CN115960026A

CN115960026A - Preparation method of organic peroxide

Info

Publication number: CN115960026A
Application number: CN202111190151.4A
Authority: CN
Inventors: 张懿旸; 夏凉; 李玉博
Original assignee: Jiahua Chemical Shanghai Co ltd
Current assignee: Jiahua Chemical Shanghai Co ltd
Priority date: 2021-10-13
Filing date: 2021-10-13
Publication date: 2023-04-14

Abstract

The invention provides a preparation method of organic peroxide. The method comprises the step of carrying out synthetic reaction on organic alcohol or organic ketone and hydrogen peroxide in a microchannel reactor under the catalysis of concentrated sulfuric acid to obtain the organic peroxide. The invention utilizes the microchannel reactor to synthesize organic peroxide, and organic alcohol, hydrogen peroxide and concentrated sulfuric acid are reacted to obtain organic peroxide with a corresponding structure; and the microchannel reactor can avoid the harm of a large amount of exothermic reaction, greatly shorten the reaction time, ensure the continuous reaction and effectively improve the yield.

Description

Preparation method of organic peroxide

Technical Field

The invention belongs to the field of material chemistry, and particularly relates to a preparation method of organic peroxide.

Background

The organic peroxide generally refers to an organic compound having a-O-peroxy functional group, which is formed by replacing a hydrogen atom in hydrogen peroxide with an organic group such as an alkyl group, an acyl group, or an aromatic group. Is characterized in that the oxygen-containing free radical is generated by decomposition after being heated to exceed a certain temperature, and is unstable and easy to decompose. The organic peroxide produced in chemical industry is mainly used as polymerization initiator and catalyst for synthetic resin. In the field of high molecular materials, it can be used as an initiator of free radical polymerization, an initiator of grafting reaction, a cross-linking agent of rubber and plastics, a curing agent of unsaturated polyester and a molecular weight and molecular weight distribution regulator in the preparation of spinning-grade polypropylene. The peroxyacyl nitrate compounds can be generated by the free radical reaction of polluted air in the environment under the action of light, and are one of the particles of photochemical oxidants.

In the field of high molecular materials, organic peroxides are used as initiators for free radical polymerization, initiators for grafting reactions, crosslinking agents for rubber and plastics, curing agents for unsaturated polyesters, and molecular weight distribution regulators in the preparation of spinning-grade polypropylene. Organic peroxides are a source of free radicals for the following uses: (1) a free radical polymerization and copolymerization initiator of a vinyl group and a diene monomer; (2) a vulcanizing agent for a thermosetting resin; (3) a crosslinking agent for elastomers and polyethylene.

In addition to the above-mentioned polymer material industry, organic peroxides are used in the film industry as photoinitiators and sensitizers, in photosensitive polymer materials, photosensitive resins, and the like, and are also commonly used in the production of epoxy resins; in the aspect of medical materials, the initiator consisting of organic peroxide and medicine is used for synthesizing medicine sustained-release dosing matrixes (such as microspheres, pellets and medicine films); in organic synthesis, organic peroxides are mainly used as oxidizing and epoxidizing agents. In addition, organic peroxides are used for disinfection of medical instruments and foods, bleaching agents, decolorants, disinfectants, cleaning agents, and the like in the daily chemical industry of textiles, paper, and the like.

The decomposition temperature of an organic peroxide at an effective rate largely determines its utility. Other important factors are cost, solubility, safety. Efficiency and the type of free radicals produced, the necessity for refrigerated storage and shipping, compatibility with production systems, possible effects on the product and the ability to be activated, etc. The organic peroxide can be decomposed at a certain speed at high temperature or room temperature to generate reactive free radicals.

All organic peroxides are thermally unstable and decompose more rapidly with increasing temperature. A common quantitative measure of the reactivity of organic peroxides is the measurement of the half-life, i.e. the time required for a certain amount of peroxide to decompose to half its initial amount at a certain temperature. The half-life data for commercial organic peroxides are now available on computer floppy disks. The appropriate peroxide can be selected for a certain polymerization or process condition using a computer menu program.

These radicals can be added to unsaturated vinyl monomers such as: styrene, vinyl chloride or methyl methacrylate. Some radicals also attack polymers such as Polyethylene (PE) to form radicals on the chain. When two such polymer radicals are combined, a crosslinked structure is formed. At present, organic peroxide is generally synthesized by organic alcohol and hydrogen peroxide under the catalysis of concentrated sulfuric acid. However, the raw materials used in this reaction are highly dangerous (strong oxidation, easy corrosion, explosive).

