阅读说明：本技术 一种1,4-丁二醇二缩水甘油醚的清洁化生产方法 (Clean production method of 1, 4-butanediol diglycidyl ether ) 是由 殷杰 于 2020-07-31 设计创作，主要内容包括：本发明公开了一种1,4-丁二醇二缩水甘油醚的清洁化生产方法,本发明先通过1,4-丁二醇与环氧氯丙烷在催化剂的作用下生成氯醇醚,再在碱的作用下进行闭环反应生成1,4-丁二醇二缩水甘油醚。本发明通过大量实验筛选得到最佳的合成路线,原料转化率高,收率可达99%以上,产生的废水少,条件温和,操作简便,适合清洁化工业生产。(The invention discloses a clean production method of 1, 4-butanediol diglycidyl ether, which comprises the steps of firstly generating chlorohydrin ether by 1, 4-butanediol and epoxy chloropropane under the action of a catalyst, and then carrying out ring-closure reaction under the action of alkali to generate the 1, 4-butanediol diglycidyl ether. The method obtains the optimal synthetic route through a large number of experimental screens, has high raw material conversion rate, yield of over 99 percent, less generated waste water, mild conditions and simple and convenient operation, and is suitable for clean industrial production.)

1. A clean production method of 1, 4-butanediol diglycidyl ether is characterized by comprising the following steps:

(1) adding 1, 4-butanediol and a catalyst into a reactor, uniformly stirring, dropwise adding epoxy chloropropane at the temperature of 60-80 ℃, wherein the dropwise adding time is 1-3 hours, and keeping for 1-2 hours;

(2) starting stirring, adding a certain amount of toluene solvent into a reactor, adding alkali at 35-45 ℃, using for 2-4 hours, and keeping for 1-2 hours after the use;

(3) and transferring the mixture to a Buchner funnel for suction filtration after the reaction is finished, adding a certain amount of phosphoric acid into the filtrate for neutralization, transferring the mixture to a separating funnel for liquid separation, and removing the toluene solvent after liquid separation to obtain the 1, 4-butanediol diglycidyl ether.

2. The clean production method of 1, 4-butanediol diglycidyl ether according to claim 1, characterized by comprising the following steps:

(1) adding 1, 4-butanediol and a catalyst into a reactor, uniformly stirring, dropwise adding epoxy chloropropane at the temperature of 60-80 ℃, wherein the dropwise adding time is 3 hours, and keeping for 1 hour;

(2) starting stirring, adding a certain amount of toluene solvent into a reactor, adding alkali at 35-45 ℃, using for 4 hours, and keeping for 1 hour after the use;

(3) and transferring the mixture to a Buchner funnel for suction filtration after the reaction is finished, adding a certain amount of phosphoric acid into the filtrate for neutralization, transferring the mixture to a separating funnel for liquid separation, and removing the toluene solvent after liquid separation to obtain the 1, 4-butanediol diglycidyl ether.

3. The method for preparing 1, 4-butanediol diglycidyl ether according to claim 1, characterized in that, in the step (1), the catalyst is boron trifluoride-diethyl ether or perchloric acid; the mass ratio of the catalyst to the 1, 4-butanediol is 5 per thousand-1%.

4. The method for producing 1, 4-butanediol diglycidyl ether according to claim 1, characterized in that the molar mass ratio of epichlorohydrin to 1, 4-butanediol in step (1) is 2.2 to 2.4: 1.

5. The method for producing 1, 4-butanediol diglycidyl ether according to claim 1, characterized in that, in the step (1), the reaction temperatures are 60 ℃ to 80 ℃ respectively.

6. The method for producing 1, 4-butanediol diglycidyl ether according to claim 1, wherein the mass ratio of toluene to 1, 4-butanediol in step (2) is 2.5: 1 to 4: 1.

7. The method for producing 1, 4-butanediol diglycidyl ether according to claim 1, characterized in that, in the step (2), the reaction temperatures are 35 ℃ to 45 ℃ respectively.

8. The method for producing 1, 4-butanediol diglycidyl ether according to claim 1, characterized in that the NaOH solution or the reinforced NaOH solution having a mass concentration of 32% to 48% is added in the step (2) over 4 hours at a molar mass ratio of NaOH to epichlorohydrin of 1: 1 to 1.1: 1.

Technical Field

The invention relates to a clean production method of 1, 4-butanediol diglycidyl ether, belonging to the technical field of high polymer materials.

Background

The 1, 4-butanediol diglycidyl ether is an important organic chemical intermediate, is widely applied to the fields of coating industry and synthetic chemical industry, can be used as an epoxy reactive diluent, belongs to a multifunctional reactive diluent, has the characteristics of good flexibility, low viscosity, small volatility, small smell, low toxicity and the like, and is used as a diluent of epoxy resin to reduce the viscosity of an epoxy system and improve the mechanical property of an epoxy cured product. Although the existing synthesis method has high yield, the generated wastewater is more, so the development of a green and environment-friendly preparation method of 1, 4-butanediol diglycidyl ether, which has the advantages of less wastewater generated in the production process, mild condition, simple and convenient operation and suitability for industrial production, is urgently needed.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide a preparation method of green and environment-friendly 1, 4-butanediol diglycidyl ether, which has the advantages of less waste water generated in the production process, mild condition, simple and convenient operation and suitability for industrial production, by screening a large number of experiments aiming at the defect of generating a large amount of waste water in the prior art.

