CN116987019A - Method for preparing di (2-ethylhexyl) peroxydicarbonate - Google Patents
Method for preparing di (2-ethylhexyl) peroxydicarbonate Download PDFInfo
- Publication number
- CN116987019A CN116987019A CN202310891815.2A CN202310891815A CN116987019A CN 116987019 A CN116987019 A CN 116987019A CN 202310891815 A CN202310891815 A CN 202310891815A CN 116987019 A CN116987019 A CN 116987019A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ethylhexyl
- solution
- temperature
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 68
- RTGLJCSUKOLTEM-UHFFFAOYSA-N 2-ethylhexyl carbonochloridate Chemical compound CCCCC(CC)COC(Cl)=O RTGLJCSUKOLTEM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 27
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 230000002194 synthesizing effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
Abstract
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a method for preparing di (2-ethylhexyl) peroxydicarbonate. The preparation method comprises the steps of mixing potassium hydroxide solution and hydrogen peroxide, and reacting to obtain a reaction solution A; adding a phase transfer catalyst into the reaction solution A, mixing with a chloroformic acid-2-ethylhexyl ester solution, and reacting to obtain a reaction solution B; the reaction solution B was cooled and washed to obtain bis (2-ethylhexyl) peroxydicarbonate. The invention adopts the microchannel reactor to continuously produce the di (2-ethylhexyl) peroxydicarbonate, the reactants react in a plurality of temperature areas, the limit of the reaction temperature (less than 44 ℃) is broken through, the di (2-ethylhexyl) peroxydicarbonate can be synthesized at high temperature, the product yield is high, the purity is high, and the repeatability is good.
Description
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a method for preparing di (2-ethylhexyl) peroxydicarbonate.
Background
The di (2-ethylhexyl) peroxydicarbonate is also called an initiator EHP, and dioctyl peroxydicarbonate, which is called EHP for short, is easy to decompose into free radicals under the condition of heating or illumination, so that the di (2-ethylhexyl) peroxydicarbonate can be widely used as an initiator for free radical reaction, such as the production of polyethylene, PVC, polyvinyl acetate and the like. The EHP is adopted as an initiator for vinyl chloride polymerization, and has the advantages of high initiation rate, short polymerization time, low polymerization temperature, small usage amount, good product quality, low residual toxicity and the like; the theoretical active oxygen content is 4.62 percent, and the content is higher than that of other initiators; the traditional kettle type EHP production process is judged as peroxidation and needs to be modified into a full-flow automatic process.
In addition, the risk of EHP is mainly represented by the following: (1) The product EHP contains peroxy (-O-O-) and belongs to an energetic substance, and the energy required by the breaking is not large due to weak bonding force of the peroxy bond, and the product EHP is extremely sensitive to heat, vibration, impact or friction and the like and is extremely easy to decompose and even explode; (2) The peroxide is in contact with metal ions such as reducing agent, copper and the like, acid and alkali and the like to have explosion danger, and the combustion explosion can be caused when the peroxide encounters high temperature and open flame; (3) is a strongly exothermic reaction.
The current kettle type production flow mainly comprises: mixing distilled water and sodium hydroxide solid, cooling to 16 ℃ by adding frozen brine, adding hydrogen peroxide solution, and controlling the reaction temperature not to exceed 23 ℃; when the temperature is lower than 6 ℃, dropwise adding 2-ethylhexyl chloroformate, wherein the dropwise adding is completed within 1 hour, reacting at a low temperature and constant temperature until ripples appear on the surface of the stock solution and the surface of the liquid level is paved, and standing and water diversion are required after the reaction is completed. In the traditional production reaction process, the temperature and concentration distribution are not uniform, the mixing property is poor, the yield of the prepared BNP is only about 80%, and the purity is poor. In the process of adding raw materials, new decanoyl chloride is required to be added dropwise to control the reaction, the reaction is greatly affected by human factors and is greatly harmful to human bodies, and finally, the purity of the product stock solution is low and the repeatability is poor.
