CN-122010812-A - Preparation method of tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content

CN122010812ACN 122010812 ACN122010812 ACN 122010812ACN-122010812-A

Abstract

The invention relates to the technical field of organic synthesis, in particular to a preparation method of tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content. The invention solves the problems of low active oxygen content and low yield of the product in the prior art. The preparation method comprises the steps of firstly clathrating and stabilizing tert-butyl hydroperoxide by using methyl-beta-cyclodextrin to construct a premixed solution, then introducing a modified catalyst into a composite solvent environment consisting of isododecane and hydrofluoroether, dropwise adding 2-ethylhexyl chloroformate through a low-temperature high-shear process to complete the reaction, and finally performing solid-phase adsorption impurity removal by using modified hydrotalcite, and distilling to obtain tert-butyl peroxy-2-ethylhexyl carbonate. According to the invention, the interfacial heat transfer is improved through the composite solvent, the reaction rate is improved by utilizing the high active site of the modified catalyst, and the anhydrous deacidification and dechlorination are realized by matching with the modified hydrotalcite.

Inventors

DING LITAO
WU GUANGLEI
MA YI
WU HUACHAO
CHEN WEI
XU YEQING
SHAN DAWEI
LI JINGE
ZHAO ZHIGANG

Assignees

宿迁市万和泰化工有限公司

Dates

Publication Date: 20260512
Application Date: 20260202

Claims (7)

1. The preparation method of the tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content is characterized by comprising the following steps: The preparation method comprises the steps of mixing a potassium hydroxide solution, methyl-beta-cyclodextrin and a tert-butyl hydroperoxide solution to obtain a premixed solution, adding a composite solvent, a modified catalyst and 2-ethylhexyl chloroformate into the premixed solution, reacting to obtain a reaction mixture, carrying out post-treatment on the reaction mixture by modified hydrotalcite to obtain the tert-butyl peroxy-2-ethylhexyl carbonate, wherein the composite solvent is obtained by mixing isododecane and hydrofluoroether, and the modified catalyst is prepared by hyperbranched polyglycidyl ether, 1, 2-epoxydodecane, potassium hydroxide and 2, 3-epoxypropyl trimethyl ammonium chloride.
2. The preparation method of the tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content according to claim 1, wherein the preparation method of the premixed solution is characterized in that the potassium hydroxide solution and the methyl-beta-cyclodextrin are added into a reaction kettle, the tert-butyl hydroperoxide solution is dropwise added in the stirring process, and the premixed solution is obtained by continuing stirring after the dropwise addition.
3. The preparation method of the tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content according to claim 1, wherein the preparation method of the reaction mixture is characterized in that the compound solvent and the modified catalyst are added into the pre-mixed solution, stirring is continued to obtain a compound emulsion, the 2-ethylhexyl chloroformate is dropwise added into the compound emulsion, and stirring and curing are carried out after the dropwise addition are finished, so as to obtain the reaction mixture.
4. The method for preparing tert-butylperoxy-2-ethylhexyl carbonate with high active oxygen content according to claim 1, wherein the weight ratio of the isododecane to the hydrofluoroether is 3-5:1.
5. The preparation method of the tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content according to claim 1, wherein the preparation method of the modified catalyst comprises the steps of adding hyperbranched polyglycidyl ether and isopropanol into a four-neck flask, stirring and dissolving, adding potassium hydroxide into the mixture to obtain an activated solution, dropwise adding 1, 2-epoxydodecane into the activated solution, carrying out reflux reaction after the dropwise adding is finished to obtain a reaction system, dropwise adding isopropanol solution containing the 2, 3-epoxypropyltrimethyl ammonium chloride into the reaction system, continuing the reaction after the dropwise adding is finished, carrying out reduced pressure distillation, precipitating, filtering and collecting solids, and carrying out vacuum drying to obtain the modified catalyst.
6. The preparation method of the tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content according to claim 1, wherein the specific process of the post-treatment of the modified hydrotalcite is that the reaction mixture is kept still for layering, water phase is separated and removed, the modified hydrotalcite is added into an oil phase in a kettle, the oil phase mixture is obtained through stirring and adsorption treatment, the oil phase mixture is filtered and adsorbed to obtain filtrate, the filtrate is subjected to adsorption column to remove the modified catalyst, effluent is collected, the effluent is distilled, and components discharged from the bottom are collected and filtered to obtain the tert-butyl peroxy-2-ethylhexyl carbonate.
7. The preparation method of the tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content according to claim 6, wherein the preparation method of the modified hydrotalcite is characterized in that a hydrotalcite precursor is put into a muffle furnace, the temperature is raised to 440-460 ℃ to bake for 3-5 hours to obtain baked hydrotalcite, sodium stearate is added into deionized water, stirring is carried out to form sodium stearate solution, the baked hydrotalcite is dispersed into absolute ethyl alcohol, the sodium stearate solution is added, stirring reflux reaction is carried out, filtering washing is carried out, and vacuum drying is carried out to obtain the modified hydrotalcite.

