CN112679403B - Method for preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide - Google Patents
Method for preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide Download PDFInfo
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Abstract
The invention relates to the field of organic synthesis, and discloses a method for preparing meta-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide, which comprises the steps of firstly contacting a material containing meta-bis- (2-hydroxyisopropyl) benzene and para-bis- (2-hydroxyisopropyl) benzene with hydrogen peroxide for reaction to obtain a reaction mixture containing the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide; and then carrying out solid-liquid separation on the reaction mixture to obtain a liquid phase containing m-diisopropylbenzene hydroperoxide and a solid phase containing p-diisopropylbenzene hydroperoxide. The purity of the meta-diisopropylbenzene hydroperoxide prepared by the method is more than 95%, the yield is more than 82%, the purity of the para-diisopropylbenzene hydroperoxide is more than 97%, the yield is more than 86%, the waste acid generation amount is small, the method is clean and environment-friendly, the reaction condition is mild, the reaction is easy to control, and the method is suitable for industrialization.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a method for preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide.
Background
Meta-diisopropylbenzene hydroperoxide (m-DHP) and para-diisopropylbenzene hydroperoxide (p-DHP) are important fine organic intermediates and are widely used for the synthesis production of resorcinol and hydroquinone. The meta-DHP and the para-DHP can be used as a polymerization initiator, an initiator for diisopropylbenzene air (oxygen) oxidation reaction, and an epoxidizing agent for synthesizing propylene oxide or butylene oxide. The activity of the hydroperoxy group is utilized, and the hydroperoxy group can also be used as a raw material for synthesizing other organic peroxides.
The traditional production process of meta-position and para-position diisopropylbenzene hydroperoxide is prepared by an oxidation synthesis process of a pure meta-position diisopropylbenzene raw material or a pure para-position diisopropylbenzene raw material.
The pure meta-position and para-position diisopropylbenzene raw materials are prepared by separating a mixture of meta-position diisopropylbenzene and para-position diisopropylbenzene. And (2) carrying out oxidation reaction on the pure meta-position or para-position diisopropylbenzene obtained after separation at a certain temperature and pressure to firstly generate diisopropylbenzene hydroperoxide MHP, continuously oxidizing the MHP to obtain diisopropylbenzene hydroperoxide DHP to prepare diisopropylbenzene oxidation liquid, wherein the MHP content in the oxidation liquid is generally more than 50%, the DHP content is only about 10%, preparing a MIBK solution containing a small amount of DHP by alkali liquor extraction and MIBK back extraction, and then carrying out secondary oxidation by hydrogen peroxide to obtain DHP.
However, m-diisopropylbenzene and p-diisopropylbenzene are isomers, m-diisopropylbenzene has a boiling point of 203 ℃, p-diisopropylbenzene has a boiling point of 210.3 ℃, the difference of boiling points is very small, relative volatility is small, a conventional rectification method needs 150 trays, separation difficulty is very high, operation time is long, energy consumption in the rectification process is high, a product is easy to generate a thermosensitive reaction, and separation efficiency is low. CN104672042A discloses a separation method of m-p mixed diisopropylbenzene, which needs to be separated by an extractive distillation and ordinary distillation two-stage distillation method, not only adopts a large amount of extractant, but also has high energy and material consumption.
CN101544586A discloses a method for preparing mixed DHP by using m-p mixed diisopropylbenzene as a raw material. In the presence of an initiator, under a certain temperature and pressure, mixing diisopropylbenzene, carrying out oxidation reaction by using air, introducing an oxidation solution containing DHP (and a small amount of HHP), MHP and DIPB obtained through the oxidation reaction into a 15-20% sodium hydroxide solution for extraction, dissolving DHP in the oxidation solution in an alkali liquor, carrying out oil-water two-phase separation on the extracted mixture, circulating an oil phase back to an oxidation system, neutralizing the water phase by using dilute sulfuric acid and the like until the pH value is 6-7, layering, and collecting an upper oil layer to obtain the DHP. Because of the use of mixed diisopropylbenzenes, the resulting DHP is also a mixture of meta and para isomers, but the invention does not relate to the separation of meta and para DHP.
