Page 177 - 《精细化工》2021年第12期

第 38 卷第 12 期 精 细 化 工 Vol.38, No.12
2021 年 12 月 FINE CHEMICALS Dec. 2021

催化与分离提纯技术
PEG1000 强化钾盐催化硫醇 β-羟乙基化反应

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卢 宁，宫 红，姜 恒 ，王 锐，李 飞
（辽宁石油化工大学 石油化工学院，辽宁 抚顺 113001）

摘要：在常压、无溶剂条件下，以聚乙二醇（PEG）为相转移剂，钾盐为催化剂，碳酸乙烯酯（EC）和硫醇（RSH）
为原料合成了 β-羟乙基烷基硫醚（RSCH 2 CH 2 OH）。系统考察了 PEG 对不同钾盐在 RSH 的 β-羟乙基化反应中的
固/液相转移作用以及 EC 用量对 RSCH 2 CH 2 OH 选择性的影响。通过 GC 和 GC-MS 计算与测定 RSH 转化率、
RSCH 2 CH 2 OH 选择性和副产物。结果表明，PEG 本身没有催化活性，与单独加入 0.5%（以 RSH 物质的量为基
准，下同）K 2 CO 3 相比，同时加入 1.0% PEG 和 0.5% K 2 CO 3 可显著提高 RSH 转化率和反应速率。PEG 相对分
子质量<1000 时，PEG 对 K 2 CO 3 催化活性的强化作用随着 PEG 链长度的增长而增强。RSCH 2 CH 2 OH 的选择性
随着 EC 与 RSH 物质的量比（≥1.02）的增大而降低，副产物为乙烯基烷基硫醚和乙二醇。无溶剂条件下，PEG
的加入能有效打破钾盐催化剂与液相反应物之间的相界面限制，增强钾盐催化活性，缩短反应时间，提高产品
收率。
关键词：硫醇；羟乙基化；聚乙二醇；固/液相转移；碳酸乙烯酯；催化技术
中图分类号：TQ227.1；TQ227.2 文献标识码：A 文章编号：1003-5214 (2021) 12-2539-07

PEG1000 enhanced potassium salt catalyzing β-hydroxyethylation of mercaptan

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LU Ning, GONG Hong, JIANG Heng , WANG Rui, LI Fei
（School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China）

Abstract: β-Hydroxyethyl alkyl sulfide (RSCH 2 CH 2 OH) was synthesized by using polyethylene glycol (PEG)
as phase transfer agent, potassium salt as catalyst, ethylene carbonate (EC) and mercaptan (RSH) as raw
materials under atmospheric pressure and solvent-free. The effect of PEG on the solid/liquid phase transfer
of different potassium salts in the β-hydroxyethylation of RSH and the effect of EC dosage on the selectivity
of RSCH 2CH 2OH were investigated. The conversion of RSH, selectivity of RSCH 2CH 2OH and by-products
were analyzed by GC and GC-MS. The results showed that PEG itself had no catalytic activity. Compared
with the addition of 0.5% (based on the molar amount of substance of RSH, the same below) K 2 CO 3 alone, the
addition of 1.0% PEG and 0.5% K 2CO 3 could significantly improve the conversion rate of RSH and reaction
rate. The enhancement effect of PEG on the catalytic activity of K 2CO 3 increased with the increase of the
length of PEG chain when relative molecular mass of PEG was less than 1000. The selectivity of
RSCH 2CH 2OH decreased with increasing the molar ratio of EC/RSH (≥1.02), the by-products were vinyl
alkyl sulfide and ethylene glycol. The addition of PEG could effectively break the phase interface limitation
between potassium salt catalyst and liquid phase reactants, enhance the catalytic activity of potassium salt,
shorten the reaction time and increase the product yield under solvent-free condition.
Key words: mercaptan; hydroxyethylation; polyethylene glycol; solid/liquid phase transfer; ethylene carbonate;
catalysis technology

通常有机合成反应需要采用各种有机溶剂作为 产过程中溶剂可以回收使用，但分离溶剂无疑会增
反应介质。许多有机溶剂对生态有害。尽管工业生 加能量消耗，同时也不可能做到 100%回收，这就意

收稿日期：2021-06-08; 定用日期：2021-08-20; DOI: 10.13550/j.jxhg.20210580
基金项目：辽宁省自然科学基金指导计划项目（2019-ZD-0053）
作者简介：卢 宁（1994—），女，硕士生，E-mail：1757787256@qq.com。联系人：姜 恒（1967—），男，教授，E-mail：hjiang78@
hotmail.com。