Method for preparing and separating dicyclopentadiene monoepoxide

Abstract

The invention provides a method for preparing dicyclopentadiene monoepoxide, which comprises the following steps: by taking dicyclopentadiene as a reaction raw material, cumyl hydroperoxide as an oxidizing agent and a titanium silicalite molecular sieve as a catalyst, carrying out catalytic oxidation reaction under the condition that the dicyclopentadiene, the cumyl hydroperoxide and the titanium silicalite molecular sieve catalyst are fully contacted in an inert solvent, thereby obtaining the dicyclopentadiene monoepoxide. DCPD and CHP are used as raw materials, a mixed solution of dicyclopentadiene monoepoxide and a, a-dimethyl benzyl alcohol is used as main products, the molar ratio of DCPD to CHP is (1-4): 1, the reaction temperature is 60-120 DEG C, and the DCPD monoepoxide with the mass fraction of 87.6%-92.0% is obtained from the reaction product through a double-tower continuous rectification separation process.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic oxidation synthesis of organic epoxy compounds and catalytic oxidation of olefins, and specifically relates to a method for preparing and separating dicyclopentadiene monoepoxide by using dicyclopentadiene as a raw material and titanium silicon molecular sieve as a catalyst. Background Art

[0002] Dicyclopentadiene (DCPD), scientific name is tricyclo[5.2.1.0 2,6 ]Decene-3,8, has two double bonds in the molecule. When dicyclopentadiene DCPD is in excess, it reacts with organic peroxides to form two monoepoxides, generally called dicyclopentadiene monoepoxides. Each molecule of this compound contains one epoxy bond and one olefin bond, and has a bifunctional structure. It has good application prospects in the fields of medicine, pesticides and other fine chemicals, epoxy resin composite materials, etc. DCPD reacts with organic peroxides to form DCPD monoepoxides, see reaction formula (1):

[0003]

[0004] DCPD monoepoxide (1), (3), scientific name: 9-oxatetracyclo[5.3.1.0 2,6 .0 8,10 ]Undec-3-ene

[0005] DCPD monoepoxide (2), (4), scientific name: 4-oxatetracyclo[6.2.1.0 2,7 .0 3,5 ]Undec-9-ene

[0006] Existing literature (Huang Zhitong, Han Xiaozu. Four (3,4), (8,9)-diepoxy-tris[5.2.1.0 2,6 [J] Synthesis and Configuration of Decane [J] Acta Chimica Sinica, 1979, 37 (1): 23-28) discloses a method for synthesizing DCPD monoepoxide: 77 g of exo-DCPD (0.58 mol) is reacted with 66.8 g (0.29 mol) of 33.6% peracetic acid to produce 28.9 g of DCPD monooxide (1) and (2), with a yield of 67%. According to the method of Pirsch (see reference: J. Pirsch, Monatsh. Chem. 85, 154, 1954), 95.3 g of endo-DCPD is reacted with 33.6% peracetic acid in an equimolar mass fraction to produce 53 g of a mixture of DCPD monoepoxide (3) and (4), with a yield of 50%.

[0007] Since peracetic acid contains 47% acetic acid, 21% water, and 5% sulfuric acid, under the catalysis of sulfuric acid, the olefin bonds in DCPD and the epoxy bonds in DCPD monoepoxides (1), (2) or (3), (4) will react with acetic acid and water to form a variety of by-products, which greatly increases the difficulty of separating and purifying the reaction products. Obviously, the existing peracetic acid method for preparing DCPD monoepoxide has poor process safety. The reaction products contain sulfuric acid and acetic acid, which are prone to side reactions, serious equipment corrosion problems, and a large amount of process wastewater. Peracetic acid is a strong oxidant and is extremely unstable. It will explode at -20°C, and it will be explosive when the concentration is greater than 45%. It will cause an explosion when exposed to high heat, reducing agents, or the presence of metal ions. Peracetic acid is included in the "List of Dangerous Chemicals that Can Be Exploded (2022 Edition)".

[0008] Since there are two double bonds in the DCPD molecule, adding an organic peroxide will generate not only dicyclopentadiene monoepoxide but also dicyclopentadiene diepoxide. In order to control the conversion of DCPD into monoepoxide, an excess of DCPD needs to be added, but an excess of DCPD brings many problems to the separation and purification of the product and also has many adverse effects on the activity of the catalyst. Summary of the invention

[0009] An object of the present invention is to provide a method for preparing dicyclopentadiene monoepoxide.

[0010] Another object of the present invention is to provide a method for separating dicyclopentadiene monoepoxide.

[0011] On the one hand, the present invention provides a method for preparing dicyclopentadiene monoepoxide, comprising: using dicyclopentadiene (DCPD) as a raw material, an organic peroxide as an oxidant, and a titanium silicon molecular sieve as a catalyst, in an inert solvent, DCPD, the oxidant and the titanium silicon molecular sieve catalyst are fully contacted to undergo a catalytic oxidation reaction to generate a mixture containing DCPD monoepoxide, and obtaining the DCPD monoepoxide through separation and purification;

[0012] The titanium silicon molecular sieve catalyst is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and its components include: TiO2 mass fraction of 0.10% to 6.42%, nano carbon fiber mass fraction of 44.68% to 64.11%, SiO2 mass fraction of 28.17% to 45.80%, magnesium oxide mass fraction of 0.01% to 1.98%, silane mass fraction of 0.44% to 6.93%;

[0013] The catalytic oxidation reaction temperature is 60 to 120° C., the molar ratio of DCPD to the oxidant is 1 to 4:1, preferably 3 to 4:1, and the DCPD monoepoxide has the structure of formula (1), (2), (3) or (4):

[0014]

[0015] Furthermore, the organic peroxide oxidant is tert-butyl hydroperoxide, tert-amyl hydroperoxide or isopropylbenzene hydroperoxide (CHP).

[0016] Furthermore, the inert solvent used in the epoxy reaction system is an organic hydrocarbon compound such as benzene, toluene, cumene, cyclohexane, heptane, octane, decane, etc., and cumene is preferably used as the solvent.

[0017] Furthermore, the reaction raw material DCPD can be an endo-structure or an exo-structure, or a mixture of endo-structure and exo-structure. Usually, DCPD with an endo-structure DCPD mass fraction of 98% and an exo-structure DCPD mass percentage of less than 1% is selected.

[0018] On the other hand, the present invention provides a method for separating dicyclopentadiene monoepoxide, comprising: conveying a mixed liquid to a distillation tower for vacuum distillation separation; the mixture comprises DCPD, DCPD monoepoxide, DCPD diepoxide, an inert solvent and α, α-dimethylbenzyl alcohol.

[0019] The advantages of the present invention are that the HMS titanium silicon molecular sieve with mesoporous characteristics is used as a catalyst to synthesize the DCPD monoepoxide process, the reaction process has high safety, few by-products, simple separation, low wastewater discharge, and easy industrialization. Specific embodiments

[0020] The following examples further illustrate the present invention, but the present invention is not limited to the examples. Some definitions in the present invention:

[0021] DCPD conversion rate = (the number of moles of DCPD monoepoxide in the epoxidation reaction product + the number of moles of DCPD diepoxide in the epoxidation reaction product) / the total number of moles of DCPD put into the epoxidation reactor * 100%;

[0022] DCPD monoepoxide selectivity = mole number of DCPD monoepoxide in the epoxidation reaction product / (mole number of DCPD monoepoxide in the epoxidation reaction product + mole number of DCPD diepoxide in the epoxidation reaction product)*100%;

[0023] DCPD distillation yield = number of moles of DCPD collected per hour at the top of the distillation tower / number of moles of DCPD in the material input into the distillation tower per hour * 100%;

[0024] Isopropylbenzene distillation yield = number of moles of propylbenzene collected per hour at the top of the distillation tower / number of moles of propylbenzene in the material input into the distillation tower per hour * 100%;

[0025] a,a-dimethylbenzyl alcohol distillation yield = number of moles of a,a-dimethylbenzyl alcohol collected per hour at the top of the distillation tower / number of moles of a,a-dimethylbenzyl alcohol in the material input into the distillation tower per hour * 100%;

[0026] DCPD monoepoxide distillation yield = number of moles of DCPD monoepoxide collected per hour in the distillation tower kettle / number of moles of DCPD monoepoxide in the material input into the distillation tower per hour * 100%;

[0027] The process yield of DCPD monoepoxide = the mole number of DCPD monoepoxide generated in each batch of epoxidation reaction / (the mole number of DCPD put into the reactor in this batch - the mole number of DCPD recovered by distillation separation in this batch)*100%.

[0028] According to the method provided by the present invention, titanium-containing hexagonal mesoporous silica for synthesizing DCPD monoepoxide is represented by Ti / HMS, and its main preparation process is as follows: (i) Preparation of hexagonal mesoporous silica powder: dissolve an appropriate amount of long-chain fatty amine in an ethanol-water solution, stir evenly to obtain solution A, and dissolve an appropriate amount of tetraethyl orthosilicate in ethanol to obtain solution B. Add solution B to solution A quickly, stir vigorously, place it at room temperature for aging to obtain a precipitate, filter, wash, dry, and calcine at high temperature to obtain pure silicon HMS powder. (ii) Carrier molding: add HMS powder and auxiliary agent to a kneader in a certain proportion, stir and mix well, add a binder to knead, extrude, extrude, dry, and calcine to obtain a molded HMS carrier. (iii) Chemical vapor deposition titanium carrier: place the molded HMS carrier in a quartz tube reactor, heat it in an inert gas and pass TiCl4 vapor, react for a period of time, and then purge it with an inert gas to obtain a Ti / HMS sample. (iv) placing the Ti / HMS sample prepared above in a quartz tube reactor, introducing a silanization agent by an inert gas, reacting for a certain period of time under dry conditions, removing excess unreacted silanization agent, and cooling to room temperature in an inert gas environment.

[0029] According to the method provided by the present invention, the titanium-containing hexagonal mesoporous silica Ti / HMS used to synthesize DCPD monoepoxide has a strong absorption peak near the wavelength of 220nm in the UV-vis spectrum of the Ti / HMS sample without silylation reaction treatment. After alkylation reaction treatment, the UV-vis spectrum of the Ti / HMS sample has a strong absorption peak near the wavelength of 215nm, and the BET surface area is 550.5m 2 / g, average pore diameter 2.7nm, pore volume 0.65cm 3 / g.

[0030] According to the method provided by the present invention, titanium-containing hexagonal mesoporous silica Ti / HMS for synthesizing DCPD monoepoxide, the preparation method thereof includes but is not limited to the method disclosed in the following documents: (i) Jin Guojie, Gao Huanxin, Yang Hongyun, et al. Characterization of post-synthesized Ti / HMS catalyst and its catalytic epoxidation performance for propylene [J]. Molecular Catalysis, 2010, 24(1): 6-11. (ii) Wang Chao, Jin Guojie, Gao Huanxin, et al. Hydrophobically modified Ti / HMS catalyst for propylene epoxidation process. [C] 2015 Proceedings of the Annual Conference of the Chemical Industry Society of China. Engineering Technology I, 2015: 1-7.

[0031] According to the method provided by the present invention, a Ti / HMS catalyst with mesoporous characteristics used for preparing DCPD monoepoxide is prepared, and its preparation method includes but is not limited to the methods disclosed in the following Chinese patents: CN102874835B, CN112723377B, CN104437636B, CN104437450B, CN104437618B, CN104437635B, CN113083358A, CN113083359A, and CN113083360A.

[0032] According to the method provided by the present invention, the reactor can be a suspended bed reactor or a solid bed reactor.

[0033] According to the method provided by the present invention, the amount of catalyst used is 0.8% to 12.5% ​​(the mass percentage of the catalyst to the total mass percentage of the liquid material put into the reactor).

[0034] According to the method provided by the present invention, pressure has no significant effect on the reaction, and the reaction can be carried out at normal pressure or under pressure, and the reaction pressure is preferably 0.1 to 1.7 MPa.

[0035] According to the method provided by the present invention, the epoxidation reaction temperature is 60 to 120° C., and the preferred contact time between the reaction material and the catalyst is 1 to 3 hours.

[0036] According to the method provided in this document, the oxidants cumene hydroperoxide, tert-butyl hydroperoxide or tert-amyl hydroperoxide are not included in the "List of Dangerous Chemicals that are Explosive or Fermentable (2022 Edition)".

[0037] The preparation method of dicyclopentadiene monoepoxide adopts titanium silicon molecular sieve to catalyze epoxidation reaction in an inert solvent, is non-corrosive, and the oxidant cumene hydroperoxide, tert-butyl hydroperoxide or tert-amyl hydroperoxide is highly safe, the product does not need to be washed with water, the reaction temperature operating range is wide, a fixed bed continuous reaction can be performed, and large-scale industrial production can be easily realized.

[0038] According to the method provided by the present invention, after the epoxidation reaction products of DCPD and isopropylbenzene hydroperoxide, tert-butyl alcohol peroxide and tert-amyl alcohol peroxide leave the reactor, they are transported to a distillation tower for vacuum distillation separation, and the separated inert solvent and DCPD are repeatedly used for DCPD monoepoxidation reaction, and α,α-dimethylbenzyl alcohol, tert-butyl alcohol and tert-amyl alcohol can be used as by-products.

[0039] In the embodiment, the reaction product used for distillation has a mass percentage composition of: DCPD 1.6% to 21.4%, DCPD monoepoxide 5.1% to 7.7%, DCPD diepoxide 0.6% to 2.5%, inert solvent 59.9% to 80.4%, a, a-dimethylbenzyl alcohol 8.7% to 11.1%, and cumene hydroperoxide <0.2%.

[0040] A double-tower series distillation separation process is adopted. The reaction material (the mixed liquid after the epoxidation reaction of DCPD and isopropylbenzene hydroperoxide is used as the distillation example raw material) is transported to the first distillation tower, the DCPD and inert solvent mixture is collected at the top of the tower, and the bottom material is transported to the second distillation tower; a, a-dimethylbenzyl alcohol is collected at the top of the second distillation tower, and a mixture of DCPD monoepoxide and DCPD diepoxide is collected at the bottom of the tower. The first distillation tower has 6 to 20 plates, a reflux ratio of 1 to 4, a top temperature of 66.4 to 98.3°C, a top pressure of 5 to 18 kPa, and a bottom temperature of 117.7 to 151.6°C; the second distillation tower has 15 to 30 plates, a reflux ratio of 4 to 8, a top temperature of 112.9 to 130.1°C, a top pressure of 5 to 10 kPa, and a bottom temperature of 126.4 to 145.9°C.

[0041] A single-tower distillation separation process is adopted. The reaction material (the mixed liquid after the epoxidation reaction of DCPD and cumene hydroperoxide is used as the distillation example raw material) is transported to the distillation tower, the solvent and DCPD are collected at the top of the tower, and the DCPD monoepoxide compound is collected in the bottom of the tower; the number of plates of the distillation tower is 6 to 20, the reflux ratio is 1 to 4, the top temperature is 65.5 to 84.9°C, the top pressure is 5 to 15 kPa, and the bottom temperature is 127.0 to 157.4°C.

[0042] The mass percentage composition of the reaction materials of the present invention is determined by gas chromatography analysis. The mass percentage of DCPD monoepoxide in the reaction product is the sum of the mass percentages of the four structures of DCPD monoepoxide in the above reaction formula (1).

[0043] The titanium silicate molecular sieve catalyst used in the following embodiments is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and its components include: TiO2 mass fraction of 0.10% to 6.42%, nano-carbon fiber mass fraction of 44.68% to 64.11%, SiO2 mass fraction of 28.17% to 45.80%, magnesium oxide mass fraction of 0.01% to 1.98%, and silane mass fraction of 0.44% to 6.93%.

[0044] Example 1

[0045] In a 150 ml stainless steel reactor with magnetic stirring, 6.4 g of DCPD (purity 98%), 9.1 g of cumene hydroperoxide (purity 82%), 43.5 g of benzene solvent (purity 99%), and 0.7 g of HMS structure titanium silicon molecular sieve were added. The catalyst composition was: nano-carbon fiber mass fraction 62.90%, TiO2 mass fraction 2.57%, SiO2 mass fraction 31.32%, MgO mass fraction 0.83%, and silane mass fraction 2.38%. The molar ratio of DCPD to cumene hydroperoxide added to the reactor was 1:1, and the amount of catalyst was 1.2% (based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). After the reactor was replaced with nitrogen, the reactor outlet valve was closed. The magnetic stirring was turned on, the oil bath was heated, the reaction temperature was controlled at 90°C, and the reaction pressure was maintained at 1.0 MPa by adjusting the valve on the air inlet pipeline connected to the nitrogen pipeline. After reacting for 2 hours, the material was cooled to room temperature, sampled, and the product composition was analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 1.6%, the mass fraction of DCPD monoepoxide was 5.1%, the mass fraction of dicyclopentadiene diepoxide was 2.5%, the DCPD conversion rate was 80.5%, and the selectivity of generating DCPD monoepoxide was 69.7%.

[0046] Example 2

[0047] In a 150 ml stainless steel reactor with magnetic stirring, 12.9 g of DCPD (purity 98%), 9.1 g of cumene hydroperoxide (purity 82%), 43.5 g of toluene (purity 99%), and 0.7 g of HMS structure titanium silicon molecular sieve were added. The catalyst composition was: nano-carbon fiber mass fraction 64.11%, TiO2 mass fraction 3.63%, SiO2 mass fraction 28.17%, MgO mass fraction 0.01%, and silane mass fraction 4.08%. The molar ratio of DCPD to cumene hydroperoxide added to the reactor was 2:1, and the amount of catalyst was 1.1% (based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). After the reactor was replaced with nitrogen, the reactor outlet valve was closed. The magnetic stirring was turned on, the oil bath was heated, the reaction temperature was controlled at 90°C, the reaction pressure was maintained at 1.0 MPa by adjusting the valve on the air inlet pipeline connected to the nitrogen pipeline, and the reaction was continued for 1.5 hours, the material was cooled to room temperature, and the sample was taken, and the product composition was analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 9.2%, the mass fraction of DCPD monoepoxide was 7.6%, the mass fraction of dicyclopentadiene diepoxide was 1.1%, the DCPD conversion rate was 45.6%, and the selectivity of DCPD monoepoxide was 88.1%.

[0048] Example 3

[0049] In a 150 ml stainless steel reactor with magnetic stirring, 19.2 g of DCPD (purity 98%), 9.1 g of cumene hydroperoxide (purity 82%), 43.5 g of cumene (purity 99%), and 0.7 g of HMS structure titanium silicon molecular sieve were added. The catalyst composition was: nano-carbon fiber mass fraction 56.16%, TiO2 mass fraction 4.81%, SiO2 mass fraction 33.13%, MgO mass fraction 0.41%, and silane mass fraction 5.49%. The molar ratio of DCPD to cumene hydroperoxide added to the reactor was 3:1, and the amount of catalyst was 1.0% (based on the ratio of the mass of the catalyst to the total mass of the liquid material added to the reactor). After the reactor was replaced with nitrogen, the reactor outlet valve was closed. The magnetic stirring was turned on, the oil bath was heated, the reaction temperature was controlled at 90°C, the reaction pressure was maintained at 1.0 MPa by adjusting the valve on the air inlet pipeline connected to the nitrogen pipeline, and the reaction was continued for 1.5 hours, the material was cooled to room temperature, and the sample was taken, and the product composition was analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 16.7%, the mass fraction of DCPD monoepoxide was 7.1%, the mass fraction of dicyclopentadiene diepoxide was 0.6%, the conversion rate of DCPD was 28.7%, and the selectivity of DCPD monoepoxide was 93.1%.

[0050] Example 4

[0051] In a 150 ml stainless steel reactor with magnetic stirring, 25.4 g of DCPD (purity 98%), 9.1 g of cumene hydroperoxide (purity 82%), 43.5 g of cyclohexane (purity 99%), and 0.7 g of HMS structure titanium silicon molecular sieve are added. The catalyst composition is: nano-carbon fiber mass fraction 53.20%, TiO2 mass fraction 6.12%, SiO2 mass fraction 38.87%, MgO mass fraction 0.47%, silane mass fraction 1.34%. The molar ratio of DCPD to cumene hydroperoxide added to the reactor is 4:1, and the amount of catalyst is 0.9% (based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). After the reactor is replaced with nitrogen, the reactor outlet valve is closed. The magnetic stirring was turned on, the oil bath was heated, the reaction temperature was controlled at 90°C, the reaction pressure was maintained at 1.0 MPa by adjusting the valve on the air inlet pipeline connected to the nitrogen pipeline, and the reaction was continued for 1.5 hours, the material was cooled to room temperature, and the sample was taken, and the product composition was analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 21.4%, the mass fraction of DCPD monoepoxide was 7.7%, the mass fraction of dicyclopentadiene diepoxide was 0.6%, the conversion rate of DCPD was 25.5%, and the selectivity of DCPD monoepoxide was 93.5%.

[0052] Example 5

[0053] In a 150 ml stainless steel reactor with magnetic stirring, 19.2 g of DCPD (purity 98%), 9.1 g of cumene hydroperoxide (purity 82%), 43.5 g of octane (purity 99%), and 9 g of HMS structure titanium silicon molecular sieve were added. The catalyst composition was: nano-carbon fiber mass fraction 45.84%, TiO2 mass fraction 0.10%, SiO2 mass fraction 45.80%, MgO mass fraction 1.98%, and silane mass fraction 6.28%. The molar ratio of DCPD to cumene hydroperoxide added to the reactor was 3:1, and the amount of catalyst was 12.5% ​​(based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). After the reactor was replaced with nitrogen, the reactor outlet valve was closed. The magnetic stirring was turned on, the oil bath was heated, the reaction temperature was controlled at 120°C, and the reaction pressure was maintained at 1.7MPa by adjusting the valve on the air inlet pipeline connected to the nitrogen pipeline. After the reaction for 1 hour, the material was cooled to room temperature, sampled, and the product composition was analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 17.8%, the mass fraction of DCPD monoepoxide was 8.2%, the mass fraction of dicyclopentadiene diepoxide was 0.7%, the conversion rate of DCPD was 30.7%, and the selectivity of DCPD monoepoxide was 92.4%.

[0054] Example 6

[0055] In a 150 ml stainless steel reactor with magnetic stirring, 19.2 g of DCPD (purity 98%), 9.1 g of cumene hydroperoxide (purity 82%), 21.4 g of heptane (purity 99%), and 0.4 g of HMS structure titanium silicon molecular sieve are added. The catalyst composition is: nano carbon fiber mass fraction 58.56%, TiO2 mass fraction 6.42%, SiO2 mass fraction 33.94%, MgO mass fraction 0.64%, silane mass fraction 0.44%. The molar ratio of DCPD to cumene hydroperoxide added to the reactor is 3:1, and the amount of catalyst is 0.8% (based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). The reactor outlet valve is opened and connected to the atmosphere. Magnetic stirring is turned on, oil bath heating is performed, and the reaction temperature is controlled at 60°C. After reacting for 3 hours, the material is cooled to room temperature, sampled, and the product composition is analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 24.4%, the mass fraction of DCPD monoepoxide was 11.5%, the mass fraction of dicyclopentadiene diepoxide was 1.0%, the DCPD conversion rate was 31.3%, and the selectivity of generating DCPD monoepoxide was 92.8%.