US5032688A discloses a process for the preparation of para-DHP by oxidation of 1, 4-bis (2-hydroxy-2-propyl) benzene (para-DC) with hydrogen peroxide. The patent adopts 72 wt% sulfuric acid as catalyst and ammonium sulfate as acid-binding agent, and excess hydrogen peroxide with 15-25% of hydrogen peroxide content reacts with para-position DC at 25-50 ℃ to prepare para-position DHP. The process has the following disadvantages: 1. the reaction conversion rate and yield are not high, and the method is not suitable for the oxidation reaction of meta-position and para-position mixed DC; 2. the use amount of the sulfuric acid is large, so that the corrosion to equipment is serious, and the method is not suitable for industrial production; 3. a large amount of acid-containing wastewater is generated, which is not beneficial to environmental protection; 4. in addition, excessive hydrogen peroxide can also react with generated hydroquinone to generate a colored by-product which is difficult to separate. The preparation method is also not suitable for a reaction system of a mixture of meta-position DC and para-position DC, because the meta-position DC and the para-position DC are insoluble in water, and the meta-position DC and the meta-position HHP are difficult to be oxidized, and the final reaction product is a mixture containing the meta-position DHP, the para-position DHP and the meta-position HHP.
Disclosure of Invention
The invention aims to solve the problems that m-diisopropylbenzene hydroperoxide (m-DHP) and p-diisopropylbenzene hydroperoxide (p-DHP) prepared from a mixture of m-bis- (2-hydroxyisopropyl) benzene (m-DC) and p-bis- (2-hydroxyisopropyl) benzene (p-DC) are not easy to separate, a large amount of acid solvent is used in the reaction to corrode equipment, and the yield of reaction products is low in the prior art, and provides a method for preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide to achieve the purposes of respectively preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide from the mixture of m-bis- (2-hydroxyisopropyl) benzene and p-bis- (2-hydroxyisopropyl) benzene, and obtaining high yield and purity.
In order to achieve the above object, the present invention provides a method for preparing meta-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide, wherein the method comprises the steps of:
(1) In the presence of a catalyst and a solvent, contacting a material containing meta-position bis- (2-hydroxy isopropyl) benzene and para-position bis- (2-hydroxy isopropyl) benzene with hydrogen peroxide for reaction to obtain a reaction mixture containing meta-position diisopropylbenzene hydroperoxide and para-position diisopropylbenzene hydroperoxide, wherein the solvent is aromatic hydrocarbon with carbon atom number not more than 9;
(2) And (3) concentrating the reaction mixture, and then carrying out solid-liquid separation to obtain a liquid phase containing the m-diisopropylbenzene hydroperoxide and a solid phase containing the p-diisopropylbenzene hydroperoxide.
The process of the invention can be illustrated by the following reaction scheme:
the inventor of the invention skillfully utilizes that the oxidation product of meta-di- (2-hydroxyisopropyl) benzene, namely meta-diisopropylbenzene hydroperoxide, and the oxidation product of para-di- (2-hydroxyisopropyl) benzene, namely para-diisopropylbenzene hydroperoxide, have larger solubility difference in certain specific solvents, so that the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide respectively exist in liquid phase and solid phase forms, and the separation of the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide is easily realized, and through further purification, the purity of the obtained meta-diisopropylbenzene hydroperoxide is more than 95 percent, the yield is more than 82 percent, the purity of the para-diisopropylbenzene hydroperoxide is more than 97 percent, and the yield is more than 86 percent.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing meta-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide, wherein the method comprises the following steps:
(1) In the presence of a catalyst and a solvent, contacting a material containing meta-position bis- (2-hydroxy isopropyl) benzene and para-position bis- (2-hydroxy isopropyl) benzene with hydrogen peroxide for reaction to obtain a reaction mixture containing meta-position diisopropylbenzene hydroperoxide and para-position diisopropylbenzene hydroperoxide, wherein the solvent is aromatic hydrocarbon with carbon atom number not more than 9;
(2) And (3) concentrating the reaction mixture or carrying out solid-liquid separation without concentration to obtain a liquid phase containing the m-diisopropylbenzene hydroperoxide and a solid phase containing the p-diisopropylbenzene hydroperoxide.
The inventor of the invention skillfully utilizes that the oxidation products of meta-di- (2-hydroxyisopropyl) benzene, namely meta-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide, have larger solubility difference in certain specific solvents and respectively exist in the form of liquid phase and solid phase, so that the separation of the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide is easily realized, the thinking of adopting a distillation method with high energy consumption and poor separation efficiency in the prior art is broken through, and the meta-di- (2-hydroxyisopropyl) benzene and the para-di- (2-hydroxyisopropyl) benzene containing raw materials are respectively used for preparing the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide with higher purity and respectively obtain higher yield.
According to the invention, the type and amount of the solvent are required to satisfy the following three conditions: 1) P-m-bis- (2-hydroxyisopropyl) benzene, p-bis- (2-hydroxyisopropyl) benzene and hydrogen peroxide have sufficient solubility to ensure the oxidation reaction; 2) No adverse effect is caused to the oxidation reaction; 3) The solubility difference between the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide is large. The aromatic hydrocarbon solvent having 9 or less carbon atoms satisfying such a condition may be selected from at least one of benzene, toluene, xylene, ethylbenzene and cumene, for example, and it is further preferable that the solvent is selected from toluene for the convenience of subsequent removal.
According to the present invention, the solvent is used in an amount of preferably 2 to 20mL, more preferably 5 to 15mL, relative to 1 g of the total amount of m-bis- (2-hydroxyisopropyl) benzene and p-bis- (2-hydroxyisopropyl) benzene.
According to the present invention, the total content of the para-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene in the material is not particularly limited, but in order to improve the separation effect, it is preferable that the total content of the para-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene in the material is not less than 98% by weight.
According to the present invention, the weight ratio of the para-bis- (2-hydroxyisopropyl) benzene to the para-bis- (2-hydroxyisopropyl) benzene in the feed is not particularly limited, but in order to enhance the effect of separation, it is preferable that the weight ratio of the para-bis- (2-hydroxyisopropyl) benzene to the para-bis- (2-hydroxyisopropyl) benzene in the feed is 1 to 4.
According to the present invention, there is no particular limitation on the ratio of the total amount of the meta-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene to the amount of the hydrogen peroxide, and it is sufficient to completely oxidize the para-bis- (2-hydroxyisopropyl) benzene and the meta-bis- (2-hydroxyisopropyl) benzene to facilitate the subsequent separation, but in order to improve the purity and yield of the meta-diisopropylbenzene hydroperoxide and the para-diisopropylbenzene hydroperoxide and to reduce the residual amount of the hydrogen peroxide in the reaction mixture, it is preferable that the molar ratio of the total amount of the meta-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene to the amount of the hydrogen peroxide is 1:3-10, more preferably, the molar ratio of the total amount of the meta-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene to the amount of the hydrogen peroxide is 1:4-6.
According to the present invention, the use mode of the hydrogen peroxide is not particularly limited, and may be a conventional use mode in the art, such as mixing hydrogen peroxide with water to form hydrogen peroxide solution, and then contacting the hydrogen peroxide solution with the material, wherein the hydrogen peroxide content in the hydrogen peroxide solution is preferably 30-70 wt%.
According to the present invention, there is no particular limitation on the ratio of the total amount of the meta-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene to the amount of the catalyst used, and preferably, the weight ratio of the total amount of the meta-bis- (2-hydroxyisopropyl) benzene and the para-bis- (2-hydroxyisopropyl) benzene to the amount of the catalyst used is 1:0.01-0.1.
According to the present invention, the kind of the catalyst is not particularly limited, and in order to improve the catalytic effect, the catalyst is preferably an acidic catalyst, and more preferably, the acidic catalyst is one or more of sulfuric acid, p-toluenesulfonic acid, perchloric acid, phosphoric acid, and hydrochloric acid.
According to the present invention, in order to improve the yield and purity of meta-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide, preferably, the reaction conditions in step (1) include: the temperature is 35-85 ℃, preferably 40-60 ℃; the pressure is 0.005-0.06MPa, preferably 0.015-0.03MPa; the time is 1 to 6 hours, preferably 2 to 5 hours. The pressure in the present invention is absolute pressure.
According to the present invention, in order to increase the content of para-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide in the reaction mixture, it is preferable that the method further comprises removing water generated by the reaction in time during the reaction of step (1).
According to the invention, the method can also comprise returning the distilled solvent to the reaction system for recycling in the reaction process of the step (1).
According to the invention, in the reaction in the step (1), the meta-bis- (2-hydroxyisopropyl) benzene is firstly oxidized into 3- (2-hydroxy-2-propyl) cumene hydroperoxide (m-HHP), then the 3- (2-hydroxy-2-propyl) cumene hydroperoxide is continuously oxidized into the meta-diisopropylbenzene hydroperoxide, the para-bis- (2-hydroxyisopropyl) benzene is firstly oxidized into 4- (2-hydroxy-2-propyl) cumene hydroperoxide (p-HHP), then the 4- (2-hydroxy-2-propyl) cumene hydroperoxide is continuously oxidized into the para-diisopropylbenzene hydroperoxide, and preferably, the reaction in the step (1) is carried out until the content of the 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the reaction mixture is less than or equal to 0.5 wt%; more preferably, the reaction in step (1) is carried out until the content of 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the reaction mixture is 0.1% by weight or less.
According to the present invention, the method for detecting the content of 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the reaction mixture is not particularly limited, and may be a detection method conventionally used in the art, such as gas chromatography or high performance liquid chromatography.
According to a preferred embodiment of the present invention, the method further comprises cooling the reaction mixture before solid-liquid separation, preferably, cooling the reaction mixture to 0 to 20 ℃ before solid-liquid separation; more preferably, the reaction mixture is cooled to 5-10 ℃ before solid-liquid separation.
According to the present invention, the solid-liquid separation method is not particularly limited, and may be a solid-liquid separation method conventionally used in the art, such as suction filtration or centrifugation.
According to the present invention, in order to improve the purity and yield of the obtained p-diisopropylbenzene hydroperoxide, the method may further comprise washing the solid phase containing p-diisopropylbenzene hydroperoxide to obtain a p-diisopropylbenzene hydroperoxide solid.
According to the present invention, the washing of the solid phase containing p-diisopropylbenzene hydroperoxide comprises washing the solid phase containing p-diisopropylbenzene hydroperoxide with a washing agent and water in this order, the source and amount of the washing agent are not particularly limited, and in order to avoid loss of p-diisopropylbenzene hydroperoxide, the washing agent may be one or more selected from toluene, ethylbenzene, cumene, and xylene, and is more preferably selected from toluene.
According to the present invention, in order to improve the purity and yield of the obtained m-diisopropylbenzene hydroperoxide, the method may further comprise the steps of: (1) Removing hydrogen peroxide in the liquid phase to obtain purified liquid containing meta-diisopropylbenzene hydroperoxide; (2) Removing the solvent in the purified solution to obtain a concentrated solution containing meta-diisopropylbenzene hydroperoxide; (3) Crystallizing the meta-diisopropylbenzene hydroperoxide in the concentrated solution.