The microchannel reactor is a continuous flow tubular reactor with high safety performance, high raw material utilization rate and low emission of green environmental pollutants, and is generally a reaction device with a microstructure manufactured by a micromachining technology and a precision machining technology; the reactor mainly adopts special glass materials and silicon carbide materials, and the size of a channel for mixing reaction raw materials in the micro-channel reactor is very small, so that compared with the traditional tubular reactor, the mixing strength and the mass and heat transfer rate are higher by 100 times, and the micro-channel reactor has no amplification effect, and can rapidly finish industrial upgrading; the micro-channel reactor is widely applied to nitration reaction, oxidation reaction, photoreaction and diazotization reaction, and can rapidly remove reaction heat and improve safety.
Chinese patent application CN201910581095.3 discloses a synthesis method of di (2-ethylhexyl) peroxydicarbonate, and the patent uses a micro-channel reactor for synthesis, the reaction adopts sectional temperature control, the first stage micro-channel reactor has a temperature of 10-15 ℃ and a residence time of 1-1.5min, the second stage micro-channel reactor has a reaction temperature of 30-44 ℃ and a residence time of 2-5min, and the patent yield is about 98%. The patent adopts high-concentration raw material production, increases the cost of the raw material, adopts the micro-channel reactor, has the length of each mixed substrate of 1-5m, has overlarge volume of the whole reactor, increases the occupied area of equipment, has the reaction temperature of 10-44 ℃, can not well carry out mass transfer to improve the reaction rate, has overlong residence time and long mixed substrates, and leads to more decomposition of products.
From the prior art, the continuous EHP preparation process still has the problems of strictly controlling normal temperature reaction, long total reaction time and the like, and increases the industrialization difficulty. In view of this, the present invention provides a process for the continuous preparation of bis (2-ethylhexyl) peroxydicarbonate using a multi-temperature zone, multi-module microchannel reactor for high temperature reactions.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for preparing the di (2-ethylhexyl) peroxydicarbonate by using a micro-channel, which can realize the high-temperature preparation of the di (2-ethylhexyl) peroxydicarbonate by using a multi-temperature-zone and multi-module micro-channel reactor, and has the advantages of short reaction time and high product yield; the damage to human body is small, and the micro-channel module can be timely replaced for local leakage without affecting the whole production.
In order to achieve the above purpose of the present invention, the present invention adopts the following specific technical scheme:
the method for preparing the di (2-ethylhexyl) peroxydicarbonate comprises the following steps:
(1) Mixing potassium hydroxide solution and hydrogen peroxide, and reacting to obtain a reaction solution A;
(2) Adding a phase transfer catalyst into the reaction solution A, then mixing with a chloroformic acid-2-ethylhexyl ester solution, and reacting to obtain a reaction solution B;
(3) And cooling and washing the reaction liquid B to obtain the catalyst.
Preferably, the concentration of the potassium hydroxide solution in the step (1) is 15-25wt%, and the flow rate of the potassium hydroxide is 20-150g/min; the concentration of the hydrogen peroxide is 20-30wt%, preferably 27.5%, and the flow rate of the hydrogen peroxide is 8-60g/min; the molar ratio of the potassium hydroxide to the hydrogen peroxide is 1:1-1.5.
Preferably, in the step (1), the potassium hydroxide solution and hydrogen peroxide are mixed in a premixing zone of the microchannel reactor; the premixing zone is formed by connecting 1-3 micro-channel reactor modules; the temperature of the reaction is 5-20 ℃; the reaction time is 5-50s.
Further preferably, the premixing zone is composed of 2 microchannel reactor module connections; the reaction temperature is 10-20 ℃; the reaction time is 10-35s.
Preferably, in the step (2), the molar ratio of the 2-ethylhexyl chloroformate to the hydrogen peroxide is 1:0.7-1.5; the flow rate of the 2-ethylhexyl chloroformate is 15-90g/min.
Preferably, in step (2), the reaction solution a and the solution of 2-ethylhexyl chloroformate are mixed in the reaction zone of the microchannel reactor; the reaction zone is formed by connecting 3-8 micro-channel reactor modules; the reaction temperature is 30-80 ℃, and the reaction time is 30-180s.
Further preferably, the reaction zone is comprised of 8 microchannel reactor module connections; the reaction temperature is 50-70 ℃, and the reaction time is 30-100s.
Preferably, the phase transfer catalyst in step (2) is 15 crown 5 ether; the addition amount of the phase transfer catalyst is 1% -5% of the mass of the hydrogen peroxide.