[0056] Example 7

[0057] In a 150 ml stainless steel reactor with magnetic stirring, 6.4 g of DCPD (purity 98%), 5.0 g of tert-amyl alcohol hydroperoxide (purity 99%), 43.5 g of decanane solvent (purity 99%), and 0.7 g of HMS structure titanium silicon molecular sieve are added. The catalyst composition is: nano carbon fiber mass fraction 48.95%, TiO2 mass fraction 5.32%, SiO2 mass fraction 38.65%, MgO mass fraction 0.67%, silane mass fraction 6.41%. The molar ratio of DCPD to tert-amyl alcohol hydroperoxide added to the reactor is 1:1, and the amount of catalyst is 1.3% (based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). After the reactor is replaced with nitrogen, the reactor outlet valve is closed. The magnetic stirring was turned on, the oil bath was heated, the reaction temperature was controlled at 90°C, and the reaction pressure was maintained at 1.0 MPa by adjusting the valve on the air inlet pipeline connected to the nitrogen pipeline. After reacting for 2 hours, the material was cooled to room temperature, sampled, and the product composition was analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 1.4%, the mass fraction of DCPD monoepoxide was 5.4%, the mass fraction of dicyclopentadiene diepoxide was 2.2%, the DCPD conversion rate was 82.5%, and the selectivity of generating DCPD monoepoxide was 73.1%.

[0058] Example 8

[0059] In a 150 ml stainless steel reactor with magnetic stirring, 19.2 g of DCPD (purity 98%), 4.3 g of tert-butyl hydroperoxide (purity 99%), 21.4 g of isopropylbenzene (purity 99%), and 1.0 g of HMS structure titanium silicon molecular sieve are added. The catalyst composition is: nano carbon fiber mass fraction 44.68%, TiO2 mass fraction 5.65%, SiO2 mass fraction 41.81%, MgO mass fraction 0.93%, silane mass fraction 6.93%. The molar ratio of DCPD to tert-butyl hydroperoxide added to the reactor is 3:1, and the amount of catalyst is 2.2% (based on the ratio of the mass of the catalyst added to the reactor to the total mass of the liquid material). The reactor outlet valve is opened and connected to the atmosphere. Magnetic stirring is turned on, oil bath heating is performed, and the reaction temperature is controlled at 60°C. After reacting for 3 hours, the material is cooled to room temperature, sampled, and the product composition is analyzed by gas chromatography. In the reaction product, the mass fraction of DCPD was 24.0%, the mass fraction of DCPD monoepoxide was 11.0%, the mass fraction of dicyclopentadiene diepoxide was 1.5%, the DCPD conversion rate was 31.5%, and the selectivity for generating DCPD monoepoxide was 89.0%.

[0060] Embodiments 9 to 14

[0061] The distillation separation operation adopts a double-tower series continuous distillation separation process. The feed rate of the first distillation tower is 50 grams per hour. The first distillation tower is 2000mm high, the inner diameter is 35mm, and the tower bottom volume is 10L. The second distillation tower is 2000mm high, the inner diameter is 35mm, and the tower bottom volume is 5L. The packing of the two towers is stainless steel θ ring packing, φ3mm*3mm. The number of distillation tower plates is adjusted by adjusting the packing height. The first and second distillation towers are fed and discharged from the tower bottom by metering pumps. The top fraction is extracted and overflowed from the condenser effluent pan into the storage tank by using the liquid level difference. The top reflux condenser uses -5℃ low-temperature water to condense and cool the material. The tower bottom material evaporation adopts electric heating. The reflux ratio controller controls the top reflux volume. Two rotary vane vacuum oil pumps are used to evacuate the two distillation towers respectively to make the distillation system pressure meet the experimental requirements. The number of tower plates is calibrated before distillation.

[0062] The reaction product prepared in Example 3 was used as the raw material for the distillation experiment, and its mass percentage composition was: cumene 66.4%, DCPD 16.7%, α,α-dimethylbenzyl alcohol 9.2%, cumene hydroperoxide ∠0.1%, DCPD monoepoxide 7.1%, and DCPD diepoxide 0.6%.

[0063] Experimental steps: (i) Add 5L of distillation raw materials to the first distillation tower kettle, turn on the vacuum oil pump, set the system pressure according to the process requirements, keep the system pressure stable, turn on the electric heating device of the first distillation tower kettle, turn on the condensing water, adjust the kettle material temperature, and when there is a fraction at the top of the first distillation tower, reflux for 3 hours. (ii) Turn on the sampling pump to deliver materials to the first distillation tower, adjust the reflux ratio, tower top pressure, tower top temperature, and tower kettle temperature (as shown in Table 1) according to the process setting requirements, and after the composition of the tower top and tower kettle materials is stable, turn on the discharge pump of the first distillation tower kettle to deliver materials to the second distillation tower, and collect DCPD and inert solvent at the top of the tower. (III) Collect 2-3 L of material in the second distillation tower kettle, turn on the electric heating device of the second distillation tower kettle, turn on the vacuum pump of the second distillation tower, adjust the top pressure of the second distillation tower and the temperature of the tower kettle material, and when there is a fraction at the top of the second distillation tower, after full reflux for 1 hour, adjust the reflux ratio, tower kettle temperature, tower top pressure and tower top temperature of the second distillation tower according to the process requirements (as shown in Table 2). After the second distillation tower runs stably, turn on the discharge pump of the second distillation tower kettle, transport the DCPD monooxide and a small amount of DCPD dioxide in the tower kettle material to the designated container, and collect a, a-dimethylbenzyl alcohol at the top of the tower.