According to the invention, the method for removing hydrogen peroxide in the liquid phase in the step (1) comprises the steps of separating the water phase in the liquid phase to obtain an oil phase containing m-diisopropylbenzene hydroperoxide, and then washing the oil phase with water until the washing liquid is neutral. Wherein the water is distilled water or deionized water. As will be understood by those skilled in the art, the oil phase refers to the organic matter after removal of the aqueous phase from the liquid phase.
According to the present invention, in order to improve the purity and yield of m-diisopropylbenzene hydroperoxide, it is preferable that the solvent in the purified solution is removed in step (2) by distilling off the solvent under reduced pressure at 40-60 ℃.
According to the present invention, there is no particular limitation on the crystallization mode, and it may be a crystallization mode conventionally used in the art, and in order to improve the purity and yield of m-diisopropylbenzene hydroperoxide, it is preferable to mix an organic solvent with the concentrated solution to crystallize m-diisopropylbenzene hydroperoxide, and it is more preferable that the organic solvent is selected from one or more of alkanes having 5 to 8 carbon atoms, cycloalkanes having 5 to 8 carbon atoms, and aromatics having 6 to 9 carbon atoms, and it is further preferable that the organic solvent is selected from one or more of pentane, cyclopentane, hexane, cyclohexane, petroleum ether, heptane, n-hexane, benzene, toluene, and it is further preferable that the organic solvent is selected from benzene and n-hexane.
The present invention will be described in detail below by way of examples. In the following examples of the present invention, the following examples,
gas chromatography: the model is Agilent 7890B; a cold Column head injector, model Agilent G3454A 0-100PSI EPC Cool On-Column Capillary, was used.
Example 1
1) 100 ml of toluene, 10 g of a feedstock containing 98% by weight of m-DC and p-DC (weight ratio of the two: 2.5: 1) 17.5 g of 50 wt% hydrogen peroxide and 0.25 g of sulfuric acid (the concentration is 98 wt%) are mixed, stirring is started, the reaction is carried out at 50 ℃ and 0.02MPa, water generated by the reaction is removed in time in the reaction process, simultaneously, the distilled toluene is returned to the reaction system for recycling, the reaction is carried out for 3 hours, the content of m-HHP in the reaction liquid is measured to be 0.09 wt% by gas chromatography, the stirring is stopped, the reaction liquid is cooled to 7 ℃ for suction filtration, the obtained filter cake is washed by a small amount of toluene and distilled water at 7 ℃, the filter cake is dried after being washed, the p-DHP product is obtained, the yield is 96%, and the purity is 99.0%.
2) Removing the water phase from the obtained filtrate to obtain an oil phase, and washing the oil phase with a small amount of distilled water until the washing liquid becomes neutral to obtain a toluene solution containing m-DHP; carrying out reduced pressure distillation on a toluene solution containing m-DHP at 50 ℃ to remove toluene, thus obtaining a concentrated solution; adding 35mL of a mixture of benzene and n-hexane into the concentrated solution for crystallization, then carrying out suction filtration to obtain crystals, and drying the obtained crystals to obtain an m-DHP product, wherein the yield is 89% and the purity is 97.1%.
Example 2
1) 150 ml of toluene, 10 g of a feedstock containing 98% by weight of m-DC and p-DC (weight ratio of the two: 2: 1) 35 g of 30 wt% hydrogen peroxide and 1.15 g of phosphoric acid (the concentration is 85 wt%) are mixed, stirring is started, reaction is carried out at 40 ℃ and 0.015MPa, water generated in the reaction is removed in time in the reaction process, simultaneously, evaporated toluene is returned to a reaction system for recycling, the reaction is carried out for 5 hours, the content of m-HHP in the reaction liquid is measured to be 0.09 wt% by gas chromatography, the reaction liquid is cooled to 10 ℃ for suction filtration, the obtained filter cake is washed by a small amount of toluene and distilled water at 10 ℃, and the filter cake is dried after being washed, so that the p-DHP product is obtained, the yield is 93.1%, and the purity is 98.6%.
