Mesoporous carbon immobilized transition metal oxychloride catalyst as well as in-situ synthesis method and application thereof

Abstract

The invention relates to a mesoporous carbon immobilized transition metal oxychloride catalyst as well as an in-situ synthesis method and application thereof, and belongs to the technical field of immobilized catalysts. The in-situ synthesis method comprises the following steps: firstly, dissolving transition metal salt, impregnating the transition metal salt onto mesoporous carbon under oxygen-free and water-free conditions, and then reacting in an inert atmosphere to obtain a mesoporous carbon immobilized transition metal compound; and carrying out in-situ reaction on the mesoporous carbon immobilized transition metal compound and an oxidizing agent to obtain the mesoporous carbon immobilized transition metal oxychloride catalyst. The mesoporous carbon immobilized transition metal oxychloride catalyst provided by the invention has relatively high activity and is stable to air and trace water. The mesoporous carbon immobilized transition metal oxychloride catalyst is used as a main catalyst for catalyzing dicyclopentadiene polymerization, and the obtained catalyst system has the advantages of good active component dispersibility, high catalyst utilization rate, high activity, good stability and stable polymerization reaction operation window, and is suitable for large-scale industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid-supported catalysts, and in particular relates to a mesoporous carbon-supported transition metal oxychloride catalyst and an in-situ synthesis method and application thereof, and in particular relates to the application of the mesoporous carbon-supported transition metal oxychloride catalyst in a catalyst system for dicyclopentadiene polymerization. Background Art

[0002] Dicyclopentadiene is a byproduct obtained by steam cracking during the production of ethylene. Its molecular structure contains two unsaturated double bonds, and both rings of the unsaturated double bonds can undergo ring-opening metathesis polymerization. When ring-opening metathesis polymerization occurs, the norbornene ring is more likely to open. As a new type of engineering plastic, polydicyclopentadiene has a wide range of applications in the fields of agricultural equipment, automobile manufacturing, chlor-alkali industry and petrochemical industry product manufacturing.

[0003] Polydicyclopentadiene is mainly processed by reaction injection molding, resin transfer molding and vacuum assisted molding. The catalyst has the greatest impact on the polymerization of dicyclopentadiene. The activity, functional group tolerance, stability and other factors of the catalyst will have a great influence on the polymerization reaction and the performance of the material, and also determine the industrial application value of the product.

[0004] In addition, in industrial production, the cost of the catalyst also needs to be considered. The earliest catalyst used in the ring-opening metathesis polymerization of cycloolefins was a two-component catalyst. The two-component catalyst is mainly composed of a main catalyst and a co-catalyst. The main catalyst is a compound of transition metals W, Mo, Ru, Ti, etc., and the co-catalyst includes alkyl aluminum or alkyl zinc, etc. Among them, the main catalyst plays a decisive role in the formation of metal carbene. The co-catalyst can promote the accelerated formation of metal carbene, and different co-catalysts play a decisive role in the activity of the metal carbene complex. This type of catalyst has high activity and low cost, but poor stability. The single-component catalyst is mainly a ruthenium metal carbene complex. This type of catalyst has high activity and good stability, but it is relatively expensive and cannot be used on a large scale in industrial production.

[0005] Since transition metal halides such as tungsten and molybdenum are easily oxidized in the air, and the prepared catalysts are very sensitive to air and water, which can easily lead to their deactivation. Therefore, ligand substances such as phenols and alcohols are often added. Due to the different steric hindrances and electron-donating abilities of different ligands, the stability and activity of the catalysts are also different. In addition, implosion often occurs during the reaction, which increases the difficulty of industrial application.

[0006] In the prior art, some researchers have used polystyrene and molecular sieve-loaded tungsten catalysts to catalyze the polymerization of dicyclopentadiene. The polystyrene-loaded catalyst has higher activity and better stability than the unloaded catalyst. The catalyst loaded with molecular sieve also has higher activity. However, the polystyrene-loaded tungsten catalyst belongs to physical embedding, and the catalyst utilization rate is low. In addition, there are some problems in the dispersion of inorganic carriers such as molecular sieves in dicyclopentadiene, which will affect the properties of polydicyclopentadiene.

[0007] Since the two-component catalyst is easily deactivated when exposed to air, and the use conditions are relatively harsh, it is difficult to store, which increases the cost of catalyst application. As a result, there has been no major research progress in bimetallic catalysts since their discovery. The stability and activity of the main catalyst have become key issues. Summary of the invention

[0008] In view of this, the purpose of the present invention is to provide a mesoporous carbon-supported transition metal oxychloride catalyst and its in-situ synthesis method and application. The mesoporous carbon-supported transition metal oxychloride catalyst of the present invention is used as a main catalyst for catalyzing the polymerization of dicyclopentadiene, and the obtained catalyst system has good dispersibility of active components, high catalyst utilization, high activity and good stability.

[0009] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0010] The present invention also provides an in-situ synthesis method of a mesoporous carbon-supported transition metal oxychloride catalyst, comprising the following steps:

[0011] (1) dissolving a transition metal salt, impregnating the salt onto the mesoporous carbon in an oxygen-free and water-free environment, and reacting the mixture in an inert atmosphere to obtain a transition metal compound immobilized on the mesoporous carbon;

[0012] (2) reacting the mesoporous carbon-supported transition metal compound with an oxidant in situ to obtain a mesoporous carbon-supported transition metal oxychloride catalyst.

[0013] Preferably, the mesoporous carbon is prepared by a sol-colloid template method;

[0014] More preferably, the template material used in the sol-colloid template method is aluminum salt, the carbon source is a soluble carbon-containing compound, and the mass ratio of the carbon source to the template material is 0.1 to 20 times;

[0015] Particularly preferably, the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate, aluminum acetate, and aluminum sulfate;

[0016] Particularly preferably, the carbon source is at least one of soluble α-starch, α-starch, β-starch, starch polysaccharides, sucrose, maltose, glucose, fructose, mannose, galactose, arabinose, xylose, and rhamnose;

[0017] Most preferably, the preparation method of the mesoporous carbon is:

[0018] S1. Take aluminum salt and dissolve it in distilled water to obtain an aluminum salt solution;

[0019] S2. Take a carbon source and dissolve it in distilled water to obtain a carbon source solution;

[0020] S3. Mix the aluminum salt solution and the carbon source solution, stir in a water bath at 40-80°C for 3-5h to obtain a mixed solution, evaporate to dryness at 80-100°C to obtain a precursor;

[0021] S4. The precursor is first placed in a tube furnace, calcined at 250-350°C for 4-6h under air, and then calcined at 700-800°C for 5-8h under an inert atmosphere to obtain a powder;

[0022] S5. The powder is placed in an acid solution, heated and stirred in an oil bath, the oil bath temperature is 90 to 110 ° C, the stirring time is 8 to 14 h, then filtered, and dried in an oven at 85 to 120 ° C for 8 to 20 h to obtain mesoporous carbon;

[0023] The acid solution is at least one of hydrochloric acid, nitric acid or sulfuric acid, the acid concentration is 0.5-2 mol / L, and the mass ratio of powder to acid solution is 1:3-1:30.

[0024] Preferably, the in situ synthesis method comprises the following steps:

[0025] (1) dissolving a transition metal salt in a solvent, impregnating the solvent onto mesoporous carbon in an oxygen-free and water-free environment, reacting the solvent under an inert atmosphere, drying the solid obtained after the reaction with an inert atmosphere, and cooling the solid to room temperature to obtain a transition metal compound immobilized on the mesoporous carbon;

[0026] The mass ratio of the transition metal salt to the mesoporous carbon is 0.15 to 0.7:1;

[0027] (2) adding the transition metal compound immobilized on the mesoporous carbon to a mixture of alcohol and solvent, heating the mixture to react, and obtaining a reaction product;

[0028] (3) drying the reaction product with an inert atmosphere and cooling it to room temperature, then adding a ligand solution and heating the reaction, drying the reaction product with an inert atmosphere and cooling it to room temperature to obtain a mesoporous carbon-supported transition metal oxychloride catalyst;

[0029] The molar ratio of the ligand to the transition metal salt in step (1) is 0.1 to 5:1.

[0030] More preferably, in step (1),

[0031] The transition metal salt is at least one of WCl6, MoCl5 and RuCl4;

[0032] The solvent is one or more of toluene, xylene, carbon disulfide, benzene, butyl ether, and carbon tetrachloride, and the molar ratio of the transition metal salt to the solvent is 1:2 to 1:40;

[0033] The reaction temperature is 30-50°C and the reaction time is 0.5-1.5h;

[0034] The inert atmosphere is at least one of argon and high-purity nitrogen;

[0035] It is particularly preferred that the molar ratio of the transition metal salt to the solvent is 1:12 to 1:37.

[0036] More preferably, in step (2), the reaction temperature is 40 to 70° C., the reaction time is 1 to 2 h, and the volume ratio of the transition metal compound supported on the mesoporous carbon to the mixed solution of the alcohol and the solvent is 1:2 to 1:8;

[0037] The alcohol includes at least one of 2-methyl-2-propanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, and 2,3-dimethyl-2-hexanol;

[0038] The solvent is at least one of toluene, xylene and butyl ether;

[0039] The volume ratio of the alcohol to the solvent is 0.08-0.2:1.

[0040] More preferably, in step (3), the molar ratio of the ligand to the transition metal salt is 0.3 to 1.8:1;

[0041] The reaction temperature is 40-60°C and the reaction time is 1-2h;

[0042] The ligand includes one or more of 2,6-di-tert-butyl-p-cresol, nonylphenol, and 6-tert-butyl-2,4-dimethylphenol.

[0043] The present invention also provides a mesoporous carbon-supported transition metal oxychloride catalyst prepared by the in-situ synthesis method.

[0044] The present invention also provides a catalyst system for dicyclopentadiene polymerization, comprising a main catalyst and a carbene initiator, wherein the main catalyst is a mesoporous carbon-supported transition metal oxychloride catalyst, and the carbene initiator is an alkyl aluminum compound.

[0045] The present invention also provides a method for catalyzing the polymerization of dicyclopentadiene using the above catalyst system, comprising the following steps:

[0046] (1) Under an inert atmosphere, a main catalyst and a carbene initiator are placed in the material to be polymerized, respectively, to prepare a material liquid A and a material liquid B;

[0047] The material to be polymerized includes dicyclopentadiene monomer;

[0048] (2) mixing the A liquid and the B liquid and performing thermal polymerization to obtain polydicyclopentadiene;

[0049] The polymerization temperature is 70-85°C.

[0050] Preferably, the molar ratio of dicyclopentadiene to carbene initiator in the A feed solution is 10-40:1; the molar ratio of dicyclopentadiene to main catalyst in the B feed solution is 200-1000:1, and the molar amounts of the main catalyst and the co-catalyst are calculated based on the molar amount of the metal element.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] The in-situ synthesis method of a mesoporous carbon-supported transition metal oxychloride catalyst provided by the present invention comprises dissolving a transition metal salt and then impregnating it onto the mesoporous carbon, wherein the mesoporous carbon does not need to be modified. The abundant functional groups -OH, -COOH, pyrone groups and phenolic hydroxyl groups on the surface of the mesoporous carbon are utilized to bond with transition metal ions, so that the desired active metal species are highly dispersed on the mesoporous carbon with a large specific surface area. This is beneficial to improving the activity of the prepared catalyst. Afterwards, alcohols are used in-situ to react with the supported transition metal species under an inert atmosphere to form the desired transition metal oxychloride component. The mesoporous carbon prepared by the present invention has a specific surface area of ​​1900 to 2100 m 2 / g. The large specific surface area mesoporous carbon can fully stabilize and disperse the transition metal chloride oxide, thereby effectively improving the stability and activity of the catalyst. The catalyst has a suitable operating window for dicyclopentadiene polymerization and is convenient for industrial production.

[0053] Compared with ordinary supported catalysts, the in-situ synthesized transition metal oxychloride catalyst provided by the present invention is very stable. First, the transition metal ions form bonds with the functional groups on the surface of the mesoporous carbon, and then are in-situ oxidized into the required oxychloride. The ordinary supported tungsten catalyst is only physically embedded, and there is no chemical bond effect, and the structure of the catalyst is unstable; further, the mesoporous carbon used in the present invention has a large specific surface area, many active species are immobilized, and the utilization rate of the catalyst is high. Ordinary supported catalysts have a small surface area and a low catalyst utilization rate. In addition, the mesoporous carbon itself has good dispersibility in the dicyclopentadiene monomer and will not affect the properties of the polydicyclopentadiene product. Furthermore, dicyclopentadiene can be polymerized in the pores of the mesoporous carbon, and the mesoporous carbon plays an overall supporting and linking role, effectively improving the various mechanical properties of the polydicyclopentadiene.

[0054] The present invention provides a catalyst system for dicyclopentadiene polymerization, comprising a main catalyst and a co-catalyst component. The main catalyst is prepared by the in-situ solid-supported oxidation method described in the above scheme. The catalyst provided by the present invention has high activity and stability, and is stable to air and a trace amount of water. When used as a catalyst for dicyclopentadiene polymerization, it has a stable polymerization operation window and is suitable for industrial production.

[0055] The present invention also provides a method for preparing a dicyclopentadiene polymer material, wherein the main catalyst and the co-catalyst are respectively dispersed in equal volumes of a material to be polymerized containing dicyclopentadiene to obtain a component A liquid and a component B liquid. The component A liquid and the component B liquid are then mixed to perform a polymerization reaction. The method provided by the present invention is easy to operate, and the obtained product has high mechanical properties. DETAILED DESCRIPTION

[0056] In order to further understand the present invention, preferred embodiments of the present invention are described below. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0057] The in-situ synthesis method of the mesoporous carbon-supported transition metal oxychloride catalyst of the present invention comprises the following steps:

[0058] (1) Firstly, a transition metal salt is dissolved and impregnated onto mesoporous carbon under oxygen-free and water-free conditions; then, the mixture is reacted under an inert atmosphere to obtain a transition metal compound immobilized on the mesoporous carbon.

[0059] (2) reacting the mesoporous carbon-supported transition metal compound with an oxidant in situ to obtain a mesoporous carbon-supported transition metal oxychloride catalyst.

[0060] The mesoporous carbon used in the present invention is prepared by a sol-colloid template method, the template material is aluminum salt, and the carbon source is a soluble carbon compound. The mass ratio of the carbon source to the template material is 0.1 to 20; preferably 1 to 4; the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate, aluminum acetate, and aluminum sulfate. More preferably, it is aluminum nitrate. The carbon source is at least one of soluble α-starch, α-starch, β-starch, starch polysaccharides, sucrose, maltose, glucose, fructose, mannose, galactose, arabinose, xylose, and rhamnose. Preferably, it is at least one of soluble α-starch, α-starch, and β-starch.

[0061] Take aluminum salt, dissolve it in 50-110mL pure water, stir for 1-4h, dissolve at 15-40℃, and configure it into aluminum salt solution. Take carbon source, dissolve it in 40-120mL pure water, stir for 1-5h, dissolve at 15-40℃, and configure it into carbon source solution. Drop the two solutions into a three-necked bottle in parallel, mix, react in a water bath, evaporate to dryness, and obtain a precursor. The water bath temperature is 80-100℃, preferably 90℃, the stirring time is 3-6h, preferably 4-5h, and the evaporation temperature is 80-100℃. The above precursor is placed in a tubular furnace and calcined at 250-350℃ for 4-6h. Preferably, it is calcined at 290-300℃ for 4.5-5.5h. Then switch to an inert atmosphere, which is argon or high-purity nitrogen, preferably argon. The mixture is calcined at 700-800°C for 5-8 hours, preferably at 740-760°C for 6-7 hours to obtain a powder.

[0062] The above powder is placed in an acid solution, and the oil bath temperature is 90-110°C, preferably 95-100°C. The stirring time is 8-14h, preferably 9-11h. The acid solution is at least one of hydrochloric acid, nitric acid or sulfuric acid, preferably hydrochloric acid; the acid concentration is 0.5-2mol / L, preferably 1-1.5mol / L. The mass ratio of powder to acid solution is 1:3-1:30, preferably 1:8-1:15. The above sample is placed in an oven at 85-120°C and dried for 8-20h. Mesoporous carbon is obtained.

[0063] Under an inert atmosphere, a transition metal salt is dissolved in a solvent and impregnated onto mesoporous carbon to obtain a mixture. The mass ratio of the transition metal salt to the mesoporous carbon is 0.15 to 0.7:1. The transition metal salt includes one or more of WCl6, MoCl5 and RuCl4, preferably WCl6 and / or MoCl5. The solvent used for dissolution is one or more of toluene, xylene, carbon disulfide, benzene, butyl ether, and carbon tetrachloride, preferably toluene and / or xylene. The molar ratio of the transition metal salt to the solvent is 1:2 to 1:40, preferably 1:12 to 1:37.

[0064] Under an inert atmosphere, the mixture is heated to react at a temperature of 30 to 50° C., preferably 35 to 45° C.; the reaction time is 0.5 to 1.5 hours, preferably 0.8 to 1.1 hours. The reaction product is dried with an inert atmosphere to room temperature. The inert atmosphere is at least one of argon and high-purity nitrogen, preferably argon. A transition metal compound supported on mesoporous carbon is obtained.

[0065] The transition metal compound supported on mesoporous carbon is added to a mixture of alcohol and solvent, and the temperature is raised to react. The reaction temperature is 40 to 70°C, preferably 50 to 60°C; the reaction time is 1 to 2 hours. The volume ratio of the transition metal compound supported on mesoporous carbon to the alcohol solution is 1:2 to 1:8, preferably 1:4 to 1:6. The alcohol includes at least one of 2-methyl-2-propanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, and 2,3-dimethyl-2-hexanol, preferably 2-methyl-2-butanol and / or 2-methyl-2-pentanol; the solvent is at least one of toluene, xylene and butyl ether, preferably toluene and / or xylene. The volume ratio of alcohol to solvent is preferably 0.08 to 0.2:1. The above reaction product is dried with an inert atmosphere and cooled to room temperature.

[0066] Add the ligand solution to the above reaction product, heat the reaction, the reaction temperature is 40-60°C, preferably 45-55°C; the reaction time is 1-2h, preferably 1.1-1.5h. The ligand includes one or more of 2,6-di-tert-butyl-p-cresol, nonylphenol, and 6-tert-butyl-2,4-dimethylphenol, preferably 2,6-di-tert-butyl-p-cresol and / or nonylphenol. The molar ratio of the ligand to the transition metal chloride is 0.1-5:1, preferably 0.2-2:1, and more preferably 0.3-1.8:1. The above product is dried with an inert atmosphere and cooled to room temperature. The desired mesoporous carbon-supported transition metal oxychloride catalyst is obtained.

[0067] The present invention takes transition metal chloride and alkyl alcohol as an example, and the reaction process is as follows:

[0068] MCl x +ROH→ROMCl x-1 +HCl→MOCl x-2 +RCl

[0069] M is a transition metal; R is an alkyl group;

[0070] The present invention also provides a mesoporous carbon-supported transition metal oxychloride catalyst prepared by the in-situ synthesis method. The active component of the mesoporous carbon-supported transition metal oxychloride catalyst includes a transition metal oxychloride complex.

[0071] The present invention also provides a catalyst system for dicyclopentadiene polymerization, comprising an independently formulated main catalyst and a carbene initiator, wherein the main catalyst is a mesoporous carbon-supported transition metal oxychloride catalyst, and the carbene initiator is an alkyl aluminum compound.

[0072] The present invention also provides a method for catalyzing the polymerization of dicyclopentadiene using the catalyst system, comprising the following steps:

[0073] (1) Under an inert atmosphere, a main catalyst and a carbene initiator are placed in a material to be polymerized to prepare a material liquid A and a material liquid B; the material to be polymerized includes a cyclopentadiene monomer;

[0074] (2) Under an inert atmosphere, the A liquid and the B liquid are mixed and thermally polymerized to obtain a polydicyclopentadiene material.

[0075] In the above scheme, the polymerization temperature is 70-85°C. The molar ratio of dicyclopentadiene to carbene initiator in liquid A is 6-40:1. The molar ratio of dicyclopentadiene to main catalyst in liquid B is 200-1000:1. It should be noted that after liquid A and liquid B are mixed, the obtained mixture is transferred to a mold at 75-80°C under a pressure of 1-2 MPa within 30-40 seconds, and cross-linked and polymerized within 1-4 minutes to obtain the polydicyclopentadiene material.

[0076] The terms used in the present invention generally have the meanings commonly understood by those skilled in the art, unless otherwise specified. High purity in the present invention refers to a purity greater than 99.9%.

[0077] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below in conjunction with embodiments.

[0078] Example 1

[0079] Weigh 20g aluminum nitrate into a three-necked flask, add 60mL purified water, and stir to dissolve. Weigh 10.0g β-starch, add 60mL purified water, and stir to dissolve. In a 90℃ water bath, drip the aluminum nitrate solution and starch solution into the three-necked flask in parallel, and stir to react for 4h.

[0080] The reaction solution was poured into a ceramic evaporating dish and heated in a water bath at 90°C to evaporate to dryness.

[0081] The dried precursor was pre-calcined in a muffle furnace at 300°C for 5 h and then ground into fine powder using an agate mortar.

[0082] After grinding, 2 g of the powder was weighed and placed in a tube furnace and calcined at 750 °C for 6 h under argon gas protection.

[0083] Weigh 1g of the calcined powder and place it in a conical flask. Add 20mL of 1.2mol / L hydrochloric acid solution and stir at 110℃ for 9h.

[0084] The above was filtered and washed with pure water.

[0085] The filter cake was placed in an oven at 100°C and dried for 16 hours to obtain mesoporous carbon C1. After testing, the specific surface area of ​​the obtained mesoporous carbon was 1991.6 m 2 / g.

[0086] Example 2

[0087] Weigh 20g aluminum nitrate into a three-necked flask, add 60mL pure water, and stir to dissolve. Weigh 10.0g α-starch, add 60mL pure water, and stir to dissolve. In a 90℃ water bath, drip the aluminum nitrate solution and starch solution into the three-necked flask in parallel and stir to react for 4h.

[0088] The reaction solution was poured into a ceramic evaporating dish and heated in a water bath at 90°C to evaporate to dryness.

[0089] The dried precursor was pre-calcined in a muffle furnace at 300°C for 5 h and then ground into fine powder using an agate mortar.

[0090] After grinding, 2 g of the powder was weighed and placed in a tube furnace and calcined at 750 °C for 6 h under argon gas protection.

[0091] Weigh 1g of the calcined powder and place it in a conical flask. Add 25mL of 1.2mol / L hydrochloric acid solution and stir at 110℃ for 9h.

[0092] The above was filtered and washed with pure water.

[0093] The filter cake was placed in an oven at 100°C and dried for 16 hours to obtain mesoporous carbon C2. After testing, the specific surface area of ​​the obtained mesoporous carbon was 1974 m 2 / g.

[0094] Example 3

[0095] Under argon protection, weigh 1.06g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 2.23g mesoporous carbon C1 and react at 40℃ for 1h.

[0096] The reaction product was dried with argon and cooled to room temperature.

[0097] Measure 0.5 mL of 2-methyl-2-propanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0098] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0099] 1 mL of 2,6-di-tert-butyl-p-cresol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0100] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0101] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-1 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0102] Example 4

[0103] Under argon protection, weigh 1.06g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 2.23g mesoporous carbon C1 and react for 1h.

[0104] The reaction product was dried with argon and cooled to room temperature.

[0105] Measure 0.5 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0106] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0107] 0.5 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0108] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0109] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-2 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0110] Example 5

[0111] Under argon protection, weigh 1.06g WCl6 and put it into a 100mL three-necked bottle. Add 5mL xylene and heat to 40℃ to dissolve for 1h. Then add 2.23g mesoporous carbon C1 and react for 1h.

[0112] The reaction product was dried with argon and cooled to room temperature.

[0113] Measure 0.5 mL of 2-methyl-2-propanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0114] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0115] 0.5 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0116] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0117] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-3 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0118] Example 6

[0119] Under argon protection, weigh 1.50g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 3.23g mesoporous carbon C1 and react for 1h.

[0120] The reaction product was dried with argon and cooled to room temperature.

[0121] Measure 0.3 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0122] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0123] 0.3 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0124] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0125] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-4 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0126] Example 7

[0127] Under argon protection, weigh 0.50g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 1.07g mesoporous carbon C1 and react for 1h.

[0128] The reaction product was dried with argon and cooled to room temperature.

[0129] Measure 0.3 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0130] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0131] 0.56 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0132] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0133] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-5 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0134] Example 8

[0135] Under argon protection, weigh 0.50g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 1.53g mesoporous carbon C1 and react for 1h.

[0136] The reaction product was dried with argon and cooled to room temperature.

[0137] Measure 0.3 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0138] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0139] 0.56 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0140] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0141] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-6 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0142] Example 9

[0143] Under argon protection, weigh 0.50g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 2.58g mesoporous carbon C1 and react for 1h.

[0144] The reaction product was dried with argon and cooled to room temperature.

[0145] Measure 0.3 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0146] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0147] 0.56 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0148] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0149] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-7 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0150] Example 10

[0151] Under argon protection, weigh 0.50g WCl6 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 3.09g mesoporous carbon C2 and react for 1h.

[0152] The reaction product was dried with argon and cooled to room temperature.

[0153] Measure 0.3 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0154] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0155] 0.56 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0156] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0157] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-8 was obtained and diluted with a solvent to a tungsten content of 0.2 mol / L.

[0158] Embodiment 11

[0159] Under argon protection, weigh 0.80g MoCl5 and put it into a 100mL three-necked bottle. Add 5mL toluene and heat to 40℃ to dissolve for 1h. Then add 3.51g mesoporous carbon C2 and react for 1h.

[0160] The reaction product was dried with argon and cooled to room temperature.

[0161] Measure 0.3 mL of 2-methyl-2-pentanol and add 3 mL of toluene, mix well. Add to the above product and stir well. Heat to 50°C and react for 1.5 hours.

[0162] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0163] 0.56 mL of nonylphenol was dissolved in 2 mL of toluene, added to the above reaction product, and stirred at room temperature for 1 h.

[0164] After the reaction was completed, the mixture was dried with argon and cooled to room temperature.

[0165] The desired mesoporous carbon-supported transition metal oxychloride catalyst ZC-9 was obtained and diluted with a solvent to a molybdenum content of 0.2 mol / L.

[0166] Example 12

[0167] Measure 3 mL of diethylaluminum monochloride, place it in a flat-bottom centrifuge tube, add 30 mL of dicyclopentadiene, seal it, and ultrasonicate it for 30 minutes to obtain feed solution A.

[0168] 5 mL of the mesoporous carbon-supported transition metal oxychloride catalyst (ZC-1) prepared in Example 3 was measured and placed in a flat-bottom centrifuge tube. 30 mL of dicyclopentadiene was added, and the tube was sealed and ultrasonicated for 30 min to obtain a feed solution B.

[0169] Component A and component B are quickly mixed together, injected into a mold preheated to 80°C, and quickly solidified to form a cross-linked solid to obtain polydicyclopentadiene.

[0170] According to the preparation method of Example 12, other series of mesoporous carbon-supported transition metal oxychloride catalysts prepared in Examples 4 to 11 are used as catalysts to prepare corresponding B liquids; according to the method of Example 12, A liquids are prepared; according to the polymerization method of Example 12, polymerization is carried out to obtain corresponding polydicyclopentadiene. The mechanical properties of polydicyclopentadiene are shown in Table 1 (ZC-1-9).

[0171] According to the preparation method of B feed solution in Example 12, B feed solution was prepared and then exposed to air for 12 hours. Then, A feed solution was prepared according to the method of preparing A feed solution in Example 12. Dicyclopentadiene polymerization was carried out according to the polymerization method in Example 12. The mechanical properties of polydicyclopentadiene are shown in Table 1 (W-ZC-1).

[0172] Table 1 Mechanical properties test results of polydicyclopentadiene

[0173]

[0174] After exposure to air, the mechanical properties of the prepared polydicyclopentadiene decreased slightly and can be considered to be basically unchanged, indicating that it has excellent stability.

[0175] It can be seen from the above examples that the mesoporous carbon-supported transition metal oxychloride in-situ synthesis catalyst provided by the present invention has high activity and stability, and is used as a main catalyst to initiate the ring-opening metathesis polymerization of dicyclopentadiene, and the product has good mechanical properties. In addition, the in-situ synthesis catalyst preparation method of the mesoporous carbon-supported transition metal oxychloride catalyst provided by the present invention is simple, can be mass-produced, and is suitable for industrial production.

[0176] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An in-situ synthesis method of a mesoporous carbon-supported transition metal oxychloride catalyst, characterized in that: The following steps are involved: (1) dissolving a transition metal salt, impregnating the salt onto the mesoporous carbon in an oxygen-free and water-free environment, and reacting the mixture in an inert atmosphere to obtain a transition metal compound immobilized on the mesoporous carbon; (2) reacting the mesoporous carbon-supported transition metal compound with an oxidant in situ to obtain a mesoporous carbon-supported transition metal oxychloride catalyst.

2. The in-situ synthesis method of the mesoporous carbon-supported transition metal oxychloride catalyst according to claim 1, characterized in that: The mesoporous carbon is prepared by a sol-colloid template method; The template material used in the sol-colloid template method is an aluminum salt, and the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate, aluminum acetate, and aluminum sulfate; The carbon source is a soluble carbon-containing compound, and the soluble carbon-containing compound is at least one of soluble α-starch, α-starch, β-starch, starch polysaccharide, sucrose, maltose, glucose, fructose, mannose, galactose, arabinose, xylose, and rhamnose; The mass ratio of the carbon source to the template material is 0.1-20.

3. The in-situ synthesis method of the mesoporous carbon-supported transition metal oxychloride catalyst according to claim 2, characterized in that: The preparation method of the mesoporous carbon carrier is: S1. Take aluminum salt and dissolve it in distilled water to obtain an aluminum salt solution; S2. Take a carbon source and dissolve it in distilled water to obtain a carbon source solution; S3. Mix the aluminum salt solution and the carbon source solution, stir in a water bath at 40-80°C for 3-5h to obtain a mixed solution, evaporate to dryness at 80-100°C to obtain a precursor; S4. The precursor is first placed in a tube furnace, calcined at 250-350°C for 4-6h under air, and then calcined at 700-800°C for 5-8h under an inert atmosphere to obtain a powder; S5. The powder is placed in an acid solution, heated and stirred in an oil bath, the oil bath temperature is 90 to 110 ° C, the stirring time is 8 to 14 h, then filtered, and dried in an oven at 85 to 120 ° C for 8 to 20 h to obtain mesoporous carbon; The acid solution is at least one of hydrochloric acid, nitric acid or sulfuric acid, the acid concentration is 0.5 to 2 mol / L, and the mass ratio of the powder to the acid in the acid solution is 1:3 to 1:

30.

4. The in-situ synthesis method of the mesoporous carbon-supported transition metal oxychloride catalyst according to claim 1, characterized in that: (1) dissolving a transition metal salt in a solvent, impregnating the solvent onto mesoporous carbon in an oxygen-free and water-free environment, reacting the solvent under an inert atmosphere, drying the solid obtained after the reaction with an inert atmosphere, and cooling the solid to room temperature to obtain a transition metal compound immobilized on the mesoporous carbon; The mass ratio of the transition metal salt to the mesoporous carbon is 0.15 to 0.7:1; (2) adding the transition metal compound immobilized on the mesoporous carbon to a mixture of alcohol and solvent, heating the mixture to react, and obtaining a reaction product; (3) drying the reaction product with an inert atmosphere and cooling it to room temperature, then adding a ligand solution and heating the reaction, drying the reaction product with an inert atmosphere and cooling it to room temperature to obtain a mesoporous carbon-supported transition metal oxychloride catalyst; The molar ratio of the ligand to the transition metal salt in step (1) is 0.1 to 5:

1.

5. The in-situ synthesis method of the mesoporous carbon-supported transition metal oxychloride catalyst according to claim 4, characterized in that: In step (1), The transition metal salt is at least one of WCl6, MoCl5 and RuCl4; The solvent is one or more of toluene, xylene, carbon disulfide, benzene, butyl ether, and carbon tetrachloride, and the molar ratio of the transition metal salt to the solvent is 1:2 to 1:40; The reaction temperature is 30-50°C and the reaction time is 0.5-1.5h; The inert atmosphere is at least one of argon and high-purity nitrogen.

6. The mesoporous carbon-supported transition metal oxychloride catalyst prepared by the in-situ synthesis method according to claim 4, characterized in that: In step (2), the reaction temperature is 40 to 70° C., the reaction time is 1 to 2 hours, and the volume ratio of the transition metal compound supported on the mesoporous carbon to the mixed solution of the alcohol and the solvent is 1:2 to 1:8; The alcohol includes at least one of 2-methyl-2-propanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, and 2,3-dimethyl-2-hexanol; The solvent is at least one of toluene, xylene and butyl ether; The volume ratio of the alcohol to the solvent is 0.08 to 0.2:1; In step (3), the reaction temperature is 40-60° C. and the reaction time is 1-2 h; The ligand includes one or more of 2,6-di-tert-butyl-p-cresol, nonylphenol, and 6-tert-butyl-2,4-dimethylphenol; The molar ratio of the ligand to the transition metal salt is 0.3-1.8:

1.

7. A mesoporous carbon-supported transition metal oxychloride catalyst prepared by the in-situ synthesis method according to any one of claims 1 to 6.

8. A catalyst system for the polymerization of dicyclopentadiene, characterized in that The invention comprises a main catalyst and a carbene initiator, wherein the main catalyst is the mesoporous carbon-supported transition metal oxychloride catalyst as claimed in claim 7, and the carbene initiator is an alkyl aluminum compound.

9. The method for polymerizing dicyclopentadiene using a catalyst system according to claim 8, characterized in that: The following steps are involved: (1) Under an inert atmosphere, a main catalyst and a carbene initiator are placed in the material to be polymerized, respectively, to prepare a material liquid A and a material liquid B; The material to be polymerized includes cyclopentadiene monomer; (2) mixing the A liquid and the B liquid and performing thermal polymerization to obtain polydicyclopentadiene; The polymerization temperature is 70-85°C.

10. The method for polymerizing dicyclopentadiene using a catalyst system according to claim 9, characterized in that: The molar ratio of dicyclopentadiene to carbene initiator in the A feed solution is 10-40:1; the molar ratio of dicyclopentadiene to main catalyst in the B feed solution is 200-1000:1, and the molar amount of the main catalyst and the co-catalyst is calculated based on the molar amount of the metal element.

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