Disclosure of Invention

In order to reduce the risk, the invention provides a preparation method of organic peroxide. The technical scheme is as follows: in a microchannel reactor, organic alcohol or organic ketone and hydrogen peroxide are subjected to synthetic reaction under the catalysis of concentrated sulfuric acid to obtain the organic peroxide. The concentrated sulfuric acid is a sulfuric acid aqueous solution with the mass fraction of more than or equal to 70%.

In some embodiments, the reaction temperature is from 0 to 80 ℃.

In some embodiments, the reaction pressure is atmospheric.

In some embodiments, the microchannel reaction time is from 10 to 60min.

In some embodiments, the equivalent ratio of the organic alcohol or the organic ketone to the hydrogen peroxide is 1:0.5-2.5.

In some embodiments, the percentage of concentrated sulfuric acid is greater than 45% of the mixed liquor; the mixed solution consists of the organic alcohol or ketone, the hydrogen peroxide and the concentrated sulfuric acid. Namely the percentage of the sulfuric acid in the mixed solution is more than 45 percent.

In some embodiments, the organic alcohol is selected from one or more of 2, 5-dimethyl-2, 5-hexanediol, 1, 4-dihydroxy-diisopropylbenzene, t-butanol, and derivatives thereof; the organic ketone is selected from one or more of butanone and homologs thereof. The homologues of butanol include acetone and pentanone.

In some embodiments, the organic peroxide is 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane; the preparation method specifically comprises the following steps: dissolving 2, 5-dimethyl-2, 5-hexanediol in hydrogen peroxide, introducing the hydrogen peroxide and concentrated sulfuric acid into a microchannel reactor, separating out solids after reaction, dissolving the solids in tert-butyl alcohol after separation, and reacting the tert-butyl alcohol with the concentrated sulfuric acid to obtain the product.

In some embodiments, the organic peroxide is di-t-butyl peroxide hexane; the preparation method specifically comprises the following steps: and (2) introducing tert-butyl alcohol and hydrogen peroxide together with concentrated sulfuric acid into the microchannel reactor in proportion, and after reaction, carrying out phase separation on the system to obtain an oil phase which is the di-tert-butyl peroxide.

In some embodiments, the organic peroxide is di-tert-butylperoxyisopropyl benzene; the preparation method specifically comprises the following steps: and (2) introducing tert-butyl alcohol and hydrogen peroxide together with concentrated sulfuric acid into a microchannel reactor according to a certain proportion, carrying out phase splitting on the system after reaction, mixing the oil phase with diperoxypro-isopropylbenzene, and introducing the mixture and the concentrated sulfuric acid into the microchannel reactor to obtain the di-tert-butylperoxyisopropylbenzene.

In some embodiments, the organic peroxide is 3,6,9-triethyl-3,6,9-trimethyl-1, 4, 7-triperoxonane; the preparation method specifically comprises the following steps: butanone and hydrogen peroxide are proportionally introduced into a microchannel reactor together with concentrated sulfuric acid, and the system is subjected to phase splitting after the reaction, so that the obtained oil phase is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane.

Microreactors, microstructured reactors, microchannel reactors refer to chemical reactions that can be completed in a range of lateral dimensions less than 1mm, and the most typical representation of such structures is microchannels. Microreactors are subjects in the field of micro-engineering, and this device (e.g. a micro-heat exchanger) is also accompanied by some physical reactions. Such microreactors are typically continuous fluid reactors (as opposed to batch reactors). Compared with conventional reaction equipment, the microreactor has advantages in many aspects, such as heat exchange efficiency, reaction speed, yield, safety, stability, monitoring performance, on-site/on-demand production and capability of more refined production control.

The invention utilizes the microchannel reactor to synthesize organic peroxide, and organic alcohol, hydrogen peroxide and concentrated sulfuric acid are reacted to obtain organic peroxide with a corresponding structure; and the microchannel reactor can avoid the harm of a large amount of exothermic reaction, greatly shorten the reaction time, ensure the continuous reaction and effectively improve the yield.

Compared with the traditional process, the invention has the following advantages:

1. compared with the traditional method for synthesizing organic peroxide, the method provided by the invention has the advantages that the damage caused by a large amount of exothermic reaction can be avoided due to the characteristics of the microchannel reactor, the reaction can be directly carried out at a higher temperature, and the reaction time is short.

2. The production efficiency is high, the microchannel reactor can continuously carry out the reaction, the steps of pretreatment and post-treatment can be reduced, and the time of the whole reaction is saved.

3. The safety factor is high, the liquid holdup of the microchannel reactor is small, the temperature control is accurate, and the safety of the production process can be guaranteed.

