CN116199648A - Method for preparing epoxy cyclic hydrocarbon - Google Patents
Method for preparing epoxy cyclic hydrocarbon Download PDFInfo
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- CN116199648A CN116199648A CN202111455256.8A CN202111455256A CN116199648A CN 116199648 A CN116199648 A CN 116199648A CN 202111455256 A CN202111455256 A CN 202111455256A CN 116199648 A CN116199648 A CN 116199648A
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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Abstract
The present invention relates to a process for the preparation of an epoxy-containing cyclic hydrocarbon, which process comprises: contacting a cycloolefin with an oxidant in the presence of a titanium-containing catalyst to perform an oxidation reaction; the titanium-containing catalyst is prepared by the following steps of (1) placing a first conductive object and a second conductive object in electrolyte containing inorganic acid, and electrolyzing for 2-10 days at a voltage of 30-100V to obtain electrolytic mixed solution; (2) Mixing the electrolytic mixed solution, the organosilicate and the block copolymer, and maintaining at 50-100 ℃ for 2-24 hours to obtain a first mixture; (3) Mixing the first mixture, the titanium source and hydrogen peroxide, maintaining at 60-90 ℃ for 1-10 hours, performing hydrothermal treatment on the obtained second mixture, taking out the solid, and drying and roasting. The titanium-containing catalyst prepared by the method has better reactivity, and can be used for the oxidation reaction of cycloolefin to improve the conversion rate of raw materials and the selectivity of target products.
Description
Technical Field
The present invention relates to a process for preparing an epoxy cyclic hydrocarbon.
Background
In the fields of hydrocarbon selective oxidation catalysis application and the like, the carbon dot and other nano carbon materials have better application prospect, but the existing carbon nano materials also need to be improved and optimized in the aspects of material performance and the like, and the vast scientific workers are required to further research and develop the carbon nano materials so as to promote the industry upgrading and transformation of petrochemical industry. In the hydrocarbon selective oxidation reaction, the oxidation preparation of oxygen-containing organic chemicals such as epoxy cycloolefin plays an important role in national production, and many aspects of the preparation of epoxy cycloolefin such as the existing catalytic oxidation production technology need to be improved.
Disclosure of Invention
The invention aims to provide a method for preparing epoxy cyclic hydrocarbon, which can improve the conversion rate of raw materials and the selectivity of target products.
In order to achieve the above object, the present invention provides a method for producing an epoxy ring hydrocarbon, comprising: contacting a cycloolefin with an oxidant in the presence of a titanium-containing catalyst to perform an oxidation reaction;
the titanium-containing catalyst is prepared by a method comprising the following steps:
(1) Placing a first conductive object and a second conductive object which are respectively connected with a positive electrode and a negative electrode of a direct current power supply into electrolyte containing inorganic acid, and electrolyzing for 2-10 days under the voltage of 30-100V to obtain electrolytic mixed solution; the first conductive material is a graphite rod, and the electrolytic mixed solution contains carbon points;
(2) Mixing the electrolytic mixed solution, the organosilicate and the block copolymer, and maintaining at 50-100 ℃ for 2-24 hours to obtain a first mixture; wherein the molecular weight of the block copolymer is 2000-100000;
(3) Mixing the first mixture, a titanium source and hydrogen peroxide, maintaining at 60-90 ℃ for 1-10 hours, performing hydrothermal treatment on the obtained second mixture, taking out solids, and drying and roasting.
Optionally, in the step (1), the concentration of carbon points in the electrolytic mixed solution is 10-1000mg/L, and the concentration of inorganic acid in the electrolyte is 5-1000mmol/L.
Optionally, in step (2), dividing the electrolytic mixed solution into a first portion of electrolytic mixed solution and a second portion of electrolytic mixed solution;
mixing the organosilicate with the first portion of the electrolytic mixing solution to obtain a third mixture, mixing the block copolymer with the second portion of the electrolytic mixing solution to obtain a fourth mixture, and mixing the third mixture and the fourth mixture to obtain a first mixture.
Optionally, in the step (2), the weight ratio of the electrolytic mixed solution, the organosilicate and the block copolymer is 100: (1-50): (1-40).
Optionally, in the step (3), the weight ratio of the first mixture, the titanium source and the hydrogen peroxide is 1000: (1-500): (1-200).