Description

Preparation method of tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content Technical Field The invention relates to the technical field of organic synthesis, in particular to a preparation method of tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content. Background The tert-butyl peroxy-2-ethylhexyl carbonate is a high-efficiency low-volatility organic peroxide and is widely applied to polymerization initiators of monomers such as ethylene, styrene, acrylic ester and the like, and curing agents of unsaturated polyesters. The molecular structure of the modified polyurethane has a peroxy bond and a carbonate group, so that the modified polyurethane has excellent heat stability and initiation activity. In industrial application, the high-purity tert-butyl peroxy-2-ethylhexyl carbonate can not only improve the polymerization rate, but also remarkably reduce the residual odor and yellowing phenomenon in polymer products, and is a key auxiliary agent for producing high-end optical-grade resin and food-contact-grade plastics. Although the tert-butyl peroxy-2-ethylhexyl carbonate has wide application, in the existing industrial preparation technology, two main core bottlenecks are faced, namely, the active oxygen content is difficult to increase, and the reaction yield is unstable. In the traditional process, tert-butyl hydroperoxide and 2-ethylhexyl chloroformate are mostly adopted to react under alkaline conditions, however, the 2-ethylhexyl chloroformate is extremely easy to generate hydrolysis side reaction in a strong alkaline aqueous phase to generate impurities consisting of 2-ethylhexyl alcohol and carbon dioxide, so that the yield is directly reduced, and hydrolysis products can wrap reactants due to emulsification to prevent the main reaction. Meanwhile, the local alkali concentration is too high and the reaction heat is not removed timely, so that sensitive peroxy bonds are thermally decomposed, and the active oxygen content of the final product is difficult to stabilize. For this purpose, a process for preparing tert-butylperoxy-2-ethylhexyl carbonate having a high active oxygen content is proposed. Disclosure of Invention The invention aims to design a preparation method of tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content. The preparation method comprises the steps of firstly clathrating and stabilizing tert-butyl hydroperoxide by using methyl-beta-cyclodextrin to construct a premixed solution, then introducing a modified catalyst into a composite solvent environment consisting of isododecane and hydrofluoroether, dropwise adding 2-ethylhexyl chloroformate through a low-temperature high-shear process to complete the reaction, and finally performing solid-phase adsorption impurity removal by using modified hydrotalcite, and distilling to obtain tert-butyl peroxy-2-ethylhexyl carbonate. According to the invention, the interfacial heat transfer is improved through the composite solvent, the reaction rate is improved by utilizing the high active site of the modified catalyst, and the anhydrous deacidification and dechlorination are realized by matching with the modified hydrotalcite. In order to achieve the above purpose, the invention provides the following technical scheme that the following parts are weight parts unless specified otherwise. The invention provides a preparation method of tert-butyl peroxy-2-ethylhexyl carbonate with high active oxygen content, which comprises the following steps: mixing potassium hydroxide solution, methyl-beta-cyclodextrin and tertiary butyl hydroperoxide solution to obtain a premixed solution, adding a composite solvent, a modified catalyst and 2-ethylhexyl chloroformate into the premixed solution, reacting and curing to obtain a reaction mixture, carrying out post-treatment on the reaction mixture by modified hydrotalcite to obtain tertiary butyl peroxy-2-ethylhexyl carbonate, wherein the composite solvent is obtained by mixing isododecane and hydrofluoroether, and the modified catalyst is prepared from hyperbranched polyglycidyl ether, potassium hydroxide, 1, 2-epoxydodecane and 2, 3-epoxypropyl trimethyl ammonium chloride. Preferably, the preparation method of the premix solution comprises the steps of adding 60 parts of 45% potassium hydroxide solution and 0.1-0.3 part of methyl-beta-cyclodextrin (average substitution degree is 1.8 and CAS number: 128446-36-6) into a reaction kettle provided with a deep cooling jacket and a high-shear dispersion disc (the diameter of the dispersion disc is 1:3) in diameter ratio, starting low-speed stirring (150 rpm), reducing the kettle temperature to 5 ℃, slowly dropwise adding 66-70 parts of 70% tertiary butyl hydroperoxide solution, controlling the dropwise adding speed to ensure that the internal temperature is not more than 8 ℃, and keeping stirring at 6 ℃ for 20min after the dropwise adding is finished to obtain the premix solution. Preferably, the preparation met