Technical solution to achieve the above object, the present invention adopts the following technical solutions:

a clean production method of 1, 4-butanediol diglycidyl ether comprises the following steps:

(1) adding 1, 4-butanediol and a catalyst into a reactor, uniformly stirring, dropwise adding epoxy chloropropane at the temperature of 60-80 ℃, wherein the dropwise adding time is 1-3 hours, and keeping for 1-2 hours;

(2) starting stirring, adding a certain amount of toluene solvent into a reactor, adding alkali at 35-45 ℃, using for 2-4 hours, and keeping for 1-2 hours after the use;

(3) and transferring the mixture to a Buchner funnel for suction filtration after the reaction is finished, adding a certain amount of phosphoric acid into the filtrate for neutralization, transferring the mixture to a separating funnel for liquid separation, and removing the toluene solvent after liquid separation to obtain the 1, 4-butanediol diglycidyl ether.

Preferably, the clean production method of 1, 4-butanediol diglycidyl ether comprises the following steps:

(1) adding 1, 4-butanediol and a catalyst into a reactor, uniformly stirring, dropwise adding epoxy chloropropane at the temperature of 60-80 ℃, wherein the dropwise adding time is 3 hours, and keeping for 1 hour;

(2) starting stirring, adding a certain amount of toluene solvent into the reactor, adding alkali at the temperature of 30-45 ℃, and keeping for 1 hour after the alkali is added;

(3) and transferring the mixture to a Buchner funnel for suction filtration after the reaction is finished, adding a certain amount of phosphoric acid into the filtrate for neutralization, transferring the mixture to a separating funnel for liquid separation, and removing the toluene solvent after liquid separation to obtain the 1, 4-butanediol diglycidyl ether.

Preferably, in the above-mentioned method for preparing 1, 4-butanediol diglycidyl ether, in the step (1), the catalyst is boron trifluoride-diethyl ether or perchloric acid; the mass ratio of the catalyst to the 1, 4-butanediol is 5 per thousand-1%. Particularly preferably, the mass ratio of boron trifluoride-diethyl ether to 1, 4-butanediol is 7 ‰.

Preferably, in the above method for producing 1, 4-butanediol diglycidyl ether, in the step (1), the molar mass ratio of epichlorohydrin to 1, 4-butanediol is 2.2: 1 to 2.4: 1; more preferably 2.2: 1, 2.3: 1, 2.4: 1; particularly preferably, the molar mass ratio of epichlorohydrin to 1, 4-butanediol is 2.3: 1.

Preferably, in the preparation method of 1, 4-butanediol diglycidyl ether, in the step (1), the reaction temperatures are respectively 60-80 ℃; more preferably 60 deg.C, 70 deg.C, 80 deg.C; particularly preferably 70 deg.c.

Preferably, in the above method for producing 1, 4-butanediol diglycidyl ether, in the step (2), the mass ratio of toluene to 1, 4-butanediol is 2.5: 1 to 4: 1; a mass ratio of toluene to 1, 4-butanediol of 3.5: 1 is particularly preferred.

Preferably, in the preparation method of 1, 4-butanediol diglycidyl ether, in the step (2), the reaction temperature is 35-45 ℃; more preferably 35 deg.C, 40 deg.C, 45 deg.C; particularly preferably 40 deg.c.

Preferably, in the above method for preparing 1, 4-butanediol diglycidyl ether, in step (2), a NaOH solution with a mass concentration of 32% and 48% or solid NaOH is added for 4 hours; solid NaOH is particularly preferred.

Preferably, in the above process for producing 1, 4-butanediol diglycidyl ether, the molar mass ratio of NaOH to epichlorohydrin in step (2) is 1: 1, 1.05: 1, or 1.1: 1; the molar mass ratio of NaOH to epichlorohydrin is particularly preferably 1.05: 1.

Has the advantages that: compared with the prior art, the invention has the following advantages:

the invention obtains the best raw material composition and proportion through a large number of experimental screens, and optimizes and selects the best catalyst, reaction raw materials and synthesis process through a large number of experiments. The whole preparation process is reasonable in design, and the 1, 4-butanediol diglycidyl ether is prepared by firstly generating chlorohydrin ether by 1, 4-butanediol and epoxy chloropropane under the action of a catalyst and then carrying out ring-closing reaction under the action of alkali. The method obtains the optimal synthetic route through a large number of experimental screens, has high raw material conversion rate, yield of over 99 percent, less generated waste water, mild conditions and simple and convenient operation, and is suitable for clean industrial production.

Drawings

FIG. 1 is a reaction scheme of the present invention.

Detailed Description