Detailed Description

The present invention will be described with reference to specific embodiments in order to make the technical means, inventive features, achievement objects and effects of the invention easy to understand. However, the present invention is not limited to the following embodiments. The flow rate of the micro-channel reactor introduced into the following examples is 0.1-50ml/min, preferably 0.1-20ml/min.

Comparative example 1

Adding 97g of hydrogen peroxide into a flask, slowly adding 63g of concentrated sulfuric acid at the temperature of 0 ℃, then adding 14.6g of 2, 5-dimethyl-2, 5-hexanediol, reacting at the temperature of 15 ℃, separating out a large amount of white solid after 3h, filtering, and washing with clear water to obtain 2, 5-dimethyl-2, 5-peroxy hexanediol with the yield of 98%; adding 1.45g of 2, 5-dimethyl-2, 5-peroxyhexanediol into the mixed solution (7.8 g of tert-butyl alcohol/4.2 g of concentrated sulfuric acid/2 g of water), heating to 40 ℃ for reaction, after 2 hours, carrying out phase separation on the reaction system, taking the upper oil phase, and washing with anhydrous sodium carbonate to obtain 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane with the yield of 77%.

Example 1

Dissolving 14.6g of 2, 5-dimethyl-2, 5-hexanediol in 97g of hydrogen peroxide, introducing the hydrogen peroxide and concentrated sulfuric acid into a microchannel reactor at 40 ℃ according to the proportion of 2; dissolving the obtained 2, 5-dimethyl-2, 5-peroxyhexanediol in a mixed solution (7.8 g of tert-butyl alcohol/4.2 g of concentrated sulfuric acid/2 g of water), heating to 40 ℃, introducing into a microchannel reactor, after 15min, carrying out phase separation on a reaction system, and separating by using a continuous phase oil-water separator to obtain 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane with the yield of 98%.

Comparative example 2

31.4g of concentrated sulfuric acid is gradually added into 13.6g of hydrogen peroxide (30%) at the temperature of 0 ℃, then 20g of tert-butyl alcohol is gradually added, the reaction is controlled at the temperature of 30 ℃ for 3 hours, the reaction system is divided into two phases, and the upper oil phase is taken and washed by anhydrous sodium carbonate to obtain the di-tert-butyl peroxide, wherein the yield is 98%.

Example 2

Mixing 20g of tert-butyl alcohol and 13.6g of hydrogen peroxide, feeding the mixture and 32g of concentrated sulfuric acid into a microchannel reactor at 60 ℃ according to a ratio of 1.

Comparative example 3

Gradually adding 5g of concentrated sulfuric acid into 10g of hydrogen peroxide (35%) at the temperature of 0 ℃, then adding 5g of tert-butyl alcohol, heating to 30 ℃ for reaction for 3 hours to obtain a phase-separated liquid, taking an upper oil phase, and washing with anhydrous sodium carbonate to obtain tert-butyl peroxide with the yield of 99%; then 0.5g of tert-butyl peroxy alcohol and 0.5g of alpha, alpha-dihydroxy-1, 4-diisopropylbenzene are mixed and dissolved in 10ml of tetrahydrofuran, 6g of concentrated sulfuric acid is gradually added at 0 ℃, after the addition is finished, the temperature is raised to 40 ℃ for reaction for 2h to obtain white turbid liquid, and after filtration, the di-tert-butylperoxyisopropylbenzene is obtained with the yield of 66%.

Example 3

Mixing tert-butyl peroxy alcohol and alpha, alpha-dihydroxy-1, 4-diisopropylbenzene according to the mass ratio of 1.

Comparative example 4

4.9g of concentrated sulfuric acid is slowly added into 11.4g of hydrogen peroxide (30%) at the temperature of 0 ℃, then 1.5g of butanone is added, the reaction is carried out for 3 hours at the temperature of 40 ℃, a phase separation system is obtained, an oil phase is taken and washed by anhydrous sodium carbonate, and 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is obtained, wherein the yield is 82%.

Example 4

Introducing a mixed solution of concentrated sulfuric acid and butanone (4.9 g of concentrated sulfuric acid/1.5 g of butanone) and 11.4g of hydrogen peroxide into a microchannel reactor at the temperature of 60 ℃ according to the proportion of 1 to 2, obtaining a phase separation system after 20min, separating by using a continuous phase oil-water separator, and taking an oil phase to obtain 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane with the yield of 94%.

Comparative example 5

Mixing 20g of tert-butyl alcohol and 13.6g of hydrogen peroxide, dripping 32g of concentrated sulfuric acid into the mixed solution at the temperature of 60 ℃ at the speed of 6ml/min, boiling the mixed solution after 3min, and exploding to obtain a reddish brown solution with coke-like substances.

