CN112679330A - 一种丁二酰丁二酸二甲酯的水解工艺 - Google Patents

一种丁二酰丁二酸二甲酯的水解工艺 Download PDF

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CN112679330A
CN112679330A CN202011552754.XA CN202011552754A CN112679330A CN 112679330 A CN112679330 A CN 112679330A CN 202011552754 A CN202011552754 A CN 202011552754A CN 112679330 A CN112679330 A CN 112679330A
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CN112679330B (zh
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许龙龙
陶俊苗
赵少丹
卫冰
张振国
王文幼
康辉
王刚
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Xian Sunward Aerospace Material Co Ltd
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Abstract

本发明公开了一种丁二酰丁二酸二甲酯的水解工艺，具体按照如下步骤实施：步骤1，将DMSS加入反应釜中，加入一定量的水，开启搅拌；步骤2，给反应釜中加入相转移催化剂，开启加热；步骤3，升至反应温度后，加入酸及过渡金属盐，开始进行水解反应。本发明的一种丁二酰丁二酸二甲酯的水解工艺，解决了现有技术中存在的DMSS水解困难，水解时间长的问题。

Description

一种丁二酰丁二酸二甲酯的水解工艺
技术领域
本发明属于有机化工技术领域，涉及一种丁二酰丁二酸二甲酯的水解工艺。
背景技术
1,4-环己二酮，英文名称1,4-cyclohexanedione,分子式为C6H8O2，是一种重要的化工中间体，可用于生产药物、农药、液晶材料、有机光电材料、超导材料等。
以丁二酰丁二酸二甲酯(DMSS)为原料通过水解工艺来制备1,4-环己二酮，具有原料来源充足、成本低的优点，但DMSS水解困难，水解时间长，副产物多，难于分离，因此，要开发以DMSS为原料来制备1,4-环己二酮的工艺，必须开发高效的DMSS水解工艺。
发明内容
本发明的目的是提供一种丁二酰丁二酸二甲酯的水解工艺，解决了现有技术中存在的DMSS水解困难，水解时间长的问题。
本发明所采用的技术方案是，一种丁二酰丁二酸二甲酯的水解工艺，具体按照如下步骤实施：
步骤1，将DMSS加入反应釜中，加入一定量的水，开启搅拌；
步骤2，给反应釜中加入相转移催化剂，开启加热；
步骤3，升至反应温度后，加入酸及过渡金属盐，开始进行水解反应。
本发明的特征还在于，
步骤1中水的用量为DMSS质量的5～20倍。
相转移催化剂为十二烷基苯磺酸、十二烷基苯磺酸钠、聚乙二醇、十二烷基三甲基氯化铵或四丁基溴化铵中的一种。
相转移催化剂的用量为水用量的0.01～0.1％。
反应温度为60～100℃。
酸为硫酸、盐酸或硝酸中的一种。
酸的加入量应使H+离子浓度为0.2～12mol/L。
过渡金属盐为铜、镍、锌或锰的硝酸盐、硫酸盐或氯化物盐中的一种或几种的组合。
盐的加入量应使金属阳离子浓度为0.01～0.1mol/L。
本发明的有益效果是：
1、本发明工艺简单，操作方便，反应时间在4～60h，远小于现有技术的水解反应时间。
2、DMSS的转化率高，可达100％，产物1,4-环己二酮的选择性高，最高可达98％以上，原因可能是金属阳离子与六元环之间产生了配位作用，增加了六元环的稳定性。
3、反应中不需要添加有机溶剂，依靠加入相转移催化剂来增加DMSS与水的接触面积，节约了有机溶剂的用量，降低了废液的产生量。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明一种丁二酰丁二酸二甲酯的水解工艺，具体按照如下步骤实施：
步骤1，将DMSS加入反应釜中，加入一定量的水，其中，水的用量为DMSS质量的5～20倍，开启搅拌；
步骤2，给反应釜中加入相转移催化剂，开启加热；
步骤3，升至反应温度60～100℃后，加入酸及过渡金属盐，开始进行水解反应。
相转移催化剂为十二烷基苯磺酸、十二烷基苯磺酸钠、聚乙二醇、十二烷基三甲基氯化铵或四丁基溴化铵中的一种，相转移催化剂的用量为水用量的0.01～0.1％。
酸为硫酸、盐酸或硝酸中的一种，酸的加入量应使H+离子浓度为0.2～12mol/L。
过渡金属盐为铜、镍、锌或锰的硝酸盐、硫酸盐或氯化物盐中的一种或几种的组合，盐的加入量应使金属阳离子浓度为0.01～0.1mol/L。
实施例1
称取200g DMSS，加入1L水，开启搅拌，加入十二烷基苯磺酸0.1g，加热至60℃；然后加入浓硫酸10g，三水硝酸铜2.4g，60h后反应完成，得橙色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为90.5％。
实施例2
称取200g DMSS，加入1L水，开启搅拌，加入十二烷基苯磺酸钠0.3g，加热至70℃；然后加入浓硫酸25g，氯化锌6.8g，50h后反应完成，得淡黄色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为95.1％。
实施例3
称取200g DMSS，加入1L水，开启搅拌，加入聚乙二醇1.0g，加热至80℃；然后加入浓硫酸156g，六水硫酸镍26.3g，35h后反应完成，得淡黄绿色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为98.3％。
实施例4
称取200g DMSS，加入1L水，开启搅拌，加入十二烷基苯磺酸0.5g，加热至100℃；然后加入浓硫酸792g，50％硝酸锰水溶液23.9g，4h后反应完成，得棕黄色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为90.2％。
实施例5
称取200g DMSS，加入2L水，开启搅拌，加入十二烷基三甲基氯化铵1g，加热至80℃；然后加入浓硫酸503g，六水硝酸锌32.7g，24h后反应完成，得淡黄色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为98.5％。
实施例6
称取200g DMSS，加入4L水，开启搅拌，加入十二烷基三甲基氯化铵2g，加热至80℃；然后加入浓硫酸1000g，六水硝酸锌水55.6g，18h后反应完成，得淡黄色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为98.0％。
实施例7
称取200g DMSS，加入2L水，开启搅拌，加入四丁基溴化铵1g，加热至80℃；然后加入浓盐酸793g，六水硝酸锌水39.6g，40h后反应完成，得淡黄色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为94.5％。
实施例8
称取200g DMSS，加入2L水，开启搅拌，加入十二烷基三甲基氯化铵1g，加热至80℃；然后加入浓硝酸703g，六水硝酸锌水36.5g，40h后反应完成，得淡黄色澄清体系，经色谱分析，DMSS转化率为100％，1,4-环己二酮选择性为94.6％。
本发明极大的缩短了DMSS水解所需的时间，水解仅需4～60h，DMSS转化率接近100％，1,4-环己二酮选择性可以达到98％以上，解决了现有的DMSS难于水解、产物复杂的问题。

Claims (9)

1.一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，具体按照如下步骤实施：
步骤1，将DMSS加入反应釜中，加入一定量的水，开启搅拌；
步骤2，给反应釜中加入相转移催化剂，开启加热；
步骤3，升至反应温度后，加入酸及过渡金属盐，开始进行水解反应。
2.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述步骤1中水的用量为DMSS质量的5～20倍。
3.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述相转移催化剂为十二烷基苯磺酸、十二烷基苯磺酸钠、聚乙二醇、十二烷基三甲基氯化铵或四丁基溴化铵中的一种。
4.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述相转移催化剂的用量为水用量的0.01～0.1％。
5.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述反应温度为60～100℃。
6.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述酸为硫酸、盐酸或硝酸中的一种。
7.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述酸的加入量应使H+离子浓度为0.2～12mol/L。
8.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述过渡金属盐为铜、镍、锌或锰的硝酸盐、硫酸盐或氯化物盐中的一种或几种的组合。
9.根据权利要求1所述的一种丁二酰丁二酸二甲酯的水解工艺，其特征在于，所述盐的加入量应使金属阳离子浓度为0.01～0.1mol/L。
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DE112021000998.2T DE112021000998T5 (de) 2020-12-24 2021-11-04 Ein Verfahren zur Herstellung von 1,4-Cyclohexandion
PCT/CN2021/128703 WO2022134884A1 (zh) 2020-12-24 2021-11-04 一种1,4-环己二酮的制备方法
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WO2022134883A1 (zh) * 2020-12-24 2022-06-30 西安向阳航天材料股份有限公司 一种1,4-环己二酮的连续化生产方法
WO2022134884A1 (zh) * 2020-12-24 2022-06-30 西安向阳航天材料股份有限公司 一种1,4-环己二酮的制备方法

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焦萍等: "依那朵林的合成", 《中国医药工业杂志》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022134883A1 (zh) * 2020-12-24 2022-06-30 西安向阳航天材料股份有限公司 一种1,4-环己二酮的连续化生产方法
WO2022134884A1 (zh) * 2020-12-24 2022-06-30 西安向阳航天材料股份有限公司 一种1,4-环己二酮的制备方法

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