Preferably, in step (3), the reaction liquid B is cooled in a cooling zone of the microchannel reactor; the cooling area is formed by connecting 1-2 micro-channel reactor modules; the cooling temperature is 10-30 ℃, and the cooling time is 2-50s.
Further preferably, the cooling temperature is 15-20 ℃ and the cooling time is 4-20s.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the microchannel reactor to continuously produce the di (2-ethylhexyl) peroxydicarbonate, the reactants react in a plurality of temperature areas, the limit of the reaction temperature (less than 44 ℃) is broken through, the di (2-ethylhexyl) peroxydicarbonate can be synthesized at high temperature, the product yield is high, the purity is high, and the repeatability is good;
2. the micro-channel reactor used in the invention has better mixing effect, can realize mixing in millisecond, has small liquid holdup of each module, low reaction risk and small occupied area of the reactor;
3. the experimental method adopted by the invention has the advantages of small raw material concentration, small reaction mole ratio, effective utilization of raw materials, high reaction temperature, better improvement of mass transfer rate, short residence time and high productivity;
4. compared with the kettle type reactor, the method has the advantages of no amplification effect, safe reaction, little harm to human body, and capability of replacing the leaked reactor without influencing the reaction if the reactor is leaked.
Drawings
FIG. 1 is a schematic of a microchannel reactor for bis (2-ethylhexyl) peroxydicarbonate according to the invention.
Detailed Description
The technical solutions of the embodiments of the present invention are further clearly described, and the described embodiments are only a part of the present invention, which are used to explain the present invention, but not to limit the present invention, so that other embodiments obtained by other persons skilled in the art without creative efforts fall within the protection scope of the present invention.
Sodium hydroxide, available from Nerngolian Erdos electric power metallurgy group Co., ltd; potassium hydroxide, available from the evolutionary industry materials, inc; hydrogen peroxide, purchased from the company of evolutionary industry materials, yinchuan, with purity of 27.5%; 2-ethylhexyl chloroformate, available from Tianjin, inc. of fine chemical industry, had a purity of 99.9%.
Example 1
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate comprises the following specific steps:
(1) Mixing a KOH solution with the concentration of 16 weight percent and hydrogen peroxide with the concentration of 27.5 weight percent in a premixing zone module of the micro-reaction device shown in figure 1, and carrying out salt forming reaction; the molar ratio of potassium hydroxide to hydrogen peroxide is 0.6:0.9, the flow rate of potassium hydroxide solution is 31.69g/min, and the flow rate of hydrogen peroxide is 16.79g/min; the reaction temperature in the premixing zone is 12 ℃ and the residence time is 20.30s, thus obtaining reaction liquid A.
(2) Adding 15 crown 5 ether into the reaction solution A (the addition amount of 15 crown 5 ether is 1% of the mass of hydrogen peroxide), uniformly mixing, and reacting with 99.9wt% of 2-ethylhexyl chloroformate in a reaction zone of a micro-reaction device, wherein the reaction zone is formed by connecting 8 micro-channel mixer modules; wherein the molar ratio of the 2-ethylhexyl chloroformate to KOH is 0.6:1, a step of; the flow rate of the 2-ethylhexyl chloroformate is 30.24g/min, the reaction temperature is 60 ℃, and the residence time is 50s, so as to obtain a reaction solution B.
(3) The reaction liquid B flows through a cooling zone of the micro-reaction device, wherein the cooling zone consists of 1 micro-channel mixer modules, the temperature of the cooling zone is 18 ℃, and the residence time is 10.15s. After the reaction is finished, the reaction solution is introduced into a separating tank for static layering, and the upper oil phase is taken to obtain the di (2-ethylhexyl) peroxydicarbonate for HPLC detection.
Example 2
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate comprises the following specific steps:
(1) Mixing a KOH solution with the concentration of 20wt% and hydrogen peroxide with the concentration of 27.5wt% in a premixing area of a micro-reaction device, wherein the molar ratio of potassium hydroxide to hydrogen peroxide is 0.5:0.7, the flow rate of the potassium hydroxide solution is 18.44g/min, and the flow rate of the hydrogen peroxide is 11.40g/min; the reaction temperature in the premixing zone was 10℃and the residence time was 32.98s, to obtain a reaction solution A.