Comparative example 6

Mixing 20g of tert-butyl alcohol and 13.6g of hydrogen peroxide, feeding the mixture and 16g of concentrated sulfuric acid into a microchannel reactor at 60 ℃ according to a ratio of 2.

Comparative example 7

20g of tert-butyl alcohol and 13.6g of hydrogen peroxide are mixed, and the mixture and 32g of concentrated sulfuric acid are fed into a microchannel reactor at 95 ℃ according to the proportion of 1.

In the invention, when the concentration of the used sulfuric acid is lower than 45 percent (namely the percentage of the sulfuric acid in the mixed solution is lower than 45 percent) or the reaction temperature exceeds 80 ℃, the target product cannot be obtained. For example, comparative examples 6 and 7, are the case when the sulfuric acid concentration is reduced outside the range and the temperature is increased outside the range, respectively, on the basis of example 2.

The method also has requirements on the reaction time (the microchannel reaction time is 10-60 min) and the proportion of the organic alcohol or the organic ketone to the hydrogen peroxide (the equivalent ratio is 1. Although deviations from the synthesis process do not occur outside the reaction times required according to the invention, their economics, i.e.the yield, and/or the time consumption, are affected. Similarly, the ratio of the hydrogen peroxide to the hydrogen peroxide does not cause qualitative difference of the target product, but has great influence on the reaction conversion rate and the economic efficiency.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims

1. The preparation method of the organic peroxide is characterized in that organic alcohol or organic ketone and hydrogen peroxide are subjected to synthetic reaction in a microchannel reactor under the catalysis of concentrated sulfuric acid to obtain the organic peroxide.

2. The process for producing an organic peroxide according to claim 1, wherein the reaction temperature is from 0 to 80 ℃; the reaction pressure was normal pressure.

3. The method of producing an organic peroxide according to claim 1, wherein the microchannel reaction time is 10 to 60min.

4. The method for producing an organic peroxide according to claim 1, wherein the equivalent ratio of the organic alcohol or the organic ketone to the hydrogen peroxide is 1:0.5-2.5.

5. The method according to claim 4, wherein the concentrated sulfuric acid is 45% or more of the mixed solution; the mixed solution consists of the organic alcohol or ketone, the hydrogen peroxide and the concentrated sulfuric acid.

6. The method for producing an organic peroxide according to claim 1, wherein the organic alcohol is one or more selected from the group consisting of 2, 5-dimethyl-2, 5-hexanediol, 1, 4-dihydroxy-diisopropylbenzene, tert-butanol, and derivatives thereof; the organic ketone is selected from one or more of butanone and homologs thereof.

7. The method for producing an organic peroxide according to claim 1, wherein the organic peroxide is 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane; the preparation method specifically comprises the following steps: dissolving 2, 5-dimethyl-2, 5-hexanediol in hydrogen peroxide, introducing the hydrogen peroxide and concentrated sulfuric acid into a microchannel reactor, separating out solids after reaction, dissolving the separated solids in tert-butyl alcohol, and reacting with the concentrated sulfuric acid to obtain the product.

8. The method for producing an organic peroxide according to claim 1, wherein the organic peroxide is di-tert-butyl peroxide hexane; the preparation method specifically comprises the following steps: and (2) introducing tert-butyl alcohol and hydrogen peroxide together with concentrated sulfuric acid into the microchannel reactor in proportion, and after reaction, carrying out phase separation on the system to obtain an oil phase which is the di-tert-butyl peroxide.

9. The method for producing an organic peroxide according to claim 1, wherein the organic peroxide is di-t-butylperoxycumene; the preparation method specifically comprises the following steps: and (2) introducing tertiary butyl alcohol and hydrogen peroxide together with concentrated sulfuric acid into a microchannel reactor according to a certain proportion, carrying out phase separation on a system after reaction to obtain an oil phase, namely tertiary butyl alcohol peroxide, mixing the oil phase with diperoxyisopropylbenzene, and introducing the mixture and the concentrated sulfuric acid into the microchannel reactor to obtain the di-tertiary butyl peroxyisopropylbenzene.

10. The method for producing an organic peroxide according to claim 1, wherein the organic peroxide is 3,6,9-triethyl-3,6,9-trimethyl-1, 4, 7-triperoxonane; the preparation method specifically comprises the following steps: butanone and hydrogen peroxide are proportionally introduced into a microchannel reactor together with concentrated sulfuric acid, and the system is subjected to phase splitting after the reaction, so that the obtained oil phase is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane.