阅读说明：本技术 一种过氧化苯甲酸叔丁酯的制备方法 (Preparation method of tert-butyl peroxybenzoate ) 是由 谷迎春 李滢 费学宁 李征 于 2020-08-13 设计创作，主要内容包括：本发明公开了一种过氧化苯甲酸叔丁酯的制备方法,具体说,是先将过氧化叔丁醇与液碱成盐；然后苯甲酰氯滴加到过氧化叔丁醇钠盐中进行偶联,偶联产物分液后洗涤2次；产物加入稳定剂并经过干燥除水抽滤得到产品过氧化苯甲酸叔丁酯。本制备方法将苯甲酰氯滴加到过氧化叔丁醇钠盐中；分液后用水洗涤2次后上层产品相加入稳定剂,同时加入无水硫酸镁干燥,抽滤即得到收率不低于95％含量不低于99％的过氧化苯甲酸叔丁酯,产品可避光储存和长途运输。(The invention discloses a preparation method of tert-butyl peroxybenzoate, which comprises the steps of salifying tert-butyl peroxide and liquid alkali; then dripping benzoyl chloride into tert-butyl peroxide sodium salt for coupling, separating the liquid of the coupled product and washing for 2 times; adding a stabilizer into the product, drying, removing water and performing suction filtration to obtain the tert-butyl peroxybenzoate product. The preparation method comprises the steps of dropwise adding benzoyl chloride into tert-butyl peroxide sodium salt; after the liquid separation, washing for 2 times by using water, adding a stabilizer into the upper product phase, simultaneously adding anhydrous magnesium sulfate for drying, and performing suction filtration to obtain tert-butyl peroxybenzoate with the yield of not less than 95% and the content of not less than 99%, wherein the product can be stored in a dark place and transported for a long distance.)

1. A preparation method of tert-butyl peroxybenzoate is characterized in that the synthetic route of the tert-butyl peroxybenzoate is as follows:

2. the method of preparing tert-butyl peroxybenzoate according to claim 1, characterized by comprising the steps of:

1) dripping 1.2 equivalent of liquid alkali into 1.0 equivalent of tert-butyl peroxide to form salt, and then, after the salt formation is finished, preparing for later use;

2) slowly dripping 1.0 equivalent of benzoyl chloride into sodium salt of tert-butyl peroxide for coupling reaction;

3) after the coupling reaction is finished, separating liquid, carrying out triple effect evaporation on the lower layer high-salt wastewater, and washing the upper layer crude product;

4) washing with purified water twice, adding 0.5% stabilizer into the lower product, adding anhydrous magnesium sulfate, drying, and vacuum filtering to obtain tert-butyl peroxybenzoate product capable of being stored in dark for long term and transported for long distance.

3. The method for preparing tert-butyl peroxybenzoate according to claim 2, characterized in that the concentration of the liquid caustic soda in the step 1) is 5 to 10%.

4. The process for producing t-butyl peroxybenzoate according to claim 2, characterized in that the dropping temperature in the step 1) is 5 to 20 ℃.

5. The process for preparing tert-butyl peroxybenzoate according to claim 2, characterized in that the dropping temperature in step 2) is 5 to 15 ℃.

6. The method for preparing tert-butyl peroxybenzoate according to claim 2, characterized in that the stabilizer in step 4) is a mixture of calcium carbonate, sodium carbonate, 8-hydroxyquinoline and paraffin oil in a weight ratio of 1:1:1: 1.

7. The method for preparing tert-butyl peroxybenzoate according to claim 2, characterized in that the amount of the stabilizer added in the step 4) is 0.5 to 5%.

8. The method for preparing tert-butyl peroxybenzoate according to claim 2, wherein the equivalent of the alkali solution is 1.2 equivalents and the equivalent of the benzoyl chloride is 1.0 to 1.1 equivalents based on 1.0 equivalent of tert-butyl peroxybenzoate.

Technical Field

The invention relates to a preparation method of tert-butyl peroxybenzoate, belonging to the field of organic chemistry.

Background

Tert-butyl peroxybenzoate is an important chemical raw material, and is widely used as an initiator in polymerization processes such as ethylene, styrene, propylene, vinyl acetate, diallyl phthalate, and isobutylene. In the unsaturated polyester curing process, the unsaturated polyester curing agent is widely applied to forming processes such as SMC, BMC, DMC drawing agent and the like, and simultaneously can also be applied to a two-component curing system formed by MEPK, BPO or TBPO and the like with higher activity.