Preferably, the weight ratio of the first mixture, the titanium source and the hydrogen peroxide is 100: (5-200): (2-100).
Optionally, in step (3), the drying is vacuum drying, and the conditions of the vacuum drying include: the temperature is 20-200 ℃, the pressure is 0-0.1MPa, and the time is 1-24 hours; the roasting conditions include: the temperature is 400-800 ℃ and the time is 1-10 hours.
Optionally, the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid and sulfurous acid;
the organic silicate is selected from tetramethyl silicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate or dimethoxy diethoxy silane, or a combination of two or three of the four;
the titanium source is selected from one or more of titanium chloride, titanium sulfate, titanate, tetrabutyl titanate and tetrapropyl titanate;
the block copolymer is a polyethylene oxide-polypropylene oxide block copolymer, preferably P123 and/or F127.
Optionally, the oxidation reaction conditions include: the temperature is 60-200deg.C, the pressure is 0.1-5MPa, and the time is 0.1-24 hours.
Optionally, the cyclic olefin is a C5-C12 substituted or unsubstituted monocyclic olefin, and/or a C8-C16 substituted or unsubstituted bicyclic olefin; the weight ratio of the cycloolefin to the titanium-containing catalyst is 100: (0.1-20).
Optionally, the oxidizing agent is an oxygen-containing gas, the oxygen concentration of the oxygen-containing gas being greater than 10% by volume; the weight ratio of oxygen in the oxygen-containing gas to the cycloolefin is greater than 1.
According to the technical scheme, the method for preparing the epoxy cyclic hydrocarbon by catalysis through the titanium-containing catalyst has the advantages of high conversion rate of reactants and higher selectivity to the target product epoxy cyclic hydrocarbon.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The present invention provides a process for preparing an epoxy cyclic hydrocarbon, the process comprising: contacting a cycloolefin with an oxidant in the presence of a titanium-containing catalyst to perform an oxidation reaction;
the titanium-containing catalyst is prepared by a method comprising the following steps:
(1) Placing a first conductive object and a second conductive object which are respectively connected with a positive electrode and a negative electrode of a direct current power supply into electrolyte containing inorganic acid, and electrolyzing for 2-10 days under the voltage of 30-100V to obtain electrolytic mixed solution; the first conductive material is a graphite rod, and the electrolytic mixed solution contains carbon points;
(2) Mixing the electrolytic mixed solution, the organosilicate and the block copolymer, and maintaining at 50-100 ℃ for 2-24 hours to obtain a first mixture; wherein the molecular weight of the block copolymer is 2000-100000;
(3) Mixing the first mixture, a titanium source and hydrogen peroxide, maintaining at 60-90 ℃ for 1-10 hours, performing hydrothermal treatment on the obtained second mixture, taking out solids, and drying and roasting.
In the present invention, the epoxycyclic hydrocarbon is epoxycyclic hydrocarbon and/or epoxycyclic olefin.
According to the present invention, the amount of the electrolyte is not particularly limited, and may be selected according to actual needs, for example, according to the sizes of the first and second conductors and the electrolysis conditions. In a preferred embodiment, the dimensions of the first conductive object match the dimensions of the second conductive object, and the dimensions of the first conductive object may vary widely, for example, the graphite rod may have a diameter of 3-20mm and a length of 5-50cm, where the length refers to the axial length of the graphite rod. The type and shape of the second conductive material are not particularly limited, and may be any conductive material, for example, iron, copper, graphite, etc., preferably graphite, and the shape may be a rod, a plate, etc., preferably a rod. When the electrolysis is performed, a certain distance between the first conductive material and the second conductive material is required to be maintained, and for example, the distance may be 5-40cm.
In one specific embodiment of the invention, in the step (1), the concentration of carbon points in the electrolytic mixed solution is 10-1000mg/L, and the concentration of inorganic acid in the electrolyte is 5-1000mmol/L. Wherein the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid and sulfurous acid.