[0064] Experimental results: After the double-tower series distillation system was operated continuously and stably, the distillation separation effect was investigated. The experimental results are shown in Tables 1 and 2.

[0065] Table 1 Operating conditions of the first distillation tower for distillation separation of DCPD monoepoxide

[0066]

[0067] Table 2 Operating process conditions of the second distillation tower for distillation separation of DCPD monoepoxide

[0068]

[0069] As shown in Tables 1 and 2, through distillation separation, the DCPD distillation yield at the top of the first distillation tower is 97.1% to 99.5%, and the isopropylbenzene distillation yield is 99.7% to 100%, which can be recycled as reaction materials; a, a-dimethylbenzyl alcohol is collected at the top of the second distillation tower, with a distillation yield greater than 96.5%, and the DCPD monoepoxide distillation yield at the bottom of the tower is greater than 99%, the mass percentage of DCPD monoepoxide is 87.6% to 92.0%, and the mass percentage of DCPD diepoxide is 8.0% to 12.4% (not listed in Table 2).

[0070] Examples 15 to 22

[0071] The distillation separation operation adopts a single-tower distillation separation process. The feed rate of the distillation tower is 50 grams per hour. The distillation tower is 2000mm high, the inner diameter is 35mm, and the tower bottom volume is 10L. The filler is a stainless steel θ ring filler with a filler specification of φ3mm*3mm. The number of distillation tower plates is adjusted by adjusting the filler height. The feed and tower bottom discharge of the distillation tower adopt a metering pump. The top fraction is extracted and overflowed from the condenser liquid tray into the storage tank by using the liquid level difference. The top reflux condenser uses -5℃ low-temperature water to condense and cool the material. The tower bottom material evaporation adopts electric heating. The reflux ratio controller controls the top reflux volume. The rotary vane vacuum oil pump evacuates the distillation tower separately to make the distillation system pressure meet the experimental requirements. The number of tower plates is calibrated before distillation.

[0072] The reaction product prepared in Example 3 was used as the raw material for the distillation experiment, and its mass percentage composition was: cumene 66.4%, DCPD 16.7%, α,α-dimethylbenzyl alcohol 9.2%, cumene hydroperoxide ∠0.1%, DCPD monoepoxide 7.1%, and DCPD diepoxide 0.6%.

[0073] Experimental steps: (i) Add 5L of distillation raw materials to the distillation tower kettle, turn on the vacuum oil pump, set the system pressure according to the process requirements, keep the system pressure stable, turn on the distillation tower kettle electric heating device, turn on the condensed water, adjust the kettle material temperature, and when there is a distillate at the top of the distillation tower, reflux for 3 hours. (ii) Turn on the sampling pump to transport materials to the distillation tower, adjust the reflux ratio according to the process setting requirements, when the system pressure, tower top temperature, tower bottom temperature, and fraction composition are stable, and the tower bottom material composition meets the process requirements, turn on the distillation tower bottom discharge pump to transport DCPD monoepoxide compounds to the tower bottom material storage tank. The effect of distillation separation of DCPD monoepoxide compounds under different process conditions was investigated. The experimental process conditions, tower top fraction composition, distillation yield, tower bottom material composition and distillation yield are shown in Tables 3, 4, and 5, respectively.

[0074] Table 3 Distillation separation of DCPD monoepoxide operating conditions

[0075]

[0076] Table 4 Distillation separation DCPD monoepoxide overhead fraction mass percentage composition and distillation yield

[0077]

[0078] Table 5 Distillation separation DCPD monoepoxide bottom material mass percentage composition and distillation yield

[0079]

[0080] It can be seen from Tables 3, 4 and 5 that the distillation yield of DCPD and cumene is greater than 99% through distillation separation, and the recovered DCPD and cumene can be recycled as reaction materials. The number of distillation tower plates is ≧10, the distillation yield of a,a-dimethylbenzyl alcohol is 92.2% to 99.3%, the number of distillation tower plates is 20, the mass fraction of DCPD monoepoxide is greater than 90%, and the distillation yield is greater than 98%.

[0081] The process of the present invention is used to synthesize DCPD monoepoxide, and the excess DCPD put into the reactor is recovered by distillation, and the distillation yield can be greater than 99%. Therefore, according to the method provided by the present invention, in the epoxidation reaction stage, the molar ratio of DCPD to CHP put into the reactor is controlled at 3 to 4:1, and after reaction and distillation separation, the process yield of DCPD monoepoxide can be greater than 90%.

Claims

1. A method for preparing dicyclopentadiene monoepoxide, comprising: Using dicyclopentadiene as a reaction raw material, cumene hydroperoxide as an oxidant, and titanium silicon molecular sieve as a catalyst, in an inert solvent, dicyclopentadiene, cumene hydroperoxide and the titanium silicon molecular sieve catalyst are fully contacted to undergo a catalytic oxidation reaction to generate a mixed solution of dicyclopentadiene monoepoxide and α,α-dimethylbenzyl alcohol as the main product, and the dicyclopentadiene monoepoxide is obtained by separation and purification; The titanium silicon molecular sieve catalyst is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and its components include: TiO2 mass fraction of 0.10% to 6.42%, nano carbon fiber mass fraction of 44.68% to 64.11%, SiO2 mass fraction of 28.17% to 45.80%, magnesium oxide mass fraction of 0.01% to 1.98%, silane mass fraction of 0.44% to 6.93%; The catalytic oxidation reaction temperature is 60-120° C., the molar ratio of dicyclopentadiene to cumene hydroperoxide is 1-4:1, and the dicyclopentadiene monoepoxide has a structure of formula (1), (2), (3) or (4): The inert solvent is an organic hydrocarbon compound including benzene, toluene, cumene, cyclohexane, heptane, octane and decanane; The catalytic oxidation reaction temperature is 60-120° C., and the contact time of the dicyclopentadiene, the oxidant and the titanium silicon molecular sieve catalyst is 1-3 hours.

2. The method according to claim 1, characterized in that The molar ratio of dicyclopentadiene to cumene hydroperoxide is 3 to 4:

1.

3. The method according to claim 1, characterized in that: The inert solvent is cumene.

4. The method according to claim 1, characterized in that The amount of the catalyst used is 0.8% to 12.5% ​​of the total mass of the dicyclopentadiene, the oxidant and the inert solvent.

5. The method according to claims 1-4, characterized in that: The mixed liquid is transported to a first distillation tower, dicyclopentadiene and an inert solvent are collected at the top of the first distillation tower, the materials in the bottom of the first distillation tower are transported to a second distillation tower, a,a-dimethylbenzyl alcohol is collected at the top of the second distillation tower, and dicyclopentadiene monoepoxide is collected in the bottom of the second distillation tower; The first distillation tower has 6 to 20 plates, a reflux ratio of 1 to 4, a top temperature of 66.4 to 98.3°C, a top pressure of 5 to 18 kPa, and a bottom temperature of 117.7 to 151.6°C. The second distillation tower has 15 to 30 plates, a reflux ratio of 4 to 8, a top temperature of 112.9 to 130.1°C, a top pressure of 5 to 10 kPa, and a bottom temperature of 126.4 to 145.9°C.

6. The method according to claim 5, characterized in that The first distillation tower has 20 plates, a reflux ratio of 1 to 4, a top temperature of 66.4 to 98.3° C., a top pressure of 5 to 18 kPa, and a bottom temperature of 117.7 to 151.6° C.; The second distillation tower has 20 to 30 plates, a reflux ratio of 4 to 8, a top temperature of 113.0 to 130.1°C, a top pressure of 5 to 10 kPa, and a bottom temperature of 126.8 to 145.9°C.

7. The method according to claim 6, characterized in that The first distillation tower has 20 plates, a reflux ratio of 4, a top temperature of 98.3°C, a top pressure of 18 kPa, and a bottom temperature of 151.6°C; The second distillation tower has 30 plates, a reflux ratio of 8, a top temperature of 129.9°C, a top pressure of 10 kPa, and a bottom temperature of 145.9°C.

8. The method according to claims 1-4, characterized in that: The mixed liquid is transported to a distillation tower, the dicyclopentadiene and the inert solvent are collected at the top of the distillation tower, and the dicyclopentadiene monoepoxide is collected at the bottom of the distillation tower; The number of plates of the distillation tower is 6 to 20, the reflux ratio is 1 to 4, the top temperature is 65.5 to 84.9°C, the top pressure is 5 to 10 kPa, and the bottom temperature is 127.0 to 157.4°C.

9. The method according to claim 8, characterized in that: The distillation tower has 10 to 20 plates, a reflux ratio of 1 to 4, a tower top temperature of 65.5 to 84.9° C., a tower top pressure of 5 to 10 kPa, and a tower bottom temperature of 127.0 to 157.4° C.

10. The method according to claim 9, characterized in that The distillation tower has 20 plates, a reflux ratio of 4, a top temperature of 84.9°C, a top pressure of 10 kPa, and a bottom temperature of 145.7°C.

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