Supported catalyst, application, method for preparing hydrogenated olefin polymer

Abstract

The present invention provides a supported catalyst, a preparation method thereof, an application thereof, and a method for preparing a hydrogenated olefin polymer. The supported catalyst includes: a first carrier and a metal catalyst supported on the first carrier; wherein, the first carrier includes at least one of the following: nano-silica, molecular sieve, MgCl2·AlCl3·nEtOH or ionic liquid carrier, and the ionic liquid carrier includes: #imgabs0# n in MgCl2·AlCl3·nEtOH is a positive integer between 2 and 6; the metal catalyst includes at least one of the following: #imgabs1##imgabs2#

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly relates to a supported catalyst, a preparation method thereof, an application thereof, and a method for preparing a hydrogenated olefin polymer. Background Art

[0002] As one of the effective methods for constructing new carbon-carbon double bonds, olefin metathesis reaction has developed many new polymer materials and new technologies. For example, ring-opening olefin metathesis polymerization reaction technology is one of them. Currently, the catalysts widely used for ring-opening olefin metathesis polymerization reaction and other metathesis reactions are catalysts based on molybdenum system and ruthenium system.

[0003] In order to develop end-capped functional polymers based on ring-opening olefin metathesis polymerization reaction, a variety of catalysts have been developed, including: Grubbs first-generation, second-generation, third-generation catalysts and Hoveyda-Grubbs first-generation, second-generation catalysts. However, these catalysts have disadvantages such as being difficult to reuse and difficult to separate products, and the subsequent catalytic hydrogenation reaction of the catalytic polymer has not been realized. Summary of the Invention

[0004] In view of this, the present invention provides a supported catalyst, a preparation method thereof, an application thereof, and a method for preparing a hydrogenated olefin polymer to solve the technical problems that the existing catalysts are difficult to reuse, difficult to separate products, and difficult to realize the subsequent catalytic hydrogenation reaction of the polymer.

[0005] To achieve the above object, the present invention provides a supported catalyst, including: a first carrier and a metal catalyst supported on the first carrier;

[0006] Wherein, the first carrier includes at least one of the following: nano-silica, molecular sieve, MgCl2·AlCl3·nEtOH or ionic liquid carrier, and the ionic liquid carrier includes:

[0007] Or n in MgCl2·AlCl3·nEtOH is a positive integer between 2 and 6; the metal catalyst includes at least one of the following: Or

[0008] According to an embodiment of the present invention, wherein the second carrier includes: nano-silica.

[0009] According to an embodiment of the present invention, wherein the mass ratio of the metal catalyst to the first carrier is 1:(20 - 2000).

[0010] The present invention also provides a method for preparing a supported catalyst, comprising: dissolving a metal catalyst in a first organic solution to obtain a precursor solution;

[0011] Dispersing a first support in a second organic solution to obtain a pretreated product;

[0012] Adding the precursor solution to the pretreated product, and after stirring and reacting for a preset time, obtaining a supported catalyst;

[0013] Wherein, the metal catalyst includes at least one of the following: Or The first support includes at least one of the following: nano-silica, molecular sieve, MgCl2·AlCl3·nEtOH or ionic liquid support, and the ionic liquid support includes:

[0014] Or In MgCl2·AlCl3·nEtOH, n is a positive integer between 2 and 6.

[0015] According to an embodiment of the present invention, wherein the second support includes: nano-silica.

[0016] According to an embodiment of the present invention, wherein the first organic solution and the second organic solution are miscible solutions, and the first organic solution and the second organic solution each include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, carbon tetrachloride, 1,4-dioxane or 1,2-dichloroethane.

[0017] According to an embodiment of the present invention, wherein the preset stirring time is 20 to 70 minutes; the preset reaction time is 10 to 120 minutes.

[0018] The present invention also provides an application of the supported catalyst in the catalytic hydrogenation reaction of olefin polymers, wherein the supported catalyst is used for catalyzing the hydrogenation reaction of olefin polymers with hydrogen; the supported catalyst is the above-mentioned supported catalyst or the one prepared by the above-mentioned preparation method.