In one embodiment of the present invention, in step (2), the electrolytic mixed solution is divided into a first portion of electrolytic mixed solution and a second portion of electrolytic mixed solution; mixing the organosilicate with the first portion of the electrolytic mixing solution to obtain a third mixture, mixing the block copolymer with the second portion of the electrolytic mixing solution to obtain a fourth mixture, and mixing the third mixture and the fourth mixture to obtain a first mixture. Preferably, the organosilicate is mixed with a first portion of the electrolytic mixing solution and the block copolymer is mixed with a second portion of the electrolytic mixing solution under stirring; stirring is well known to those skilled in the art, and for example, mechanical stirring can be used, and by adopting the method, a titanium-containing catalyst with better catalytic performance can be prepared, and the selectivity to the epoxy ring hydrocarbon can be further improved when the titanium-containing catalyst is used in the method for preparing the epoxy ring hydrocarbon.
In a specific embodiment of the present invention, in the step (2), the weight ratio of the electrolytic mixed solution, the organosilicate and the block copolymer may be varied within a wide range, for example, may be 100: (1-50): (1-40), preferably 100: (5-40): (2-30), more preferably 100: (10-30): (5-20). Among them, organosilicates are well known to those skilled in the art and may include, but are not limited to, tetramethyl silicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, or dimethoxydiethoxysilane, or a combination of two or three thereof. The weight average molecular weight of the block copolymer is preferably 3000-50000, preferably a polyethylene oxide-polypropylene oxide based block copolymer, which may include, for example, but not limited to, P123 and/or F127.
In a specific embodiment of the present invention, in the step (3), the weight ratio of the amounts of the first mixture, the titanium source and the hydrogen peroxide may be varied within a wide range, for example, may be 1000: (1-500): (1-200), preferably 1000: (5-200): (2-100), more preferably 1000: (10-100): (5-50). Wherein the titanium source is conventionally adopted by those skilled in the art, and can be selected from organic titanium sources and/or inorganic titanium sources, wherein the inorganic titanium sources can comprise one or more of titanium chloride, titanium sulfate and titanate, and the organic titanium sources can comprise one or more of tetrabutyl titanate and tetrapropyl titanate.
In a preferred embodiment, step (3) further comprises: mixing the first mixture, the titanium source and the solvent, adding hydrogen peroxide to the obtained mixture, and maintaining at 0-90 ℃ for 1-24 hours, preferably at 10-80 ℃ for 2-12 hours. Among them, the solvent is water or an organic solvent such as ketone, alcohol, acid, ester, sulfone, ether, etc., preferably water.
According to the present invention, the method of removing the solid is not particularly limited, and the solid may be removed, for example, by centrifugation or filtration, and the removed solid is preferably washed and dried, and the solution used for washing is not particularly limited, and for example, washing may be performed with deionized water, ethanol or the like, and drying may be performed in a vacuum drying oven, preferably, vacuum drying is performed at a temperature of 40 to 160 ℃ and a pressure of 0 to 0.1MPa for 1 to 24 hours.
In a preferred embodiment, in step (3), the drying is vacuum drying, and the conditions of the vacuum drying include: the temperature is 20-200 ℃, the pressure is 0-0.1MPa, and the time is 1-24 hours. Calcination is a well known operation to those skilled in the art, and may be performed in a muffle furnace or a tube furnace, for example, the atmosphere of calcination is not limited by the present invention, and may be an air atmosphere or an inert atmosphere, for example. In one embodiment, the firing conditions include: the temperature is 400-800 ℃ for 1-10 hours, preferably the roasting temperature is 450-750 ℃ for 2-8 hours.
According to the invention, the cycloolefins can be C5-C12 substituted or unsubstituted monocyclic olefins and/or C8-C16 substituted or unsubstituted bicyclic olefins. Further, when the cyclic olefin is selected from a C5-C12 substituted monocyclic olefin and/or a C8-C16 substituted bicyclic olefin, the substituents thereof may include, but are not limited to, halogen, methyl, ethyl, propyl, butyl, and the like. In a preferred embodiment, the cyclic olefin may be cyclohexene, cyclooctene, cycloheptene, dicyclopentadiene, bicyclohexene, methylcyclohexene, halogenated cyclohexene, methylcyclopentene, bromocyclohexene, chlorocyclopentene and the like, preferably cyclooctene, dicyclopentadiene.
In a preferred embodiment, the catalyst is a titanium-containing catalyst of the present invention, and the weight ratio of cycloolefin to catalyst may be 100: (0.1-20), preferably 100: (0.5-5).
The oxidation reaction according to the invention may be carried out in catalytic reactors known to the person skilled in the art, for example in batch tank reactors, fixed bed reactors, moving bed reactors, suspended bed reactors or slurry bed reactors. The amount of the catalyst may be appropriately selected depending on the amounts of the cycloolefin and the oxidizing agent, and the reactor.