(2) Adding 15 crown 5 ether into the reaction solution A (the addition amount of 15 crown 5 ether is 3% of the mass of hydrogen peroxide), uniformly mixing, and reacting with 99.8wt% of 2-ethylhexyl chloroformate in a reaction zone of a micro-reaction device, wherein the reaction zone is formed by connecting 8 micro-channel mixer modules; wherein the molar ratio of the 2-ethylhexyl chloroformate to KOH is 0.5:1; the flow rate of the aqueous solution of 2-ethylhexyl chloroformate was 26.39g/min. The reaction temperature was 50℃and the residence time was 70s, to give a reaction solution B.
(3) The reaction liquid B flows through a cooling zone of the micro-reaction device, wherein the cooling zone consists of 1 micro-channel mixer modules, the temperature of the cooling zone is 20 ℃, and the residence time is 16.49s. After the reaction is finished, the reaction solution is introduced into a separating tank for static layering, and the upper oil phase is taken to obtain the di (2-ethylhexyl) peroxydicarbonate for HPLC detection.
Example 3
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate comprises the following specific steps:
(1) Mixing a KOH solution with the concentration of 22wt% and hydrogen peroxide with the concentration of 27.5wt% in a premixing area of a micro-reaction device, wherein the molar ratio of potassium hydroxide to hydrogen peroxide is 1.14:1.16, the flow rate of the potassium hydroxide solution is 60.05g/min, and the flow rate of the hydrogen peroxide is 29.68g/min; the reaction temperature in the premixing zone was 13℃and the residence time was 10.97s, to obtain a reaction solution A.
(2) Adding 15 crown 5 ether into the reaction solution A (the addition amount of 15 crown 5 ether is 5% of the mass of hydrogen peroxide), uniformly mixing, and reacting with 99.8wt% of 2-ethylhexyl chloroformate in a reaction zone of a micro-reaction device, wherein the reaction zone is formed by connecting 8 micro-channel mixer modules; wherein the molar ratio of the 2-ethylhexyl chloroformate to KOH is 1.14:1; the flow rate of the aqueous solution of 2-ethylhexyl chloroformate is 41.47g/min, the reaction temperature is 70 ℃, and the residence time is 30s, so as to obtain a reaction solution B.
(3) The reaction liquid B flows through a cooling zone of the micro-reaction device, wherein the cooling zone consists of 1 micro-channel mixer modules, the temperature of the cooling zone is 15 ℃, and the residence time is 5.48s. After the reaction is finished, the reaction solution is introduced into a separating tank for static layering, and the upper oil phase is taken to obtain the di (2-ethylhexyl) peroxydicarbonate for HPLC detection.
Example 4
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate comprises the following specific steps:
(1) Mixing a KOH solution with the concentration of 25wt% and hydrogen peroxide with the concentration of 27.5wt% in a premixing zone of a micro-reaction device, wherein the molar ratio of potassium hydroxide to hydrogen peroxide is 1.3:1.5, the flow rate of the potassium hydroxide solution is 21.30g/min, and the flow rate of the hydrogen peroxide is 8.68g/min; the reaction temperature in the premixing zone was 12℃and the residence time was 11.86s, to obtain reaction solution A.
(2) Adding 15 crown 5 ether into the reaction solution A (the addition amount of 15 crown 5 ether is 5% of the mass of hydrogen peroxide), uniformly mixing, and then carrying out the reaction with 99wt% of 2-ethylhexyl chloroformate aqueous solution in a reaction zone of a micro-reaction device, wherein the molar ratio of the 2-ethylhexyl chloroformate to KOH is 1.3:1; the flow rate of the aqueous solution of the 2-ethylhexyl chloroformate is 9.20g/min, and the reaction zone is formed by connecting 8 micro-channel mixer modules; the reaction temperature was 65℃and the residence time was 100s, to give a reaction solution B.
(3) The reaction liquid B flows through a cooling zone of the micro-reaction device, wherein the cooling zone consists of 1 micro-channel mixer modules, the temperature of the cooling zone is 18 ℃, and the residence time is 5.93s. After the reaction is finished, the reaction solution is introduced into a separating tank for static layering, and the upper oil phase is taken to obtain the di (2-ethylhexyl) peroxydicarbonate for HPLC detection.
