Preparation method of tricyclodecene compound

Abstract

The invention relates to a preparation method of a tricyclodecene compound, belongs to the technical field of organic synthesis, and solves at least one of the problems of low yield, low efficiency, complex process and the like of the existing method. According to the preparation method disclosed by the invention, cyclopentadiene and the polymerization inhibitor are selected to be dropwise added into cyclopentene at a constant speed for reaction, and the constant-speed dropwise adding time is the same as the Diels-Alder reaction time, so that by adopting cyclopentadiene, the reaction activity and selectivity are higher, the side reaction is less, the product yield is higher, and the yield of the product is higher. The concentration of cyclopentadiene in the reaction liquid can be effectively reduced through constant-speed dropwise adding, the self-polymerization reaction is reduced, and the generation of by-products is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing a tricyclodecene compound. Background Art

[0002] Cyclic olefin polymers are a type of amorphous transparent polymer material formed by the copolymerization of cycloolefins and ethylene or alpha olefins. They have the advantages of excellent optical transparency, low water absorption, high strength, high heat resistance, and high chemical corrosion resistance. They are suitable for the production of optical components and high-end pharmaceutical packaging materials and other products. They are polymer materials that have attracted great attention in industry and academia in recent years.

[0003] Cyclic olefin materials have many excellent performance characteristics, but they also have some limitations. Currently, an important method to improve their performance is to introduce large steric hindrance monomers into the polymer. By introducing large steric hindrance monomers, a higher glass transition temperature can be achieved at a relatively low insertion rate of cycloolefin monomers. At this time, more ethylene segments are still retained in the polymer chain, making the molecular chain more flexible and the chain entanglement density larger, thereby improving the toughness of the material. Therefore, in order to achieve better COC product performance, the first task is to develop an efficient method for preparing colorless, high-purity large steric hindrance cycloolefin monomers.

[0004] In the prior art, dicyclopentadiene and cyclopentene are usually mixed and then subjected to a Diels-Alder addition reaction to prepare tricyclodecene compounds. Although the tricyclodecene compounds prepared by this method have a high purity, the yield is low. Summary of the invention

[0005] In view of the above analysis, the present invention aims to provide a method for preparing a tricyclodecene compound, so as to solve at least one of the problems of low yield, low efficiency and complex process in the existing method.

[0006] In a first aspect, the present invention provides a method for preparing a tricyclodecene compound, comprising mixing cyclopentadiene and a polymerization inhibitor, uniformly dropping the mixture into cyclopentene, heating the mixture under the protection of an inert gas to perform a Diels-Alder reaction, and purifying the mixture to obtain the tricyclodecene compound;

[0007] Among them, the flow rate of uniform dripping is F, and F satisfies the following formula:

[0008]

[0009] m is the total mass of cyclopentadiene and inhibitor, and t is the Diels-Alder reaction time.

[0010] Furthermore, the molar ratio of cyclopentadiene to cyclopentene is 1:1.0 to 1.5.

[0011] Furthermore, the mass of the polymerization inhibitor is 0.1-0.5% of the total mass of cyclopentadiene and cyclopentene.

[0012] Furthermore, the Diels-Alder reaction temperature is 200-260°C, and the reaction time is 4-6h.

[0013] Furthermore, before heating, the pressure of the inert gas is 0.5 to 3 MPa.

[0014] Furthermore, the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butylhydroquinone, bisphenol A, 4-cinnamylphenol, p-phenylenediamine, benzidine, and phenothiazine.

[0015] Furthermore, the inert gas is one of nitrogen, helium and argon.

[0016] Furthermore, the purification specifically includes: firstly performing atmospheric distillation to recover cyclopentene, and then performing reduced pressure distillation to purify and collect the tricyclodecene compound.

[0017] Furthermore, the temperature of atmospheric distillation is 70-85°C.

[0018] Furthermore, the temperature of the reduced pressure distillation is 130-150°C.

[0019] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0020] (1) In the preparation method of the present invention, cyclopentadiene and a polymerization inhibitor are uniformly added dropwise to cyclopentene for reaction, and the uniform addition time is the same as the Diels-Alder reaction time. The method of the present invention uses cyclopentadiene to make the reaction activity and selectivity higher, the side reaction is less, and the product yield is higher. The uniform addition can effectively reduce the concentration of cyclopentadiene in the reaction solution, reduce the self-polymerization reaction, and reduce the generation of by-products;

[0021] (2) The method of the present invention can also reduce the amount of cyclopentene used, so that a high molar ratio of cyclopentene to cyclopentadiene can be maintained at a lower cyclopentene amount, thereby reducing the recovery cost of cyclopentene; finally, by adding a specific feed ratio and a free radical inhibitor, as well as selecting an appropriate temperature, the free radical polymerization of cyclopentadiene can be effectively inhibited, the generation of by-products can be reduced, and the reaction efficiency can be improved. The excess cyclopentene can be recovered and reused by a simple distillation purification method, thereby reducing the loss of raw materials;

[0022] (3) The method of the present invention has a simple process, the raw materials for the production process are cheap and easily available, the requirements for experimental equipment are relatively low, and the entire process is safe and controllable.

[0023] In the present invention, the above-mentioned technical solutions can also be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description, and some advantages can become obvious from the description, or can be understood by practicing the present invention. The purpose and other advantages of the present invention can be achieved and obtained through the contents particularly pointed out in the description. DETAILED DESCRIPTION

[0024] The preferred embodiments of the present invention are described in detail below, wherein the embodiments of the present invention are used to illustrate the principles of the present invention but are not used to limit the scope of the present invention.

[0025] A specific embodiment of the present invention discloses a method for preparing a tricyclodecene compound, comprising mixing cyclopentadiene and a polymerization inhibitor, uniformly adding the mixture dropwise to cyclopentene, heating under the protection of an inert gas to perform a Diels-Alder reaction, and purifying the mixture to obtain the tricyclodecene compound;

[0026] Among them, the flow rate of uniform dripping is F, and F satisfies the following formula:

[0027]

[0028] m is the total mass of cyclopentadiene and inhibitor, and t is the Diels-Alder reaction time.

[0029] In the preparation method of the present invention, cyclopentadiene and a polymerization inhibitor are uniformly added to cyclopentene for reaction, and the uniform dropping time is the same as the Diels-Alder reaction time. The method of the present invention adopts cyclopentadiene to make the reaction activity and selectivity higher, the side reaction is less, and the product yield is higher. The uniform dropping can effectively reduce the concentration of cyclopentadiene in the reaction solution, reduce the self-polymerization reaction, and reduce the generation of by-products. The method of the present invention can also reduce the amount of cyclopentene, so that the molar ratio of high cyclopentene to cyclopentadiene can be maintained under a lower amount of cyclopentene, thereby reducing the recovery cost of cyclopentene. Finally, by adding a specific feed ratio and a free radical polymerization inhibitor, and selecting an appropriate temperature, the free radical polymerization of cyclopentadiene can be effectively inhibited, the generation of by-products can be reduced, and the reaction efficiency can be improved. The excess cyclopentene can be recovered and reused by a simple distillation purification method, thereby reducing the loss of raw materials. At the same time, the method of the present invention has a simple process, the raw materials of the production process are cheap and easy to obtain, the requirements for experimental equipment are low, and the whole process is safe and controllable.

[0030] It should be noted that the structural formula of the tricyclodecene compound described in the present invention is as follows:

[0031]

[0032] Specifically, the cyclopentadiene is cracked by dicyclopentadiene at 170-200° C. (e.g., 170° C., 180° C., 190° C., 200° C.) for 2-6 hours, e.g., 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h.

[0033] After a large number of experiments, it was found that when cracking cyclopentadiene, if the cracking time is insufficient, the cracking of dicyclopentadiene will be incomplete and the conversion rate will be reduced. If the cracking time is too long, it will lead to an increase in by-products and a decrease in reaction selectivity. Preferably, the time for cracking dicyclopentadiene to prepare cyclopentadiene is 4 to 5 hours.

[0034] Specifically, the molar ratio of cyclopentadiene to cyclopentene is 1:1.0 to 1.5, for example, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5.

[0035] It should be noted that in the present invention, cyclopentadiene and cyclopentene adopt the above-mentioned range, because there is a competitive relationship between the main reaction of cyclopentadiene and cyclopentene and its self-polymerization reaction. By adjusting the molar ratio of the two, the selectivity and yield of the reaction can be effectively regulated. Specifically, when the molar ratio of cyclopentene to cyclopentadiene is increased, that is, when the amount of cyclopentene is increased, the concentration of cyclopentadiene in the reaction solution is reduced, thereby slowing down the speed of its self-polymerization reaction. This not only improves the selectivity and yield of the main reaction, but also reduces the occurrence of side reactions. However, too large a ratio will cause the reaction rate and efficiency to decrease, and increase the recovery cost, causing a waste of resources. When the molar ratio of cyclopentene to cyclopentadiene is reduced, that is, when the amount of cyclopentene is reduced, the concentration of cyclopentadiene in the reaction solution increases, and the number of dienophiles increases, thereby increasing the collision probability and contact frequency between molecules, and accelerating the reaction rate. But if the ratio is too low, the generation of by-products will be promoted, affecting the purity and yield of the final product.

[0036] Specifically, the mass of the polymerization inhibitor is 0.1-0.5% of the total mass of cyclopentadiene and cyclopentene, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%.

[0037] It should be noted that if the content of the inhibitor is too high, the yield will be reduced, and if the content is too low, the formation of by-products will increase, the conversion rate will decrease, and the yield will decrease.

[0038] Specifically, the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butylhydroquinone, bisphenol A, 4-cinnamylphenol, p-phenylenediamine, benzidine, and phenothiazine.

[0039] Specifically, the inert gas is one of nitrogen, helium and argon, preferably nitrogen.

[0040] Specifically, the Diels-Alder reaction temperature is 200-260°C, for example, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, and the reaction time is 4-6h, for example, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5.0h, 5.2h, 5.4h, 5.6h, 5.8h, 6h.

[0041] In the present invention, when the Diels-Alder reaction is carried out at a temperature below 180°C, the reaction is difficult to proceed, the reaction conversion rate is significantly reduced or almost no reaction occurs. When the reaction temperature is too high, unnecessary side reactions will occur between cyclopentadiene and cycloolefins, reducing the selectivity and yield of the reaction. Preferably, the reaction temperature of the Diels-Alder reaction is 200 to 260°C, preferably, the temperature is 230°C, and the reaction time is 4h.

[0042] Specifically, before heating, the pressure of the inert gas is 0.5 to 3 MPa, for example, 0.5 MPa, 0.7 MPa, 0.9 MPa, 1.0 MPa, 1.2 MPa, 1.4 MPa, 1.5 MPa, 1.7 MPa, 1.9 MPa, 2.0 MPa, 2.2 MPa, 2.4 MPa, 2.5 MPa, 2.7 MPa, 2.9 MPa, and 3 MPa.

[0043] It should be noted that the selectivity of the Diels-Alder reaction carried out under a certain pressure is significantly higher than that of the normal pressure or low pressure reaction using the same protective gas. However, when the pressure is too high, the reaction yield is not greatly improved, and the requirements for the reaction equipment are increased, which increases the cost.

[0044] Specifically, the purification specifically includes: firstly performing atmospheric distillation to recover cyclopentene, and then performing reduced pressure distillation to purify and collect the tricyclodecene compound.

[0045] Preferably, the temperature of atmospheric distillation is 70-85°C, for example, 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 85°C.

[0046] The boiling point of cyclopentene at normal pressure is 44-46°C. The impurities in the mixed solution after the reaction mainly include excess unreacted cyclopentene and by-product polymers. In order to effectively separate these components, the temperature is raised to 70-85°C to remove unreacted cyclopentene. If the temperature is too low, it will lead to incomplete distillation.

[0047] Preferably, the pressure of the reduced pressure distillation is 0.1 MPa, the temperature is 130-150°C, for example, 130°C 135°C, 140°C, 145°C, 150°C, and the distillation temperature is 95-105°C, for example, 95°C, 97°C, 99°C, 101°C, 103°C, 105°C.

[0048] The boiling point of tricyclodecene monomer is 200℃ under normal pressure, and it can be separated from the mixed liquid at 130℃ under reduced pressure distillation. If the temperature is too low, the monomer product cannot be separated, and if the temperature is too high, the distillation product will contain polymer impurities.

[0049] The tricyclodecene compound prepared by the method of the present invention has a yield greater than 85%, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, preferably, the yield is 85.3-92.5%, and the purity is greater than 99%.

[0050] The yield in the present invention is the mass percentage of the weight of the target product to the total weight of the added cycloolefin and cyclopentadiene.

[0051] The technical solution of the present invention is further explained below in conjunction with specific embodiments.

[0052] The cyclopentadiene in the following examples and comparative examples was prepared by cracking dicyclopentadiene at 180° C. for 4.5 h.

[0053] Example 1

[0054] A method for preparing a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g (3mol) of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave with nitrogen three times, and filling the autoclave with 0.5MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 200°C, and the reaction time is 4h. After reaching a predetermined temperature, 132g of cyclopentadiene (2mol) and 0.336g of 2,6-di-tert-butyl-p-cresol (mass percentage is 0.1%) are added dropwise to the autoclave at a uniform rate within 4h. After the addition is completed, the autoclave is naturally cooled to room temperature, the autoclave is opened to transfer the reactants to the distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed liquid was transferred to a reduced pressure distillation apparatus, the vacuum degree was controlled at 0.1 MPa, the distillation temperature was 130° C., and the product with a fraction of 95 to 105° C. was collected, which was the tricyclodecene compound. The yield and purity of the target product were measured and are shown in Table 1.

[0055] Example 2

[0056] A preparation method of a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave three times with nitrogen, and filling the autoclave with 0.5MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 0.336g of hydroquinone are added dropwise to the reactor in a uniform dropwise manner within 4h. After the dropwise addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a vacuum distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product with a fraction of 95-105°C is collected, which is a tricyclodecene compound, and the target product yield and purity are measured as shown in Table 1.

[0057] Example 3

[0058] A preparation method of a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave with nitrogen three times, and filling the autoclave with 0.5MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 260°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 0.336g of 2-tert-butylhydroquinone are added dropwise to the reactor at a uniform rate within 4h. After the dropwise addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a vacuum distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product with a fraction of 95-105°C is collected, which is a tricyclodecene compound, and the target product yield and purity are measured as shown in Table 1.

[0059] Example 4

[0060] A preparation method of a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave three times with nitrogen, and filling the autoclave with 1MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 0.336g of 4-cinnamon phenol are added dropwise to the reactor in a uniform dropwise manner within 4h. After the dropwise addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a vacuum distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product with a fraction of 95-105°C is collected, which is a tricyclodecene compound, and the target product yield and purity are measured as shown in Table 1.

[0061] Example 5

[0062] A preparation method of a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave three times with nitrogen, and filling the autoclave with 2MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 0.336g of p-phenylenediamine are added dropwise to the reactor in a uniform dropwise manner within 4h. After the dropwise addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a vacuum distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product of the fraction of 95-105°C is collected, which is a tricyclodecene compound, and the target product yield and purity are measured as shown in Table 1.

[0063] Example 6

[0064] A preparation method of a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave three times with nitrogen, and filling the autoclave with 3MPa of nitrogen for the last time. Stirring is turned on, and the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 0.336g of benzidine are added dropwise to the reactor in a uniform dropwise manner within 4h. After the dropwise addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a vacuum distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product of the fraction of 95-105°C is collected, which is a tricyclodecene compound, and the target product yield and purity are measured as shown in Table 1.

[0065] Example 7

[0066] A method for preparing a tricyclodecene compound of the present embodiment comprises the following steps: adding 136g (2mol) of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave with nitrogen three times, and filling the autoclave with 2MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g (2mol) of cyclopentadiene and 0.268g of 2,6-di-tert-butyl-p-cresol are added dropwise to the autoclave at a uniform rate within 4h. After the addition is completed, the autoclave is naturally cooled to room temperature, the autoclave is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed liquid was transferred to a reduced pressure distillation apparatus, the vacuum degree was controlled at 0.1 MPa, the distillation temperature was 130° C., and the product with a fraction of 95 to 105° C. was collected, which was the tricyclodecene compound. The yield and purity of the target product were measured and are shown in Table 1.

[0067] Example 8

[0068] A method for preparing a tricyclodecene compound of the present embodiment comprises the following steps: adding 170g (2.5mol) of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave with nitrogen three times, and filling the autoclave with 2MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g (2mol) of cyclopentadiene and 0.302g of 2,6-di-tert-butyl-p-cresol are added dropwise to the autoclave at a uniform rate within 4h. After the addition is completed, the autoclave is naturally cooled to room temperature, the autoclave is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed liquid was transferred to a reduced pressure distillation apparatus, the vacuum degree was controlled at 0.1 MPa, the distillation temperature was 130° C., and the product with a fraction of 95 to 105° C. was collected, which was the tricyclodecene compound. The yield and purity of the target product were measured and are shown in Table 1.

[0069] Example 9

[0070] A method for preparing a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave with nitrogen three times, and filling the autoclave with 2MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 1.008g of 2,6-di-tert-butyl-p-cresol are added dropwise to the reactor at a uniform rate within 4h. After the addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a vacuum distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product with a fraction of 95-105°C is collected, which is a tricyclodecene compound, and the target product yield and purity are measured as shown in Table 1.

[0071] Example 10

[0072] A method for preparing a tricyclodecene compound of the present embodiment comprises the following steps: adding 204g of cyclopentene to a 500mL autoclave, sealing the autoclave, replacing the autoclave with nitrogen three times, and filling the autoclave with 2MPa of nitrogen for the last time. Stirring is turned on, the reaction temperature is set to 230°C, and the reaction time is 4h. After rising to a predetermined temperature, 132g of cyclopentadiene and 1.68g of 2,6-di-tert-butyl-p-cresol are added dropwise to the reactor at a uniform rate within 4h. After the addition is completed, the reactor is naturally cooled to room temperature, the reactor is opened to transfer the reactants to a distillation apparatus, the temperature is set to 70-90°C, and the excess cyclopentene is recovered by atmospheric distillation. Subsequently, the remaining mixed solution is transferred to a reduced pressure distillation apparatus, the vacuum degree is controlled to 0.1Mpa, the distillation temperature is 130°C, and the product with a fraction of 95-105°C is collected, which is a tricyclodecene compound, and the yield and purity of the target product are measured as shown in Table 1.

[0073] Comparative Example 1

[0074] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that the molar ratio of cyclopentadiene to cyclopentene is 1:0.9. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0075] Comparative Example 2

[0076] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that the molar ratio of cyclopentadiene to cyclopentene is 1:1.6. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0077] Comparative Example 3

[0078] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that the mass of the polymerization inhibitor is 0.08% of the total mass of cyclopentadiene and cyclopentene. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0079] Comparative Example 4

[0080] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that the mass of the polymerization inhibitor is 0.6% of the total mass of cyclopentadiene and cyclopentene. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0081] Comparative Example 5

[0082] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that cyclopentadiene and 2,6-di-tert-butyl-p-cresol are mixed and then directly added to the cyclopentene. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0083] Comparative Example 6

[0084] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that the nitrogen pressure is 0.4 MPa. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0085] Comparative Example 7

[0086] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that the nitrogen pressure is 3.5 MPa. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0087] Comparative Example 8

[0088] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that no polymerization inhibitor is added. The yield and purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0089] Comparative Example 9

[0090] The preparation method of a tricyclodecene compound in this comparative example is the same as that in Example 1, except that cyclopentadiene is replaced by dicyclopentadiene. The yield and GC analysis purity of the tricyclodecene compound prepared in this comparative example are shown in Table 1.

[0091] Table 1

[0092] Group Yield (%) purity(%) Example 1 85.3 ＞99 Example 2 88.5 ＞99 Example 3 86.1 ＞99 Example 4 88.3 ＞99 Example 5 92.5 ＞99 Example 6 88.7 ＞99 Example 7 87.9 ＞99 Example 8 89.2 ＞99 Example 9 88.5 ＞99 Example 10 85.6 ＞99 Comparative Example 1 75.7 96 Comparative Example 2 80.1 ＞99 Comparative Example 3 81.5 98 Comparative Example 4 78.8 ＞99 Comparative Example 5 60.2 ＞99 Comparative Example 6 75.2 ＞99 Comparative Example 7 83.6 ＞99 Comparative Example 8 66.7 98 Comparative Example 9 70.9 96

[0093] By comparing Examples 1-10 with Comparative Examples 1-9, the tricyclodecene compound prepared by the method of the present invention has both high yield and purity, the yield can reach more than 85%, and the purity is greater than 99%.

[0094] Compared with Example 1, the molar ratio of cyclopentadiene to cyclopentene in Comparative Example 1-2 is not within the scope of the present invention, and the yield of the prepared tricyclodecene compound is significantly reduced.

[0095] Compared with Example 1, in Comparative Example 3-4, the mass of the polymerization inhibitor, i.e., the total mass of cyclopentadiene and cyclopentene, is not within the scope of the present invention, and the yield of the prepared tricyclodecene compound is significantly reduced.

[0096] Comparative Example 5 Compared with Example 1, cyclopentadiene and 2,6-di-tert-butyl-p-cresol are mixed and then directly added to cyclopentene instead of adding at a uniform rate. The yield of the prepared tricyclodecene compound is significantly reduced.

[0097] Compared with Example 1, in Comparative Examples 6-7, the nitrogen pressure is not within the scope of the present invention, and the yield of the prepared tricyclodecene compound is significantly reduced.

[0098] Compared with Example 1, when no polymerization inhibitor was added, the yield and purity of the prepared tricyclodecene compound were significantly reduced in Comparative Example 8.

[0099] In Comparative Example 9, compared with Example 1, cyclopentadiene was replaced by dicyclopentadiene, and the yield and purity of the prepared tricyclodecene compound were significantly reduced.

[0100] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a tricyclodecene compound, characterized in that: The method comprises mixing cyclopentadiene and a polymerization inhibitor, uniformly dropping the mixture into cyclopentene, heating the mixture under the protection of an inert gas to carry out a Diels-Alder reaction, and purifying the mixture to obtain the tricyclodecene compound; Among them, the flow rate of uniform dripping is F, and F satisfies the following formula: m is the total mass of cyclopentadiene and inhibitor, and t is the Diels-Alder reaction time.

2. The method for preparing a tricyclodecene compound according to claim 1, characterized in that: The molar ratio of cyclopentadiene to cyclopentene is 1:1.0-1.

5.

3. The method for preparing a tricyclodecene compound according to claim 1, characterized in that: The mass of the polymerization inhibitor is 0.1-0.5% of the total mass of cyclopentadiene and cyclopentene.

4. The method for preparing a tricyclodecene compound according to any one of claims 1 to 3, characterized in that: The Diels-Alder reaction temperature is 200-260°C and the reaction time is 4-6h.

5. The method for preparing a tricyclodecene compound according to any one of claims 1 to 3, characterized in that: Before heating, the pressure of the inert gas is 0.5 to 3 MPa.

6. The method for preparing a tricyclodecene compound according to claim 1, characterized in that: The polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butylhydroquinone, bisphenol A, 4-cinnamylphenol, p-phenylenediamine, benzidine and phenothiazine.

7. The method for preparing a tricyclodecene compound according to claim 1, characterized in that: The inert gas is one of nitrogen, helium and argon.

8. The method for preparing a tricyclodecene compound according to claim 1, characterized in that: The purification specifically includes: firstly performing atmospheric distillation to recover cyclopentene, and then performing reduced pressure distillation to purify and collect the tricyclodecene compound.

9. The method for preparing a tricyclodecene compound according to claim 8, characterized in that: The temperature of atmospheric distillation is 70-85°C.

10. The method for preparing a tricyclodecene compound according to claim 8, characterized in that: The temperature of the reduced pressure distillation is 130-150°C.

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