In one embodiment, the oxidation reaction is carried out in a slurry bed reactor, and the catalyst may be used in an amount of 0.1 to 10g, preferably 0.5 to 5g, based on 100mL of cycloolefin, based on the titanium-containing catalyst of the present invention contained in the catalyst. In another embodiment, the oxidation reaction is carried out in a fixed bed reactor, the weight hourly space velocity of the cycloolefin may be from 0.01 to 10h -1 Preferably 0.05-2h -1 。
In one embodiment of the present invention, the oxidation reaction conditions include: the temperature is 60-200 ℃, the pressure is 0.1-5MPa, and the time is 0.1-24 hours; preferably, the temperature is 100-150 ℃, the pressure is 0.1-2.5MPa, and the time is 1-20 hours.
According to the invention, the oxidizing agent is conventionally used by those skilled in the art, for example, the oxidizing agent is an oxygen-containing gas, preferably air or oxygen, and the oxidation reaction can be performed without using an initiator, the effect is similar to that of the condition that the initiator exists, the addition of the initiator can be avoided, and the subsequent separation and purification process is simplified. In one embodiment, the oxygen concentration of the oxygen-containing gas may be greater than 10% by volume. The molar ratio of cycloolefin to oxygen in the oxygen-containing gas may vary within a wide range, for example, the molar amount of oxygen in the oxygen-containing gas may be 1 to 20 times the theoretical value of oxygen demand for the desired product for the oxidation of cycloolefin. In a specific embodiment, the mass ratio of oxygen in the oxygen-containing gas to cycloolefin is greater than 1, preferably (2-10): 1.
the invention is further illustrated by the following examples, which are not intended to be limiting in any way. The reagents used in the invention are all commercially available analytically pure reagents.
Preparation example 1
S1, adding 5000mL of sulfuric acid with the concentration of 120mmol/L into a beaker as electrolyte, placing an anode graphite rod (with the diameter of 8mm and the length of 50 cm) and a cathode graphite rod (with the diameter of 8mm and the length of 50 cm) in the beaker, keeping the distance between the anode graphite rod and the cathode rod to be 10cm, connecting the anode graphite rod with the positive electrode of a direct current power supply, connecting the cathode rod with the negative electrode of the direct current power supply, and applying a voltage of 25V for electrolysis for 5 days to obtain an electrolysis mixed solution; the concentration of carbon points in the electrolytic mixed solution is 210mg/L;
s2, dividing a proper amount of electrolytic mixed solution into two parts with equal volume, mixing tetraethyl silicate with the first part of electrolytic mixed solution, and stirring the mixture with the assistance of the auxiliary stirring in the process to obtain a third mixture; mixing the segmented copolymer P123 with the second part of electrolytic mixed solution, wherein stirring can be assisted in the process to obtain a fourth mixture; slowly and uniformly mixing the third mixture and the fourth mixture to obtain a first mixture, wherein the weight ratio of the electrolytic mixed solution to the organosilicate to the block copolymer is 100:15:10;
s3, under stirring, the weight ratio of the first mixture to the tetrabutyl titanate to the hydrogen peroxide is 1000:50:50, maintaining at 80deg.C for 6 hours to obtain a second mixture; transferring the second mixture into a high-pressure reaction kettle for sealing, carrying out hydrothermal treatment on the mixture at 150 ℃ for 24 hours, cooling and filtering to obtain a solid, and carrying out vacuum drying at 80 ℃ and 0.02MPa for 6 hours and roasting at 500 ℃ for 5 hours to obtain the titanium-containing catalyst A1.
Preparation example 2
The titanium-containing catalyst A2 was produced in the same manner as in production example 1 except that in step S2, the weight ratio of the electrolytic mixed solution, the organosilicate and the block copolymer was used in an amount of 100:9:45.
preparation example 3
The titanium-containing catalyst A3 was produced in the same manner as in production example 1 except that in step S3, the weight ratio of the amounts of the first mixture, tetrabutyl titanate and hydrogen peroxide was 1000:1:110.
preparation example 4
A titanium-containing catalyst A4 was produced in the same manner as in production example 1 except that in step S4, it was dried and then calcined at 400℃for 5 hours.
Preparation example 5
The titanium-containing catalyst A5 was prepared in the same manner as in preparation example 1 except that in step S2, the electrolytic mixed solution was not divided into two equal volumes, but the electrolytic mixed solution, tetrabutyl titanate and hydrogen peroxide were directly mixed to obtain a first mixture.
Preparation of comparative example 1
A titanium-containing catalyst DB1 was produced in the same manner as in production example 1 except that in step S2, an electrolytic mixed solution, hydrochloric acid and a block copolymer were mixed to obtain a first mixture.
Preparation of comparative example 2
Titanium-containing catalyst DB2 was prepared in the same manner as in preparation example 1 except that hydrogen peroxide was not used in step S3, except that the first mixture, tetrabutyl titanate and deionized water were mixed and maintained at 80 ℃ for 6 hours to obtain a second mixture.
Preparation of comparative example 3
The titanium-containing catalyst DB3 was prepared by the same method as in preparation example 1 except that in step S3, the solids in the second mixture were directly collected and dried and calcined without performing the hydrothermal treatment.
Preparation of comparative example 4
The titanium-containing catalyst DB4 was prepared by the same method as that of preparation example 1 except that in step S2, a proper amount of the electrolytic mixed solution was divided into two parts with equal volume, tetraethyl silicate was mixed with the first part of the electrolytic mixed solution, and stirring was assisted in the process to obtain a third mixture; mixing polyethylene glycol with molecular weight equivalent to P123 with the second part of electrolytic mixed solution, and stirring to obtain a fourth mixture; slowly and uniformly mixing the third mixture and the fourth mixture to obtain a first mixture, wherein the weight ratio of the electrolytic mixed solution to the organosilicate to the polyethylene glycol is 100:15:10.
in the following examples, the oxidation products were analyzed by gas chromatography (GC: agilent, 7890A) and gas chromatography-mass spectrometry (GC-MS: thermo Fisher Trace ISQ). The following formulas are used on this basis to calculate the feedstock conversion and target product selectivity, respectively:
% cycloolefin conversion = (molar amount of cycloolefin added before reaction-molar amount of cycloolefin remaining after reaction)/molar amount of cycloolefin added before reaction x 100%;
target product selectivity% = (molar amount of target product formed after reaction)/molar amount of cycloolefin added before reaction x 100%.
Example 1
75mg of the titanium-containing catalyst A1 prepared in the preparation example and 100mL of cyclooctene were added into a 250mL autoclave, the autoclave was sealed, oxygen was introduced (the molar ratio of oxygen to cyclooctene was 8:1), the mixture was stirred at 120℃and 2.5MPa for reaction for 4 hours, the catalyst was separated by centrifugation and filtration after cooling and pressure relief sampling, and the results of analysis of the oxidation products were shown in Table 1.
Examples 2 to 5
An epoxycycloalkane was produced in the same manner as in example 1 except that the titanium-containing catalysts A1 were replaced with the titanium-containing catalysts A2 to A5 prepared in preparation examples 2 to 5, respectively, and the results of analysis of the oxidation products are shown in Table 1.
Example 6
An epoxycycloalkane was produced in the same manner as in example 1 except that the reaction temperature was 80℃and the reaction pressure was 2.0MPa for 4 hours.
Comparative examples 1 to 4
An epoxycycloalkane was produced in the same manner as in example 1 except that the catalysts DB1-DB4 prepared in comparative examples 1-4 were used in place of the titanium-containing catalyst A1, respectively, and the results of analysis of the oxidation products are shown in Table 1.
TABLE 1
Example 7
75mg of the titanium-containing catalyst A1 prepared in preparation example 1 and 100mL of dicyclopentadiene are added into a 250mL autoclave, the autoclave is sealed, oxygen is introduced (the molar ratio of oxygen to cycloolefin is 8:1), the mixture is stirred at 120 ℃ and 2.5MPa for reaction for 4 hours, the temperature is reduced, the pressure is relieved, the sample is taken, the catalyst is centrifuged and filtered, and the result of analysis of the oxidation product is shown in Table 2.
Comparative example 5
75mg of the titanium-containing catalyst DB1 prepared in preparation comparative example 1 and 100mL of dicyclopentadiene were added into a 250mL autoclave, the autoclave was sealed, oxygen gas was introduced (the molar ratio of oxygen gas to cycloolefin was 8:1), the mixture was stirred at 120℃and 2.5MPa for reaction for 4 hours, the catalyst was separated by centrifugation and filtration after cooling and pressure relief sampling, and the results of analysis of the oxidized products were shown in Table 2.
