CN103880659A - 一种关于乙二醇二甲酸酯的合成工艺 - Google Patents

一种关于乙二醇二甲酸酯的合成工艺 Download PDF

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CN103880659A
CN103880659A CN201410136931.4A CN201410136931A CN103880659A CN 103880659 A CN103880659 A CN 103880659A CN 201410136931 A CN201410136931 A CN 201410136931A CN 103880659 A CN103880659 A CN 103880659A
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glycol
diformate
acid
formic acid
glycol diformate
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CN103880659B (zh
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彭学东
张梅
赵金召
申造
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Wuyang lelexin Biological Medicine Co Ltd
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Jiangsu Swithin Biological Medicine Engineering Research Center Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

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Abstract

本发明涉及一种制取乙二醇二甲酸酯的方法，包括以下步骤：1）向反应器中加入有机溶剂、反应物乙二醇、50%甲酸水溶液（工业甲酸）、酸性催化剂，升高反应体系温度，分水；2）反应一段时间，收集150-170℃的馏分，得到乙二醇二甲酸酯产品。反应稳定、安全，收率高，成本低，工艺简单，易于工业化。

Description

一种关于乙二醇二甲酸酯的合成工艺
技术领域
本发明属于精细化工技术领域，具体涉及一种乙二醇二甲酸的制备方法。
背景技术                                                               
乙二醇二甲酸酯是白色透明液体，沸点175℃/760mmHg，广泛应用于纺织领域。
经过半个多世纪的发展，全世界的表面活性剂工业已趋成熟。近年来纺织工业生产中心由于众所周知的原因已从传统的欧洲、美国逐步向亚洲转移，使得亚洲地区的纺织助剂需求量快速增长。
中国纺织助剂市场只占世界市场的10％左右。其产量与纺织纤维产量之比约3.5：100，只有世界平均水平的一半。尽管如此，近年来中国的纺织助剂工业及应用取得了长足的进步，20世纪70年代纺织助剂的年消耗还只有数千吨，到90年代末消耗量已达到24万吨～25万吨／年，其中国产助剂超过21.5万吨，进口助剂约2.2万吨，国产助剂的自给率达到了90％。
乙二醇二甲酸酯的市场需求量越来越大，其作为染色工艺的酸化剂，比普通酸的腐蚀性小，且pH调节的波动性小，使生产过程更加安全，稳定。
目前对乙二醇二甲酸酯的合成工艺未有有效的合成文献报道，对此产品的研究、开发及应用具有很好前景。
  发明内容
本发明的目的是提供一种制取乙二醇二甲酸酯的方法，使乙二醇二甲酸酯反应稳定、安全，提高产品收率，降低成本。
本发明采用以下技术方案解决上述技术问题，达到本发明的目的：
一种合成乙二醇二甲酸酯的方法，包括以下步骤：
1）向反应器中加入有机溶剂、反应物乙二醇、50%甲酸水溶液（工业甲酸）、酸性催化剂，升高反应体系温度，分水；
2）反应一段时间，收集150-170℃的馏分，得到乙二醇二甲酸酯产品。
所述的步骤1）中，所述有机溶剂是正庚烷、环己烷、甲苯，优选于甲苯；与乙二醇的体积比为1:0.7～1.5。
所述的步骤1）中，反应物乙二醇：50%甲酸水溶液：酸性催化剂的体积比为1:3～6:0.2～0. 5。
所述的步骤1)中，控制体系温度为95-115℃。
所述的步骤1)中，所述酸性催化剂是浓硫酸、盐酸、磷酸、三氟乙酸、对甲苯磺酸，优选于浓硫酸；与乙二醇的体积比为0.1～0.5:1。
本发明采用安全、经济的溶剂和催化剂合成乙二醇二甲酸酯，所提供的乙二醇二甲酸酯合成方法工艺简单，安全方便，条件温和，收率达到85%以上，且所用的反应溶剂可循环使用，易实现工业化生产。
具体实施方式
下面对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细地实施方式和过程，但本发明的保护范围不限于下述的实施例。 
实施例1
向反应器中加入反应物乙二醇200L、50%甲酸水溶液（工业甲酸）600L、对甲苯磺酸40L、环己烷200L，升温搅拌，加热回流，控制内温在95-102℃，分水，计算水的体积，搅拌8～10小时，减压蒸馏，回收环己烷溶剂，收集150-170℃/40mmHg的馏分，得到纯度大于98%的乙二醇二甲酸酯300L， 收率为78.9%。
实施例2
向反应器中加入反应物乙二醇200L、50%甲酸水溶液（工业甲酸）600L、浓硫酸40L、环己烷200L，升温搅拌，加热回流，控制内温在95-102℃，分水，计算水的体积，搅拌8～10小时，减压蒸馏，回收环己烷溶剂，收集150-170℃/40mmHg的馏分，得到纯度大于98%的乙二醇二甲酸酯310L， 收率为81.6%。
实施例3
向反应器中加入反应物乙二醇200L、50%甲酸水溶液（工业甲酸）600L、浓硫酸40L、甲苯200L，升温搅拌，加热回流，控制内温在95-102℃，分水，计算水的体积，搅拌8～10小时，减压蒸馏，回收环己烷溶剂，收集150-170℃/40mmHg的馏分，得到纯度大于98%的乙二醇二甲酸酯330L， 收率为86.8%。