US 2567615 discloses the preparation of peroxyesters by reacting an acid chloride or a carboxylic anhydride with a tertiary alkyl hydroperoxide in the presence of an alkali metal hydroxide, a product comprising, in addition to the peroxyester, alkyl hydroperoxide which remains unreacted being obtained when the organic phase obtained in the reaction is washed with 10% strength sodium carbonate and with water.

US 3138627 discloses the similar preparation of tert-butyl peroxyesters from lower aliphatic carboxylic acids using solvents. This document teaches to the person skilled in the art that the peroxyester is removed from the alkaline mixture as quickly as possible to prevent hydrolysis by the alkaline solution.

US 4075236 discloses a continuous process for the preparation of peroxyesters, wherein an acid chloride is reacted with a hydroperoxide and an alkali metal hydroxide, wherein a biphasic reaction mixture is obtained. In this reaction, a 0-50% excess of hydroperoxide is used. The pH of the aqueous phase is in the range of 10-14. After the reaction, the aqueous phase is removed and the organic phase is washed in a plurality of mixer-settler stages. The aqueous phase was discarded in its entirety. Recovery of unreacted hydroperoxide is not disclosed.

US 3849468 discloses a continuous process for the preparation of acyl peroxides, wherein an acid chloride is reacted with hydrogen peroxide or a tertiary hydroperoxide in the presence of a solvent in a biphasic reaction mixture, and sodium hydroxide is added to form a pH value in the range of 3-10. Wherein a 10-20% molar excess of tertiary hydroperoxide is used.

In the method, the problems of low conversion rate of impurities and large wastewater quantity exist; meanwhile, the product is easy to decompose and deteriorate in the process of storage and transportation.

Disclosure of Invention

The invention aims to provide a preparation method of tert-butyl peroxybenzoate, which has stable quality, higher yield and safe transportation, aiming at the defects of the prior art.

In order to solve the existing technical problems, the technical scheme of the invention is as follows:

a preparation method of tert-butyl peroxybenzoate comprises the following steps:

further, the method comprises the following steps:

1) dripping 1.2 equivalents of liquid alkali into 1.0 equivalent of tert-butyl peroxide to form salt, and then, after the salt formation is finished, keeping for later use;

2) slowly dripping 1.0 equivalent of benzoyl chloride into sodium salt of tert-butyl peroxide for coupling reaction;

3) after the coupling reaction is finished, separating liquid, carrying out triple effect evaporation on the lower layer high-salt wastewater, and washing the upper layer crude product;

4) washing twice with purified water, adding stabilizer into the lower product, adding anhydrous magnesium sulfate, drying, and vacuum filtering to obtain tert-butyl peroxybenzoate product capable of being stored in dark place for long term and transported for long distance.

Further, the concentration of the liquid caustic soda in the step 1) is 5-10%.

Further, the dropping temperature in the step 1) is 5-20 ℃.

Further, the dropping temperature in the step 2) is 5-15 ℃.

Further, in the step 4), the stabilizer is a mixture of calcium carbonate, sodium carbonate, 8-hydroxyquinoline and paraffin oil according to a weight ratio of 1:1:1: 1.

Further, the adding amount of the stabilizer in the step 4) is 0.5-5%.

Further, when the basic equivalent of the tert-butyl peroxide in the step 1) and the step 2) is 1.0, the equivalent of the alkali liquor is 1.2 equivalents, and the equivalent of the benzoyl chloride is 1.0-1.1 equivalents

The preparation method of the tert-butyl peroxybenzoate disclosed by the invention is summarized as follows:

the invention has the advantages that: 1) the reaction yield is more than 95 percent; the content is more than 99 percent; 2) the washing times are less, and the waste water is less; 3) the mixed stabilizer can be stored for a long time and transported for a long distance.

Drawings

FIG. 1 is a GC spectrum of example 1 (apparatus: gas chromatograph 9790 plus; detector: hydrogen flame detector (FID); capillary column KB-5, 30m 0.32mm 0.25 um; detector: 260 ℃; injection port: 220 ℃; heating mode: thermostating).

Detailed Description

The invention will be further illustrated by the following examples.