TABLE 2
| Catalyst numbering | Dicyclopentadiene conversion% | Selectivity of epoxycycloolefin% | |
| Example 7 | A1 | 72 | 89 |
| Comparative example 5 | DB1 | 42 | 55 |
From the above, the method of the invention adopts the titanium-containing catalyst prepared by the specific method, the titanium-containing catalyst has better reactivity, and the titanium-containing catalyst can be used for the oxidation reaction of cycloolefin to improve the conversion rate of raw materials and the selectivity of target product epoxy cyclic hydrocarbon.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A process for preparing an epoxycyclic hydrocarbon, which process comprises: contacting a cycloolefin with an oxidant in the presence of a titanium-containing catalyst to perform an oxidation reaction;
the titanium-containing catalyst is prepared by a method comprising the following steps:
(1) Placing a first conductive object and a second conductive object which are respectively connected with a positive electrode and a negative electrode of a direct current power supply into electrolyte containing inorganic acid, and electrolyzing for 2-10 days under the voltage of 30-100V to obtain electrolytic mixed solution; the first conductive material is a graphite rod, and the electrolytic mixed solution contains carbon points;
(2) Mixing the electrolytic mixed solution, the organosilicate and the block copolymer, and maintaining at 50-100 ℃ for 2-24 hours to obtain a first mixture; wherein the molecular weight of the block copolymer is 2000-100000;
(3) Mixing the first mixture, a titanium source and hydrogen peroxide, maintaining at 60-90 ℃ for 1-10 hours, performing hydrothermal treatment on the obtained second mixture, taking out solids, and drying and roasting.
2. The method according to claim 1, wherein in the step (1), the concentration of carbon dots in the electrolytic mixed solution is 10-1000mg/L, and the concentration of inorganic acid in the electrolytic solution is 5-1000mmol/L.
3. The method of claim 1, wherein in step (2), the electrolytic mixed solution is divided into a first portion of electrolytic mixed solution and a second portion of electrolytic mixed solution;
mixing the organosilicate with the first portion of the electrolytic mixing solution to obtain a third mixture, mixing the block copolymer with the second portion of the electrolytic mixing solution to obtain a fourth mixture, and mixing the third mixture and the fourth mixture to obtain a first mixture.
4. The method of claim 1, wherein in step (2), the electrolytic mixed solution, the organosilicate, and the block copolymer are used in an amount of 100 by weight: (1-50): (1-40).
5. The method of claim 1, wherein in step (3), the weight ratio of the first mixture, the titanium source, and the hydrogen peroxide is 1000: (1-500): (1-200);
preferably, the weight ratio of the first mixture, the titanium source and the hydrogen peroxide is 100: (5-200): (2-100).
6. The method of claim 1, wherein in step (3), the drying is vacuum drying, and the conditions of the vacuum drying include: the temperature is 20-200 ℃, the pressure is 0-0.1MPa, and the time is 1-24 hours; the roasting conditions include: the temperature is 400-800 ℃ and the time is 1-10 hours.
7. The method of claim 1, wherein the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, and sulfurous acid;
the organic silicate is selected from tetramethyl silicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate or dimethoxy diethoxy silane, or a combination of two or three of the four;
the titanium source is selected from one or more of titanium chloride, titanium sulfate, titanate, tetrabutyl titanate and tetrapropyl titanate;
the block copolymer is a polyethylene oxide-polypropylene oxide block copolymer, preferably P123 and/or F127.
8. The method of claim 1, wherein the oxidation reaction conditions comprise: the temperature is 60-200deg.C, the pressure is 0.1-5MPa, and the time is 0.1-24 hours.
9. The process of claim 1, wherein the cyclic olefin is a C5-C12 substituted or unsubstituted monocyclic olefin, and/or a C8-C16 substituted or unsubstituted bicyclic olefin; the weight ratio of the cycloolefin to the titanium-containing catalyst is 100: (0.1-20).
10. The method of claim 1, wherein the oxidant is an oxygen-containing gas having an oxygen concentration of greater than 10% by volume; the weight ratio of oxygen in the oxygen-containing gas to the cycloolefin is greater than 1.
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