[0019] The present invention also provides a method for preparing a hydrogenated olefin polymer based on a supported catalyst, comprising:

[0020] Using the supported catalyst to carry out a catalytic polymerization reaction on an olefin and a polar monomer to obtain an olefin polymer;

[0021] Adding the olefin polymer, the supported catalyst and the reaction solution to a high-pressure hydrogenation device, introducing hydrogen to carry out a catalytic hydrogenation reaction, and obtaining a hydrogenated olefin polymer;

[0022] Among them, the pressure of high-pressure hydrogen is 2 MPa to 10 MPa, and the supported catalyst is the above-mentioned supported catalyst or the one prepared by the above-mentioned preparation method.

[0023] According to an embodiment of the present invention, in which a catalytic polymerization reaction of an olefin and a polar monomer is carried out using a supported catalyst to obtain an olefin polymer, including:

[0024] Immerse a container containing different volumes of the supported catalyst, reaction solution, polar monomer, and olefin in an oil bath at a preset temperature for a preset time to obtain a reaction product, where the preset temperature is 30 to 60 °C, and the preset time in the oil bath is 1 to 3 hours;

[0025] Filter and evaporate the reaction product to obtain a separated polymer;

[0026] Wash and dry the separated polymer to obtain an olefin polymer.

[0027] Based on the above technical solutions, the present invention can at least achieve one of the following technical effects:

[0028] (1) In the present invention, an ionic liquid is introduced into the second carrier to form an ionic liquid carrier. Based on the ionic liquid carrier and a metal catalyst loading to form a supported catalyst, the ionic liquid changes the surface morphological characteristics of the second carrier, and forms a medium for anchoring the metal catalyst on the surface of the second carrier, which can prevent the direct interaction between the surface of the second carrier and the homogeneous metal catalyst, and reduce the steric hindrance and poisoning effect of the second carrier on the metal center.

[0029] (2) The supported catalyst provided by the present invention changes the homogeneous metal catalyst into a heterogeneous catalyst, so that the supported catalyst can improve the catalyst utilization efficiency and ash removal by recovering the catalyst, increase the reuse of the catalyst and product separation, reduce the heavy metal content and lighten the polymer color.

[0030] (3) The supported catalyst provided by the present invention can be applied to provide the catalytic performance for subsequent hydrogenation of unsaturated polymers in this polymerization system. Description of the Drawings

[0031] Figure 1 Schematically shows a flowchart of a preparation method of a supported catalyst according to an embodiment of the present invention;

[0032] Figure 2 Schematically shows a schematic diagram of a preparation method of a supported catalyst according to an embodiment of the present invention;

[0033] Figure 3 Schematically shows a flowchart of a method for preparing a hydrogenated olefin polymer based on a supported catalyst according to an embodiment of the present invention;

[0034] Figure 4 Schematically shows the nuclear magnetic resonance spectra before and after hydrogenation of the olefin polymer. Detailed implementation manners

[0035] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to specific embodiments and the accompanying drawings.

[0036] Regarding the problems in the prior art that the commonly used catalysts are difficult to reuse and separate products in olefin metathesis ring-opening polymerization, and for the application of realizing subsequent hydrogenation catalysis of catalytic polymers with hydrogen, in view of this, it is necessary for those skilled in the art to develop a catalyst system to solve at least some of the above technical problems.

[0037] Based on this, on the one hand, the present invention provides a supported catalyst, including: a first carrier and a metal catalyst supported on the first carrier.

[0038] According to an embodiment of the present invention, the first carrier may include at least one of the following: nano-silica, molecular sieve, MgCl2·AlCl3·nEtOH (magnesium dichloride aluminum trichloride ethanol complex) or ionic liquid carrier.

[0039] According to an embodiment of the present invention, n in MgCl2·AlCl3·nEtOH is a positive integer between 2 and 6.

[0040] According to an embodiment of the present invention, the ionic liquid carrier can be formed by introducing an ionic liquid onto the surface and / or inside of a second carrier to form an ionic liquid carrier.

[0041] According to an embodiment of the present invention, the ionic liquid carrier may include:

[0042] or

[0043] According to an embodiment of the present invention, the second carrier may be nano-silica.

[0044] According to an embodiment of the present invention, by introducing an ionic liquid into the second carrier, the ionic liquid will change the surface morphological characteristics of the second carrier, cover the surface of the carrier to form a medium for anchoring the metal catalyst, and can prevent the direct interaction between the surface of the second carrier and the metal catalyst, reducing the steric hindrance and poisoning effect of the second carrier on the metal center.

[0045] According to an embodiment of the present invention, the metal catalyst has a catalytic activity function and is supported on the surface and / or inside of the first carrier.

[0046] According to an embodiment of the present invention, the metal catalyst may include at least one of the following metal complexes: Grubbs second-generation catalyst Grubbs third-generation catalyst Hoveyda-Grubbs second-generation catalyst or ionic liquid-substituted Hoveyda-Grubbs second-generation catalyst

[0047] According to an embodiment of the present invention, the mass ratio of the metal catalyst to the first support may be 1:(20 - 2000), preferably, it may be 1:20, 1:50, 1:100, 1:200, 1:500, 1:800, 1:1000, 1:1500, 1:2000.

[0048] According to an embodiment of the present invention, through the above mass ratio of the metal catalyst to the first support, the metal catalyst can be uniformly loaded on the first support to obtain a high loading amount.

[0049] According to an embodiment of the present invention, through the supported catalyst provided by the present invention, the homogeneous metal catalyst can be transformed into a heterogeneous catalyst, so that the supported catalyst can improve the catalyst utilization efficiency and ash removal by recycling the catalyst, increase the reuse of the catalyst and product separation, reduce the heavy metal content and lighten the polymer color.

[0050] The following exemplarily shows the structures of several supported catalysts of the present invention so that those skilled in the art can better understand the technical solution.

[0051] Specifically, the supported catalyst having the structure of the present invention may have the structure of any one of the following structural formulas (I1)-(I6), for example:

[0052]

[0053]

[0054] It should be noted that the structures of the supported catalysts shown above are merely exemplary and do not limit the protection scope of the present invention. In some other embodiments, different types or forms of supported catalyst structures may be selected according to actual needs, which are not limited herein.

[0055] On the other hand, the present invention also provides a preparation method based on the above supported catalyst.

[0056] Figure 1 Schematically shows a flowchart of the preparation method of the supported catalyst according to an embodiment of the present invention; Figure 2A schematic diagram showing a method for preparing a supported catalyst according to an embodiment of the present invention is schematically illustrated.

[0057] As Figure 1 , the preparation method may include: operations S110 to S130.

[0058] In operation S110, a metal catalyst is dissolved in a first organic solution to obtain a precursor solution.

[0059] In operation S120, a first support is dispersed in a second organic solution to obtain a pretreated product.

[0060] In operation S130, the precursor solution is added to the pretreated product, and after stirring and reacting for a preset time, a supported catalyst is obtained.

[0061] According to an embodiment of the present invention, in an inert gas atmosphere, a metal catalyst can be dissolved in a first organic solvent to form a precursor solution of the supported catalyst.

[0062] According to an embodiment of the present invention, the metal catalyst may include at least one of the following metal complexes:

[0063] Grubbs second-generation catalyst Grubbs third-generation catalyst Hoveyda-Grubbs second-generation catalyst or an ionic liquid-substituted Hoveyda-Grubbs second-generation catalyst

[0064] According to an embodiment of the present invention, the pretreated product may be a solution in which a first support is dispersed.

[0065] According to an embodiment of the present invention, the first support includes at least one of the following: nano-silica, molecular sieve, MgCl2·AlCl3·nEtOH or ionic liquid support, and n in MgCl2·AlCl3·nEtOH is a positive integer between 2 and 6.

[0066] According to an embodiment of the present invention, the ionic liquid support may include:

[0067] or

[0068] According to an embodiment of the present invention, the second support may include nano-silica.

[0069] According to an embodiment of the present invention, the first organic solvent and the second organic solvent may be a miscible solution, and each of the first organic solution and the second organic solution may include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, carbon tetrachloride, 1,4-dioxane or 1,2-dichloroethane.

[0070] According to an embodiment of the present invention, the precursor solution is added to the pretreated product, stirred for a preset time, reacted for a preset time during the stirring process, and then filtered, the solid is rinsed, and dried by suction to obtain the supported catalyst.

[0071] According to an embodiment of the present invention, the preset stirring time may be 20 to 70 minutes; the preset reaction time may be 10 to 120 minutes.

[0072] Combined Figure 2 As shown, according to an embodiment of the present invention, the reaction can be understood as a process in which the metal catalyst in the precursor solution is loaded on the first support in the pretreated product, and finally a supported catalyst is formed.

[0073] The following further describes in detail a method for preparing a supported catalyst using an ionic liquid support as an example with specific examples. It should be noted that although the following describes the preparation method of the supported catalyst of the present invention using an ionic liquid support as an example, it can be understood that this specific example can implement the supported catalyst of the present invention in various forms, rather than limiting the present invention.

[0074] Examples 1 to 2 exemplarily illustrate the preparation of the ionic liquid support, and Examples 3 to 8 exemplarily illustrate the preparation of the supported catalyst using the ionic liquid support as the first support.

[0075] Example 1

[0076] Preparation of ionic liquid support I, the structure of this ionic liquid support I is:

[0077]

[0078] The preparation of ionic liquid support I may include: in an inert gas atmosphere, 17.47 g of 1-methyl-3-butylimidazolium chloride and 26.67 g of anhydrous AlCl3 are added to a round-bottom flask, stirred for at least 24 hours to obtain an ionic liquid. This ionic liquid is added to the calcined silica, stirred again for at least 24 hours, and then rinsed with hot dichloromethane to obtain ionic liquid support I.

[0079] Example 2

[0080] Preparation of ionic liquid support II, the structure of this ionic liquid support II is:

[0081]

[0082] The preparation of the ionic liquid support II may include: under an inert gas atmosphere, adding 27.65 g of 1-methyl-3-[3-(triethylsiloxy)propyl]imidazolium chloride to the calcined silica, stirring for at least 24 hours, then adding 2 equivalents (26.67 g) of anhydrous AlCl3 and stirring overnight, and subsequently rinsing with hot dichloromethane to obtain the ionic liquid support II.

[0083] Example 3

[0084] The process for preparing the supported catalyst with the structural formula (I1) above:

[0085]

[0086] Specifically, under an inert gas atmosphere, dissolve 10 mg of the Grubbs second-generation catalyst metal complex in dichloromethane, add it to the dichloromethane solution in which 1 g of the ionic liquid support I is dispersed, stir for 60 minutes, filter and wash the solid after the reaction, and dry it by suction to obtain the supported catalyst (I1).

[0087] Example 4

[0088] The process for preparing the supported catalyst with the structural formula (I2) above:

[0089]

[0090] Specifically, under an inert gas atmosphere, dissolve 10 mg of the Grubbs third-generation catalyst metal complex in dichloromethane, add it to the dichloromethane solution in which 1 g of the ionic liquid support I is dispersed, stir for 60 minutes, filter and wash the solid after the reaction, and dry it by suction to obtain the supported catalyst (I2).

[0091] Example 5

[0092] The process for preparing the supported catalyst with the structural formula (I3) above:

[0093]

[0094] Specifically, under an inert gas atmosphere, dissolve 10 mg of the ionic liquid-substituted Hoveyda-Grubbs second-generation catalyst metal complex in dichloromethane, add it to the dichloromethane solution in which 1 g of the ionic liquid support I In a dichloromethane solution, after stirring for 60 minutes, the reaction mixture was filtered, and the solid was rinsed. After drying by suction, the supported catalyst (I3) was obtained.

[0095] Example 6

[0096] Process for preparing the supported catalyst with the structural formula (I4) above:

[0097]

[0098] Specifically, under an inert gas atmosphere, 10 mg of the Grubbs second-generation catalyst metal complex was dissolved in dichloromethane and added to a dichloromethane solution containing 1 g of ionic liquid support II After stirring for 60 minutes, the reaction mixture was filtered, and the solid was rinsed. After drying by suction, the supported catalyst (I4) was obtained.

[0099] Example 7

[0100] Process for preparing the supported catalyst with the structural formula (I5) above:

[0101]

[0102] Specifically, under an inert gas atmosphere, 10 mg of the Grubbs third-generation catalyst metal complex was dissolved in dichloromethane and added to a dichloromethane solution containing 1 g of ionic liquid support II After stirring for 60 minutes, the reaction mixture was filtered, and the solid was rinsed. After drying by suction, the supported catalyst (I5) was obtained.

[0103] Example 8

[0104] Process for preparing the supported catalyst with the structural formula (I6) above:

[0105]

[0106] Specifically, under an inert gas atmosphere, 10 mg of the ionic liquid-substituted Hoveyda-Grubbs second-generation catalyst metal complex was dissolved in dichloromethane and added to a dichloromethane solution containing 1 g of ionic liquid support II After stirring for 60 minutes, the reaction mixture was filtered, and the solid was rinsed. After drying by suction, the supported catalyst (I6) was obtained.

[0107] On the other hand, the present invention also provides an application of a supported catalyst in the catalytic hydrogenation reaction of olefin polymers. The supported catalyst can be any supported catalyst with the above structures or a supported catalyst prepared by the above preparation method.

[0108] According to an embodiment of the present invention, the supported catalyst can be used for catalyzing the hydrogenation reaction of olefin polymers.

[0109] On the other hand, the present invention also provides a method for preparing a hydrogenated olefin polymer based on a supported catalyst.

[0110] Figure 3 A flowchart of a method for preparing a hydrogenated olefin polymer based on a supported catalyst according to an embodiment of the present invention is schematically shown.

[0111] As Figure 3 shown, the method may include: operation S310 to operation S320.

[0112] In operation S310, a catalytic polymerization reaction of an olefin and a polar monomer is carried out using a supported catalyst to obtain an olefin polymer.

[0113] In operation S320, the olefin polymer, the supported catalyst, and the reaction solution are added to a high-pressure hydrogenation device, and hydrogen is introduced to carry out a catalytic hydrogenation reaction to obtain a hydrogenated olefin polymer.

[0114] According to an embodiment of the present invention, the supported catalyst can be a supported catalyst of any structure of the above structure, or a supported catalyst prepared by the above preparation method.

[0115] According to an embodiment of the present invention, the pressure of the high-pressure hydrogen can be 2 MPa to 10 Mpa, the olefin can include one or both of cyclooctene or norbornene; the polar monomer can include at least one of the following: 1,4-butenediol, dimethyl maleate, butenediamide, maleic acid, 1,4-acetoxy-2-butene or 1,4-dichloro-2-butadiene.

[0116] According to an embodiment of the present invention, the polymerization temperature of the polymerization reaction can include 30 to 60 °C. Preferably, the polymerization temperature can be 30 °C, 40 °C, 50 °C, 60 °C. The polymerization pressure of the polymerization reaction can be atmospheric pressure polymerization.

[0117] According to an embodiment of the present invention, the polymerization reaction is generally carried out in an organic solvent, such as an organic solvent of hydrocarbons, cycloalkanes or aromatic hydrocarbons. For more favorable reactor operation and polymerization products, in some preferred embodiments, the organic solvent can also be a hydrocarbon having less than 12 carbons, for example, including but not limited to dichloromethane, tetrahydrofuran, toluene and their mixtures.

[0118] According to an embodiment of the present invention, the above descriptions of the temperature, pressure, type of olefin, organic solvent, and polymerization process used in the polymerization reaction are merely exemplary, so that those skilled in the art can understand the solution of the present invention, and are not intended to limit the protection scope of the present invention. In some other embodiments, settings can be made according to actual needs, which are not limited herein.

[0119] According to an embodiment of the present invention, a supported catalyst is used to catalytically polymerize an olefin and a polar monomer to obtain an olefin polymer, including:

[0120] Containers containing different volumes of supported catalyst, reaction solution, polar monomer, and olefin are immersed in an oil bath at a preset temperature for a preset time to obtain a reaction product, wherein the preset temperature is 30 - 60 °C, and the preset time in the oil bath is 1 - 3 hours. The reaction product is filtered and evaporated to obtain a separated polymer. The separated polymer is washed and dried to obtain an olefin polymer.

[0121] According to an embodiment of the present invention, different volumes of supported catalyst, reaction solution, polar monomer, and olefin can be transferred to a flask container through a syringe, and continuous purging with nitrogen is carried out.

[0122] According to an embodiment of the present invention, the flask container containing different volumes of supported catalyst, reaction solution, polar monomer, and olefin is placed under vacuum, then filled with nitrogen, and immediately immersed in an oil bath at a preset temperature for a preset time to obtain a reaction product.

[0123] According to an embodiment of the present invention, the reaction product can be filtered to separate the supported catalyst and the solution. The solution is evaporated under vacuum and precipitated into formaldehyde to obtain a separated polymer. The separated polymer is washed and vacuum dried for a preset time to obtain a white solid olefin polymer.

[0124] The following further describes in detail the polymerization reaction of olefin polymer using the above supported catalyst in specific embodiments to produce olefin polymer. It should be noted that although the following describes the process of the present invention based on the supported catalyst as an example, it can be understood that the specific embodiment can implement the preparation of the olefin polymer of the present invention in various forms, and is not used to limit the present invention.

[0125] Example 9 exemplarily illustrates the preparation process of catalytic polymerization to generate olefin polymer based on the supported catalyst and the polymerization result of the olefin polymer; Example 10 exemplarily illustrates the hydrogenated olefin polymer obtained after the hydrogenation reaction of the polymer prepared in Example 9.

[0126] Example 9

[0127] In this example, the supported catalyst of one of the above structures was used for the polymerization of cyclooctene and polar internal olefin monomers. Specifically:

[0128] The supported catalyst (250 mg), anhydrous dichloromethane (40 mL), 1, polar internal olefin monomer (for example, 4-acetoxy-2-butene (0.3 mmol)), and cyclooctene (15 mmol) were transferred to a 100 mL flask container by syringe and continuously purged with nitrogen. The flask and its contents were placed under vacuum and then refilled with nitrogen. Immediately after that, the flask was immersed in an oil bath at 40 °C for 2 hours. Then, the supported catalyst and the solution were separated by filtration. The solution was then evaporated to dryness under vacuum and then precipitated into 200 mL of methanol to obtain the separated polymer. It was washed with methanol (3 × 50 mL) and dried under vacuum for 6 hours to obtain a white solid olefin polymer.

[0129] Table 1 shows the polymerization reaction results of the prepared olefin polymer.

[0130] Table 1

[0131]

[0132] It should be noted that in Table 1, a represents the polymerization conditions of the polymerization reaction, that is, 15 mmol of cyclooctene, 0.3 mmol of internal olefin monomer, 250 mg (support) supported catalyst, and 40 ml of dichloromethane; b represents the average value of the yields of at least two repeated runs; c represents according to 1 the reaction percentage of the polar internal olefin monomer in the polymer calculated from the integral ratio of the repeating unit and the internal olefin proton in the 1H NMR (nuclear magnetic resonance) spectrum; d represents the molecular weight determined by multi-angle light scattering with a polystyrene standard by gel permeation chromatography (SEC).

[0133] As can be seen from Table 1, the supported catalyst provided by the present invention can catalyze the polymerization reaction of cyclooctene and polar internal olefin monomers under certain conditions to produce an olefin polymer, and the value range of the number average molecular weight is 20×10 3 ~70×10 3 , and the molecular weight distribution is between 1 and 1.6.

[0134] Example 10

[0135] The reaction solution at the end of the reaction without recrystallization treatment in Example 9 and the supported catalyst system (including the polymerized olefin polymer and the supported catalyst) were transferred to a high-pressure hydrogenation device and hydrogen was introduced for the hydrogenation reaction of the polymer. The specific process is as follows:

[0136] A portion of the olefin polymer was taken out from the reactor as a sample before hydrogenation for testing, and then the remaining reaction solution was added to a high-pressure hydrogenation device. Under a hydrogen pressure of 3 MPa, hydrogen was introduced and the reaction was carried out for 8 hours. Then, the reaction product was purified to extract the hydrogenated olefin polymer and 1 1H NMR spectrum test was performed.

[0137] It should be noted that the purification treatment of the reaction product may include: separating the supported catalyst and the solution by filtration, then evaporating the solution to dryness under vacuum, and then precipitating it into 200 mL of methanol to obtain the separated polymer. The polymer was washed with methanol (3×50 mL) and dried under vacuum for 6 hours to obtain a white solid hydrogenated olefin polymer.

[0138] Figure 4 The nuclear magnetic resonance spectra of the olefin polymer before and after hydrogenation are schematically shown.

[0139] As Figure 4 shown, from Figure 4 it can be seen that under the standard where the integral intensity of the carbon-carbon double bond nuclear magnetic peak is 1, compared with the integral of the non-double-bond ortho-methylene peak with an integral of 4.14 before hydrogenation, the integral of the non-double-bond ortho-methylene peak with an integral of 6.67 after hydrogenation increases. This is because some of the carbon-carbon double bonds in the molecular chain become saturated carbon-carbon single bonds, resulting in some double bonds and the ortho-methylene adjacent to the double bonds becoming non-double-bond ortho-methylene. Therefore, the integral of the non-double-bond ortho-methylene peak of the hydrogenated olefin polymer after hydrogenation increases. Thus, it can be shown that the supported catalyst provided by the present invention can catalyze the hydrogenation reaction of olefin polymers with hydrogen under certain conditions. Through nuclear magnetic integral calculation, the hydrogenation catalytic efficiency can reach 56.3%.