2) Removing the water phase from the obtained filtrate to obtain an oil phase, and washing the oil phase with a small amount of distilled water until the washing liquid becomes neutral to obtain a toluene solution containing m-DHP; carrying out reduced pressure distillation on a toluene solution containing m-DHP at 50 ℃ to remove toluene, thus obtaining a concentrated solution; adding 30mL of a mixture of benzene and n-hexane into the concentrated solution for crystallization, then carrying out suction filtration to obtain crystals, and drying the obtained crystals to obtain an m-DHP product, wherein the yield is 88.5% and the purity is 96.4%.
Example 3
1) 50 ml of toluene, 10 g of a feedstock containing 98% by weight of m-DC and p-DC (weight ratio of the two: 3: 1) 10 g of 70 wt% hydrogen peroxide and 0.14 g of perchlorate (the concentration is 70 wt%) are mixed, stirring is started, reaction is carried out at 60 ℃ and 0.03MPa, water generated by the reaction is removed in time in the reaction process, simultaneously steamed toluene is returned to the reaction system for recycling, the reaction is carried out for 3.5 hours, the content of m-HHP in the reaction liquid is measured by chromatography and is 0.1 wt%, the reaction liquid is cooled to 5 ℃ for suction filtration, the obtained filter cake is washed by a small amount of toluene and distilled water at 5 ℃, and the filter cake is dried after being washed, so that the p-DHP product is obtained, the yield is 92.3%, and the purity is 98.0%.
2) Removing the water phase from the obtained filtrate to obtain an oil phase, and washing the oil phase with a small amount of distilled water until the washing liquid becomes neutral to obtain a toluene solution containing m-DHP; carrying out reduced pressure distillation on a toluene solution containing m-DHP at 50 ℃ to remove toluene, thus obtaining a concentrated solution; and adding 40mL of a mixture of benzene and n-hexane into the concentrated solution for crystallization, then carrying out suction filtration to obtain crystals, and drying the obtained crystals to obtain the m-DHP product, wherein the yield is 86.0% and the purity is 96.0%.
Example 4
10 g of a starting material containing 98% by weight of m-DC and p-DC (2.5% by weight of both: 1) were treated in the same manner as in example 1 except that the reaction temperature in step 1) was 85 ℃ to give a yield of m-DHP of 82.3% and a purity of 95.2% and a yield of p-DHP of 86% and a purity of 97%.
Example 5
10 g of a starting material containing 98% by weight of m-DC and p-DC (2.5 in terms of weight ratio: 1) were treated in the same manner as in example 1 except that the reaction pressure in step 1) was 0.06MPa, resulting in a yield of m-DHP of 83%, a purity of 95.3%, a yield of p-DHP of 88% and a purity of 97.8%.
Example 6
When 10 g of a starting material containing 98% by weight of m-DC and p-DC (2.5% by weight of both: 1) was treated in accordance with the method of example 1 and the mixture of benzene and n-hexane in step 2) was replaced with an equal amount of n-hexane, the yield of m-DHP was 83%, the purity was 95%, the yield of p-DHP was 96%, and the purity was 99%.
Comparative example 1
10 g of a starting material containing 98% by weight of m-DC and p-DC (2.5% by weight of both.
As can be seen from the results of the above experiments, the method of the present invention produces m-DHP and p-DHP from m-DC and p-DC-containing raw materials, respectively, and has excellent effects, i.e., the yield of m-DHP is 82% or more, the purity is 95% or more, the yield of p-DHP is 86% or more, and the purity is 97% or more.
As can be seen from the results of example 1 and examples 4-5, m-DHP and p-DHP prepared using the preferred embodiment of the present invention are higher in purity and yield.
As can be seen from the results of example 1 and example 6, the yield and purity of m-DHP obtained in example 1 using a mixture of benzene and n-hexane are higher.
As can be seen from the results of example 1 and comparative example 1, the yield and purity of m-DHP and p-DHP obtained using the solvent of the present invention are significantly higher.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. A process for preparing meta-diisopropylbenzene hydroperoxide and para-diisopropylbenzene hydroperoxide, comprising the steps of:
(1) Contacting a material containing m-di- (2-hydroxyisopropyl) benzene and p-di- (2-hydroxyisopropyl) benzene with hydrogen peroxide in the presence of a catalyst and a solvent to react to obtain a reaction mixture containing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide, wherein the solvent is at least one selected from benzene, toluene, xylene, ethylbenzene and cumene;
(2) And (3) concentrating the reaction mixture, and then carrying out solid-liquid separation to obtain a liquid phase containing the m-diisopropylbenzene hydroperoxide and a solid phase containing the p-diisopropylbenzene hydroperoxide.
2. The method of claim 1, wherein the total content of meso-bis- (2-hydroxyisopropyl) benzene and para-bis- (2-hydroxyisopropyl) benzene in the feed is greater than or equal to 98 wt%.
3. A process according to claim 1 or 2, wherein the weight ratio of meso-bis- (2-hydroxyisopropyl) benzene to para-bis- (2-hydroxyisopropyl) benzene in the feed is 1-4.
4. The process according to claim 1 or 2, wherein the solvent is used in an amount of 2 to 20mL relative to 1 g of the total amount of m-bis- (2-hydroxyisopropyl) benzene and p-bis- (2-hydroxyisopropyl) benzene.
5. The process according to claim 1 or 2, wherein the solvent is used in an amount of 5 to 15mL relative to 1 g of the total amount of m-bis- (2-hydroxyisopropyl) benzene and p-bis- (2-hydroxyisopropyl) benzene.
6. The process according to claim 1 or 2, wherein the molar ratio of the total amount of meta-bis- (2-hydroxyisopropyl) benzene and para-bis- (2-hydroxyisopropyl) benzene used to the amount of hydrogen peroxide used is 1:3-10.
7. The process according to claim 1 or 2, wherein the molar ratio of the total amount of meta-bis- (2-hydroxyisopropyl) benzene and para-bis- (2-hydroxyisopropyl) benzene used to the amount of hydrogen peroxide used is 1:4-6.
8. The process of claim 1 or 2, wherein the weight ratio of the total amount of meta-bis- (2-hydroxyisopropyl) benzene and para-bis- (2-hydroxyisopropyl) benzene used to the amount of catalyst used is 1:0.01-0.1.
9. The process of claim 1 or 2, wherein the catalyst is an acidic catalyst.
10. The process according to claim 9, wherein the acidic catalyst is selected from one or more of sulfuric acid, p-toluenesulfonic acid, perchloric acid, phosphoric acid, hydrochloric acid.
11. The process of claim 1 or 2, wherein the conditions of the reaction in step (1) comprise: the temperature is 35-85 ℃; the pressure is 0.005-0.06MPa; the time is 1-6 hours.
12. The process of claim 1 or 2, wherein the conditions of the reaction in step (1) comprise: the temperature is 40-60 ℃.
13. The process according to claim 1 or 2, wherein the conditions of the reaction in step (1) comprise: the pressure is 0.015-0.03MPa.
14. The process according to claim 1 or 2, wherein the conditions of the reaction in step (1) comprise: the time is 2-5 hours.
15. The process of claim 1 or 2, wherein the reaction is carried out until the 3- (2-hydroxy-2-propyl) cumene hydroperoxide content in the reaction mixture is < 0.1 wt.%.
16. The process of claim 1 or 2, wherein the process further comprises reducing the temperature of the reaction mixture prior to solid-liquid separation.
17. A process according to claim 1 or 2, wherein the reaction mixture is cooled to 0-20 ℃.
18. The process of claim 1, wherein the reaction mixture is cooled to 5-10 ℃.
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