一步法高压合成硫化异丁烯产物分析及反应机理

doi:10.11944/j.issn.1000-0518.2015.07.140397

摘要/Abstract

摘要：

以正辛胺为催化剂,硫磺和异丁烯为原料在160~190 ℃条件下通过一步法高压合成硫化异丁烯。采用气相色谱、红外光谱和¹H NMR谱等技术手段分析了产物硫化异丁烯的化学组成。分析结果表明,产物中含有链状和环状的叔丁基多硫醚,其中链状多硫醚是主产物,同时伴有副产物4-甲基-3H-1,2-二硫杂茂-3-硫酮(MDTT)、叔丁基硫醇和少量的尾气如H₂S产生。硫化过程中主要的副反应是碱催化下硫磺与异丁烯的脱氢反应,生成MDTT和H₂S,H₂S与异丁烯进行马氏加成反应生成叔丁基硫醇,叔丁基硫醇与硫磺反应生成链状的叔丁基多硫醚。

关键词: 硫化异丁烯, 甲基-3H-二硫杂茂-硫酮, 链状叔丁基多硫醚, 反应机理

Abstract:

Sulfurized isobutylene was prepared from sulfur and isobutylene via high pressure one-step method at 160~190 ℃ with n-octylamine as catalyst. GC, FT-IR and ¹H NMR analyses of the final products show that it contains chain-like and cyclic polysulfides, chain-like polysulfides are main products, accompanied with the byproducts 4-methyl-3H-1,2-dithiole-3-thione (MDTT), tert-butyl mercaptan, and a small amount of exhaust gas such as H₂S. The formation of MDTT and H₂S is the result of the hydrogen abstraction reaction from isobutylene catalyzed by alkali in the sulfurization process. H₂S then reacts with isobutylene by Markovnikov addition to the formation of tert-butyl mercaptan which is converted to linear polysulfides by reaction with sulfur.

Key words: sulfurized isobutylene, methyl-3H-dithiole-thione, chain-like tert-butyl polysulfides, reaction mechanism

中图分类号:

李飞, 姜恒, 赵杉林, 李萍. 一步法高压合成硫化异丁烯产物分析及反应机理[J]. 应用化学, 2015, 32(7): 771-776.

LI Fei, JIANG Heng, ZHAO Shanlin, LI Ping. Product Analysis and Reaction Mechanism of High-Pressure Synthesis of Sulfurized Isobutylene by One-Step Method[J]. Chinese Journal of Applied Chemistry, 2015, 32(7): 771-776.

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