Claims (5)

1.本发明具体涉及一种一种合成乙二醇二甲酸酯的方法，其特征在于包括如下步骤：
1）向反应器中加入有机溶剂、反应物乙二醇、50%甲酸水溶液（工业甲酸）、酸性催化剂，升高反应体系温度，分水；
2）反应一段时间，收集150-170℃的馏分，得到乙二醇二甲酸酯产品。
2.如权利要求1中所述的制取乙二醇二甲酸酯的方法，所述的步骤1）中，所述有机溶剂是正庚烷、环己烷、甲苯，优选于甲苯；与乙二醇的体积比为1:0.7～1.5。
3.如权利要求1中所述的制取乙二醇二甲酸酯的方法，所述的步骤1）中，反应物乙二醇：50%甲酸水溶液：酸性催化剂的体积比为1:3～6:0.2～0. 5。
4.如权利要求1中所述的制取乙二醇二甲酸酯的方法，所述的步骤1)中，控制体系温度为95-115℃。
5.如权利要求1中所述的制取乙二醇二甲酸酯的方法，所述的步骤1)中，所述酸性催化剂是浓硫酸、盐酸、磷酸、三氟乙酸、对甲苯磺酸，优选于浓硫酸；与乙二醇的体积比为0.1～0.5:1。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107814716A (zh) * 2017-10-16 2018-03-20 上海邦高化学有限公司 一种制取乙二醇二甲酸酯的工业化方法
CN109364991A (zh) * 2018-10-15 2019-02-22 沈阳化工大学 一种咪唑类离子液体催化剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2212493A (en) * 1987-11-18 1989-07-26 Bp Chem Int Ltd Production of di- or tri- esters
CN103347602A (zh) * 2011-09-22 2013-10-09 戴维加工技术有限公司 设备和方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2212493A (en) * 1987-11-18 1989-07-26 Bp Chem Int Ltd Production of di- or tri- esters
CN103347602A (zh) * 2011-09-22 2013-10-09 戴维加工技术有限公司 设备和方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHARLES G. CARLSON 等: ""The Preparation of Esters of Formic Acid using Boron Oxide"", 《CAN. J. CHEM.》, vol. 65, 31 December 1987 (1987-12-31), pages 2461 - 2463 *
KUKHAREV, B. F. 等: ""Improved method for the manufacture of ethylene glycol diformate"", 《ZHURNAL PRIKLADNOI KHIMII (SANKT-PETERBURG)》, vol. 77, no. 11, 31 December 1998 (1998-12-31), pages 1921 - 1922 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107814716A (zh) * 2017-10-16 2018-03-20 上海邦高化学有限公司 一种制取乙二醇二甲酸酯的工业化方法
CN109364991A (zh) * 2018-10-15 2019-02-22 沈阳化工大学 一种咪唑类离子液体催化剂

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