Example 5
The procedure of example 1 was repeated and the reproducibility of the method was examined.
Comparative example 1
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate, which is the same as that of example 1, except that: the catalyst added in the step (2) is tetra-n-butyl ammonium hydroxide.
Comparative example 2
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate, which is the same as that of example 1, except that: the feeding ratio is different, and the mole ratio of the reaction is potassium hydroxide: hydrogen peroxide: 2-ethylhexyl chloroformate=1.4:1.1:1.
Comparative example 3
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate, which is the same as that of example 1, except that: the concentration of the potassium hydroxide solution was varied to 30wt%.
Comparative example 4
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate, which is the same as that of example 1, except that: the reaction temperature of the reaction zone was 90℃and the temperatures of the corresponding pre-mixing zone and cooling zone were set to 5℃and 10℃respectively.
Comparative example 5
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate, which is the same as that of example 1, except that: the residence times are different; the residence time in the reaction zone was 120s.
Comparative example 6
A method for synthesizing di (2-ethylhexyl) peroxydicarbonate, which is the same as that of example 1, except that: KOH replaces NaOH as the alkaline material.
Comparative example 7
A synthesis method of di (2-ethylhexyl) peroxydicarbonate adopts a traditional kettle reactor for reaction, wherein the molar ratio of the reaction is potassium hydroxide: hydrogen peroxide: 2-ethylhexyl chloroformate=0.6:0.9:1, the reaction mass was added to a kettle reactor and reacted at 20℃for 195min, after which foam ripples were applied to the surface of the liquid surface, the reaction was completed, and the treatment method was the same as in example 1.
The test results of examples 1 to 5 and comparative examples 1 to 7 are shown in Table 1.
Table 1 test results
The results show that the concentration, the feeding ratio, the reaction temperature and the residence time of the alkaline solution have influence on the purity and the yield of the product, and especially the addition of the phase transfer catalyst 15 crown 5 accelerates the migration speed of sodium salt in the oil phase, thereby effectively improving the experimental yield and the purity; compared with the traditional kettle type production, the micro-channel production product has the advantages of high purity of 98.87%, high yield of 99.79%, fast mass transfer, quick removal of reaction heat, seamless amplification and the like, so that the invention can break through the limitation brought by low-temperature reaction under the experimental condition, obtain the high-purity and high-yield bis (2-ethylhexyl) peroxydicarbonate in the optimal feeding ratio and shorter residence time, and realize the intrinsically safe and green low-carbon production.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (10)
1. A process for the preparation of di (2-ethylhexyl) peroxydicarbonate comprising the steps of:
(1) Mixing potassium hydroxide solution and hydrogen peroxide, and reacting to obtain a reaction solution A;
(2) Adding a phase transfer catalyst into the reaction solution A, then mixing with a chloroformic acid-2-ethylhexyl ester solution, and reacting to obtain a reaction solution B;
(3) And cooling and washing the reaction liquid B to obtain the catalyst.
2. The method according to claim 1, wherein the concentration of the potassium hydroxide solution in the step (1) is 15 to 25wt%, and the flow rate of the potassium hydroxide solution is 20 to 150g/min; the concentration of the hydrogen peroxide is 20-30wt%, and the flow rate of the hydrogen peroxide is 8-60g/min; the molar ratio of the potassium hydroxide to the hydrogen peroxide is 1:1-1.5.
3. The method of claim 1, wherein the potassium hydroxide solution and hydrogen peroxide solution in step (1) are mixed in a premixing zone of a microchannel reactor; the premixing zone is formed by connecting 1-3 micro-channel reactor modules; the temperature of the reaction is 5-20 ℃; the reaction time is 5-50s.
4. A method according to claim 3, wherein the premixing zone consists of 2 microchannel reactor module connections; the reaction temperature is 10-20 ℃; the reaction time is 10-35s.
5. The method according to claim 1, wherein the molar ratio of 2-ethylhexyl chloroformate to hydrogen peroxide in step (2) is 1:0.7-1.5; the flow rate of the 2-ethylhexyl chloroformate is 15-90g/min.
