缩水甘油醚的催化剂也就成为了研究重点。