[0140] According to the embodiments of the present invention, after preparing an olefin polymer with the supported catalyst having the above structure, hydrogen is introduced to continuously catalyze the polymer to obtain a hydrogenated olefin polymer, so as to achieve the application in the subsequent catalytic hydrogenation reaction of olefin polymers and obtain a hydrogenated olefin polymer with higher molecular force and saturation.

[0141] The above specific embodiments have further detailed the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. Use of a supported catalyst in the catalytic hydrogenation reaction of olefin polymers, wherein, The supported catalyst is used for catalyzing the hydrogenation reaction of the olefin polymer; The supported catalyst includes a first carrier and a metal catalyst supported on the first carrier; the first carrier includes an ionic liquid carrier, and the ionic liquid carrier includes: or ; the metal catalyst includes at least one of the following: , , or ; wherein, the mass ratio of the metal catalyst to the first carrier is 1:(20 - 2000).

2. The use according to claim 1, wherein, The second carrier includes: the nano-silica.

3. The use according to claim 1, wherein, The supported catalyst is prepared by the following method: Dissolve the metal catalyst in a first organic solution to obtain a precursor solution; Disperse the first carrier in a second organic solution to obtain a pretreated product; Add the precursor solution to the pretreated product, and after stirring and reacting for a preset time, obtain the supported catalyst.

4. The use according to claim 3, wherein, The first organic solution and the second organic solution are mutually soluble solutions, and the first organic solution and the second organic solution both include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, carbon tetrachloride, 1,4-dioxane or 1,2-dichloroethane.

5. The use according to claim 3, wherein, The preset time for stirring is 20 to 70 minutes; the preset time for the reaction is 10 to 120 minutes.

6. A method for preparing a hydrogenated olefin polymer based on a supported catalyst, comprising: Use the supported catalyst to carry out a catalytic polymerization reaction on an olefin and a polar monomer to obtain an olefin polymer; Add the olefin polymer, the supported catalyst and the reaction solution to a high-pressure hydrogenation device, introduce hydrogen to carry out a catalytic hydrogenation reaction, and obtain a hydrogenated olefin polymer; Wherein, the pressure of the high-pressure hydrogen is 2 MPa to 10 Mpa, the supported catalyst includes a first carrier and a metal catalyst supported on the first carrier; the first carrier includes an ionic liquid carrier, and the ionic liquid carrier includes: or ; the metal catalyst includes at least one of the following: , , or ; wherein, the mass ratio of the metal catalyst to the first carrier is 1:(20 - 2000).

7. The method according to claim 6, wherein, The use of the supported catalyst to carry out a catalytic polymerization reaction on an olefin and a polar monomer to obtain an olefin polymer includes: Immerse containers containing different volumes of the supported catalyst, the reaction solution, the polar monomer and the olefin in an oil bath at a preset temperature for a preset time to carry out a reaction, and obtain a reaction product, wherein the preset temperature is 30 to 60 °C, and the preset time in the oil bath is 1 to 3 hours; Filter and evaporate the reaction product to obtain a separated polymer; Wash and dry the separated polymer to obtain the olefin polymer.

8. The method according to claim 6, wherein, The second carrier includes: the nano-silica.

9. The method according to claim 6, wherein, The supported catalyst is prepared by the following method: Dissolve the metal catalyst in a first organic solution to obtain a precursor solution; Disperse the first carrier in a second organic solution to obtain a pretreated product; Add the precursor solution to the pretreated product, and after stirring and reacting for a preset time, obtain the supported catalyst.

10. The method according to claim 9, wherein, The first organic solution and the second organic solution are mutually soluble solutions, and the first organic solution and the second organic solution both include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, carbon tetrachloride, 1,4-dioxane or 1,2-dichloroethane.

11. The method according to claim 9, wherein, The preset time for stirring is 20 to 70 minutes; the preset time for the reaction is 10 to 120 minutes.

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