6. The process of claim 1, wherein in step (2) the reaction solution a and 2-ethylhexyl chloroformate solution are mixed in the reaction zone of the microchannel reactor; the reaction zone is formed by connecting 3-8 micro-channel reactor modules; the reaction temperature is 30-80 ℃, and the reaction time is 30-180s.
7. The method of claim 6, wherein the reaction zone is comprised of 8 microchannel reactor module connections; the reaction temperature is 50-70 ℃, and the reaction time is 30-100s.
8. The process of any one of claims 1-7, wherein the phase transfer catalyst in step (2) is 15 crown 5 ether; the addition amount of the phase transfer catalyst is 1% -5% of the mass of the hydrogen peroxide.
9. The process according to claim 1, wherein in step (3) the reaction liquid B is cooled in a cooling zone of a microchannel reactor; the cooling area is formed by connecting 1-2 micro-channel reactor modules; the cooling temperature is 10-30 ℃, and the cooling time is 2-50s.
10. The method of claim 9, wherein the cooling is at a temperature of 15-20 ℃ for a time of 4-20s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310891815.2A CN116987019A (en) | 2023-07-19 | 2023-07-19 | Method for preparing di (2-ethylhexyl) peroxydicarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310891815.2A CN116987019A (en) | 2023-07-19 | 2023-07-19 | Method for preparing di (2-ethylhexyl) peroxydicarbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116987019A true CN116987019A (en) | 2023-11-03 |
Family
ID=88529365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310891815.2A Pending CN116987019A (en) | 2023-07-19 | 2023-07-19 | Method for preparing di (2-ethylhexyl) peroxydicarbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116987019A (en) |
-
2023
- 2023-07-19 CN CN202310891815.2A patent/CN116987019A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1338239C (en) | Process for the preparation of internal olefin sulphonates | |
| CN105330549A (en) | Method for preparing isooctyl nitrate in micro-channel reactor | |
| CN106243344B (en) | A kind of continuous open loop production technology of epoxy radicals end-blocking polyethers | |
| CN111217712B (en) | Method for preparing o-phenylenediamine from aniline | |
| CN104529794B (en) | The preparation method of Boscalid intermediate 2-(4-chlorphenyl) aniline | |
| CN113292470A (en) | Continuous flow synthesis process of peroxy-2-ethylhexyl tert-butyl carbonate without amplification effect | |
| US9249088B2 (en) | Continuous production and reaction of a diazo compound | |
| CN108752175B (en) | Continuous preparation method of benzil or derivatives thereof | |
| CN116987019A (en) | Method for preparing di (2-ethylhexyl) peroxydicarbonate | |
| CN106588734B (en) | A kind of cumene oxidation prepares the method and device of cumyl hydroperoxide | |
| CN111039829A (en) | Method for producing p-acetamido benzene sulfonyl chloride by two-temperature zone two-stage method based on continuous flow reaction | |
| RU2443717C2 (en) | Method for free-radical polymerisation or cross-linking in presence of selected organic peroxide obtained ex situ | |
| CN113214120B (en) | Preparation method of perfluorohexyl ethyl sulfonate | |
| EP0482573B1 (en) | Process for producing polyhydroperoxy aromatic compound | |
| CN110256320B (en) | Synthesis method of peroxydicarbonate di (2-ethylhexyl) ester | |
| CN115385838B (en) | Preparation method of cumyl peroxyneodecanoate | |
| CN106831362A (en) | The production method of 2 propoxyl group chloroethanes | |
| CN113248355B (en) | Preparation method of p-chlorobenzaldehyde | |
| CN112661648A (en) | Process method for co-producing sulfur magnesium fertilizer by isooctyl nitrate | |
| KR960000015B1 (en) | Enhanced gas-liquid reactions | |
| CN110204472B (en) | Synthesis method of di-tert-butyl peroxide | |
| CN112898209B (en) | Method for synthesizing 5-nitro-2- (propylthio) pyrimidine-4, 6-diol by continuous nitration | |
| CN116478075A (en) | Method for preparing tert-butyl peroxyneodecanoate by micro-channels | |
| CN117924136A (en) | Continuous synthesis method of methyl ethyl ketone peroxide | |
| CN115043960B (en) | Emulsion peroxide initiator and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |