Catalysts, processes for their production and use, hydrogenation of cyclic olefin polymers and polymers

Abstract

The application discloses a catalyst, a preparation method and application thereof, a hydrogenation method of a cyclic olefin polymer, and the polymer. The catalyst comprises a carrier and a nickel element supported on the carrier; the carrier comprises a base material and a light rare earth element; the base material is SiO2 and / or Al2O3; the proportion of the nickel element is 5wt.%-30wt.% based on the total mass of the catalyst; the proportion of the light rare earth element is 0.5wt.%-10wt.%; the proportion of the base material is 60wt.%-94.5wt.%; and the specific surface area of the catalyst is not less than 80m 2 / g. When the catalyst is used for hydrogenation of the cyclic olefin polymer, the catalyst has high activity, is easy to separate, has long service life, and can be recycled.

Description

Technical Field

[0001] This invention relates to a catalyst, its preparation method and application, a hydrogenation method for cyclic olefin polymers, and the polymers thereof. Background Technology

[0002] Cyclic olefin polymers (COPs) are a class of high-performance plastics obtained by ring-opening polymerization of cyclic olefin monomers followed by hydrogen saturation. The polymer precursor obtained from the ring-opening polymerization of cyclic olefin monomers has 50% of its repeating units being C=C, requiring further hydrogen saturation to obtain COP materials.

[0003] Currently, hydrogenation of precursors can be performed using homogeneous catalysis or heterogeneous catalysis. For example, US20030050406A1 discloses a method for preparing cyclic olefin polymers via ring-opening polymerization (ROMP) and further hydrogenation. The catalyst used in the hydrogenation process has no special requirements and can be a metal-supported heterogeneous catalyst, a metal-organic complex, or a homogeneous catalytic system composed of other two-component transition metal compounds. Another example is CN104169322B, which discloses a method for preparing ring-opening metasolidated polymer hydrides, where the catalyst used for hydrogenation can be either a homogeneous or heterogeneous catalyst. For methods using homogeneous catalysts to hydrogenate ring-opening metasolidated polymers, the catalyst is difficult to separate after the reaction, and the hydrogenation catalyst is generally not recyclable. While heterogeneous support methods for homogeneous catalysts allow for catalyst recovery and recycling, these catalysts have complex structures and generate significant amounts of organic wastewater during the preparation process, which is detrimental to environmental protection. In contrast, using heterogeneous catalysts for precursor hydrogenation offers the advantages of easy catalyst separation and recycling compared to homogeneous catalyst hydrogenation. Among them, Ni-based heterogeneous catalysts (such as Raney nickel and supported nickel catalysts) are commonly used hydrogenation catalysts in industrial applications, with the advantages of low cost and good hydrogenation activity.

[0004] However, Raney nickel catalysts are highly reactive and prone to accidents if not handled properly, and the pretreatment of the catalyst generates a large amount of strongly alkaline waste liquid. Therefore, in this field, supported nickel catalysts using (composite) oxides as supports are often used. This can greatly improve the safety of the reaction process and avoid the generation of alkaline waste liquid. For example, JP2001098016A discloses a method for hydrogenating polymers obtained from the ring-opening polymerization of cyclic olefin monomers, which discloses that the catalyst used has the following characteristics: at least one of nickel, palladium, and platinum is used as the supporting metal, and alumina, titanium dioxide, silicon dioxide, silicon-aluminum composite oxide, diatomaceous earth, or activated carbon is used as the support, wherein the average particle size of the supported metal particles is within the range of [missing information]. Within this range. However, the following problems arise when using supported Ni catalysts for hydrogenation: Due to the high temperature of hydrogenation of hydrocarbon solutions containing polymer precursors, the supported Ni metal on the catalyst surface is prone to agglomeration in the hydrogen atmosphere, leading to reduced catalyst activity. Simultaneously, the high reaction temperature can also cause the supported Ni metal to peel off from the metal surface in the reaction solution, resulting in reduced catalytic activity or even deactivation, severely impacting catalyst lifetime. Furthermore, since the substrate in the hydrocarbon solution containing polymer precursors is a polymer with an unsaturated structure, chain transfer reactions easily occur under the influence of acidic sites on the catalyst surface, resulting in a significantly broadened molecular weight distribution of the final COP material. Summary of the Invention

[0005] To address the shortcomings of existing supported nickel catalysts, such as high-temperature agglomeration, easy stripping, and low activity, this invention provides a catalyst, its preparation method and application, a method for hydrogenating cyclic olefin polymers, and the resulting polymer. When used for the hydrogenation of cyclic olefin polymers, the catalyst of this invention exhibits high activity, ease of separation, long catalyst lifetime, and recyclability.

[0006] The present invention mainly solves the above technical problems through the following technical solutions:

[0007] This invention provides a catalyst comprising a support and a nickel element supported on the support;

[0008] The carrier comprises a substrate and light rare earth elements; the substrate is SiO2 and / or Al2O3.

[0009] Based on the total mass of the catalyst, the proportion of nickel is 5 wt.% to 30 wt.%; the proportion of light rare earth elements is 0.5 wt.% to 10 wt.%; and the proportion of the substrate is 60 wt.% to 94.5 wt.%.

[0010] The specific surface area of ​​the catalyst is not less than 80 m². 2 / g.

[0011] In this invention, the nickel element may exist in the form of metallic nickel and / or nickel oxide.

[0012] Preferably, the metallic nickel (nickel in the 0-valence state) accounts for no less than 80% of the total nickel content by mass.

[0013] In this invention, the proportion of nickel is preferably 5 wt.% to 24 wt.%, for example 10 wt.% or 15 wt.%.

[0014] In this invention, the light rare earth elements may exist in the form of light rare earth oxides.

[0015] In this invention, the light rare earth elements can be distributed on the surface of the substrate.

[0016] In this invention, the light rare earth element may be La and / or Ce;

[0017] Preferably, the La exists in the form of La2O3.

[0018] Preferably, the Ce is CeO 2-x It exists in the form of , where 0 < x ≤ 0.5, preferably 0 < x ≤ 0.1.

[0019] In this invention, the proportion of the light rare earth elements is preferably 0.5 wt.% to 7.5 wt.%, more preferably 0.5 to 5 wt.%, for example 3 wt.% or 5 wt.%.

[0020] In this invention, the proportion of the substrate is preferably 65 wt.% to 90 wt.%, for example 80 wt.%, 82 wt.%, or 85 wt.%.

[0021] In this invention, the specific surface area of ​​the catalyst is preferably 96–179 m². 2 / g, for example 137m 2 / g、142m 2 / g、153m 2 / g、161m 2 / g.

[0022] The present invention also provides a method for preparing a catalyst, comprising the following steps:

[0023] S1. The carrier raw material composition is impregnated or precipitated, and then subjected to a first calcination to obtain the carrier; the carrier raw material composition includes a substrate, a light rare earth element source, and a solvent; the substrate includes SiO2 and / or Al2O3;

[0024] S2. The support is impregnated in a nickel source solution and then calcined a second time to obtain a catalyst precursor;

[0025] S3. The catalyst precursor is activated and reduced to obtain the catalyst.

[0026] In this invention, in step S1, the light rare earth element source can be a light rare earth metal salt and / or a derivative of a light rare earth metal salt.

[0027] The light rare earth metal salt may be one or more of lanthanum nitrate, lanthanum acetate, lanthanum chloride, cerium(III) nitrate, cerium(IV) ammonium nitrate and cerium(III) trichloride, preferably lanthanum nitrate and cerium(III) nitrate.

[0028] The derivative of the light rare earth metal salt may be one or more of the following: a derivative of lanthanum nitrate, a derivative of lanthanum acetate, a derivative of lanthanum chloride, a derivative of cerium nitrate, a derivative of cerium ammonium nitrate, and a derivative of cerium trichloride, preferably a derivative of lanthanum nitrate and a derivative of cerium nitrate.

[0029] In step S1, the specific surface area of ​​the substrate is preferably not less than 100 m². 2 / g, for example, 115m 2 / g、153m 2 / g or 187m 2 / g.

[0030] In step S1, the carrier raw material composition may further include tartaric acid. The tartaric acid can enhance the dispersion of light rare earth elements.

[0031] In a preferred embodiment of the present invention, the carrier raw material composition is impregnated and then subjected to a first calcination to obtain the carrier.

[0032] In step S1, the impregnation preferably includes the following steps: dissolving the light rare earth element source in a solvent to obtain a light rare earth precursor solution, and then mixing the substrate with the light rare earth precursor solution for impregnation.

[0033] The solvent may be a conventional solvent in the art that can dissolve the raw materials and is easy to remove, such as deionized water.

[0034] During the impregnation process, a polyethylene film can be used to seal the container opening to prevent contamination.

[0035] The impregnation temperature can be 0 to 60°C, for example, 25°C or 30°C.

[0036] The soaking time can be 1 to 24 hours, for example, 6 hours or 12 hours.

[0037] In a preferred embodiment of the present invention, the carrier raw material composition includes tartaric acid, and the impregnation preferably includes the following steps: the substrate is thoroughly mixed with an aqueous tartaric acid solution by stirring to obtain a tartaric acid-substrate slurry; the light rare earth element source is dissolved in a solvent to obtain a light rare earth precursor solution; and the tartaric acid-substrate slurry and the light rare earth precursor solution are mixed for impregnation.

[0038] The stirring time can be 0.1 to 12 hours, for example, 0.5 hours, 1 hour or 2 hours.

[0039] In step S1, the precipitation preferably includes the following steps: adjusting the pH of the dispersion comprising the substrate, the light rare earth element source and the solvent to 11.5, carrying out the precipitation reaction, and then sequentially performing filtration and washing.

[0040] The pH of the dispersion can be adjusted using a NaOH-NaHCO3 mixed alkaline solution. Preferably, the mass ratio of NaOH to NaHCO3 in the NaOH-NaHCO3 mixed alkaline solution is 5:1 to 1:5. The mass concentration of the NaOH-NaHCO3 mixed alkaline solution can be conventional in the art, for example, 10%.

[0041] The washing process involves washing the filter cake obtained through vacuum filtration, with the purpose of adjusting the pH of the filter cake to neutral.

[0042] The dispersion can be prepared by dispersing the substrate in the solvent and then adding the light rare earth element source.

[0043] In a preferred embodiment of the present invention, the carrier raw material composition includes tartaric acid, and the dispersion can be prepared by the following method: dispersing the substrate in the solvent, adding the tartaric acid and stirring thoroughly to dissolve, and then adding the light rare earth metal salt.

[0044] The stirring time can be 0.5 to 6 hours, for example, 0.5 hours.

[0045] In step S1, before the first calcination, the product being impregnated or precipitated may be subjected to a first desolventizing, a first drying, and a first grinding step.

[0046] The first solvent removal can be performed using conventional methods in the art, such as first drying.

[0047] The temperature of the first drying step can be a conventional temperature in the art, preferably 40–80°C; for example, 60°C. The drying time of the first step can be selected according to the actual situation, preferably 1–24 hours; for example, 2–4 hours.

[0048] The temperature of the first drying step can be 80–140°C, for example, 110°C. The drying time can be 3–24 hours, for example, 6 hours or 12 hours.

[0049] In step S1, the temperature of the first calcination can be 350-600℃, for example 500℃ or 550℃.

[0050] In step S1, the rate of heating to the temperature of the first calcination can be 1 to 10 °C / min, for example, 1 °C / min.

[0051] In step S1, the first calcination time can be 1 to 8 hours, for example, 3 hours or 4 hours.

[0052] In step S1, the atmosphere for the first calcination can be air.

[0053] In this invention, in step S2, the nickel source in the nickel source solution may be a nickel salt and / or a derivative of a nickel salt.

[0054] Preferably, the nickel salt is one or more of nickel nitrate, nickel chloride, and nickel acetate and their derivatives. The nickel nitrate may be a hydrate of nickel nitrate, preferably nickel nitrate hexahydrate.

[0055] Preferably, the nickel salt derivative is one or more of nickel nitrate derivatives, nickel chloride derivatives, and nickel acetate derivatives.

[0056] In step S2, solvent A in the nickel source solution can be a conventional solvent in the art that can dissolve the nickel source and other components and is easy to remove, such as deionized water.

[0057] In step S2, during the impregnation process, the nickel source solution and the carrier can be thoroughly mixed by stirring. The stirring time can be 0.1 to 2 hours, for example, 0.5 hours.

[0058] In step S2, during the impregnation process, a polyethylene film can be used to seal the container opening to prevent contamination.

[0059] In step S2, the impregnation temperature can be 0 to 80°C, for example, 25°C or 30°C.

[0060] In step S2, the soaking time can be 1 to 24 hours, for example, 6 hours or 12 hours.

[0061] In step S2, after impregnation and before the second calcination, the impregnated product may be subjected to a second desolventizing, a second drying, and a second grinding step.

[0062] The second solvent removal can be performed using conventional methods in the art, such as a second drying process.

[0063] The temperature of the second drying step can be a conventional temperature in the art, preferably 40–100°C, such as 60°C. The drying time can be selected according to the actual situation, preferably 1–24 hours, such as 2 hours or 4 hours.

[0064] The temperature for the second drying is preferably 80–140°C, for example, 110°C. The drying time for the second drying is preferably 2–24 hours, for example, 6 hours or 12 hours.

[0065] In step S2, the temperature of the second calcination is preferably 350-600°C, for example 500°C or 550°C.

[0066] In step S2, the rate of heating to the temperature of the second calcination is preferably 1 to 10°C, for example, 1°C / min.

[0067] In step S2, the second calcination time is preferably 2 to 8 hours, for example 3 hours or 4 hours.

[0068] In step S2, the atmosphere for the second calcination is preferably air.

[0069] In this invention, the purpose of the activation and reduction in step S3 is to partially or completely reduce the nickel element in the catalyst precursor, which exists in the form of nickel oxide, to metallic nickel.

[0070] In step S3, the activation and reduction temperature can be 300-400℃, for example 350℃.

[0071] In step S3, the activation and reduction time can be 1 to 6 hours, for example, 3 hours.

[0072] In step S3, the activation and reduction atmosphere is typically hydrogen.

[0073] In step S3, after the activation and reduction, the specific surface area of ​​the catalyst is preferably not less than 80 m². 2 / g.

[0074] In a preferred embodiment of the present invention, the method for preparing the catalyst includes the following steps:

[0075] S1. Dissolve the light rare earth element source in the solvent to obtain a light rare earth precursor solution, then mix the substrate with the light rare earth precursor solution for impregnation, and then perform a first calcination to obtain a carrier.

[0076] S2. Dissolve the nickel salt in solvent A to prepare a nickel precursor solution; impregnate the support in the nickel precursor solution and then calcine it a second time to obtain the catalyst precursor;

[0077] S3. The catalyst precursor is activated and reduced to obtain the catalyst.

[0078] In one specific embodiment of the present invention, the method for preparing the catalyst includes the following steps:

[0079] S1. The substrate is thoroughly mixed with tartaric acid aqueous solution by stirring to obtain tartaric acid-substrate slurry; the light rare earth metal salt is dissolved in the solvent to obtain light rare earth precursor solution; the tartaric acid-substrate slurry and the light rare earth precursor solution are mixed and impregnated, and then subjected to the first calcination to obtain the carrier.

[0080] S2. Dissolve the nickel salt in solvent A to prepare a nickel precursor solution; impregnate the support in the nickel precursor solution and then calcine it a second time to obtain the catalyst precursor;

[0081] S3. The catalyst precursor is activated and reduced to obtain the catalyst.

[0082] In another preferred embodiment of the present invention, the method for preparing the catalyst includes the following steps:

[0083] S1. Adjust the pH of the dispersion containing the substrate, the light rare earth element source and the solvent to 11.5, carry out a precipitation reaction, and then sequentially perform filtration, washing and first calcination to obtain the carrier;

[0084] S2. Dissolve the nickel salt in solvent A to prepare a nickel precursor solution; impregnate the support in the nickel precursor solution and then calcine it a second time to obtain the catalyst precursor;

[0085] S3. The catalyst is activated and reduced to obtain the catalyst.

[0086] In one specific embodiment of the present invention, the method for preparing the catalyst includes the following steps:

[0087] S1. After dispersing the substrate in the solvent, add the tartaric acid and stir thoroughly to dissolve it. Then add the light rare earth metal salt to obtain a dispersion. Adjust the pH of the dispersion to 11.5 and carry out a precipitation reaction. Then, perform suction filtration, washing and first calcination in sequence to obtain the carrier.

[0088] S2. Dissolve the nickel salt in solvent A to prepare a nickel precursor solution; impregnate the support in the nickel precursor solution and then calcine it a second time to obtain the catalyst precursor;

[0089] S3. The catalyst precursor is activated and reduced to obtain the catalyst.

[0090] The present invention also discloses a catalyst prepared by the catalyst preparation method described above.

[0091] The present invention also discloses a method for hydrogenating cyclic olefin polymers, which uses the catalyst described above to catalytically hydrogenate the cyclic olefin polymers to obtain hydrogenated cyclic olefin polymers.

[0092] In this invention, the hydrogenation target is the carbon-carbon (C=C) double bond on the main chain of the cyclic olefin polymer, and the hydrogenation refers to hydrogenating the carbon-carbon double bond on the main chain of the cyclic olefin polymer into a carbon-carbon single bond.

[0093] In this invention, the cyclic olefin polymer comprises structural units as shown in formula (I):

[0094]

[0095] In equation (Ⅰ), m is 0, 1, 2 or 3;

[0096] R1 to R4 are each independently hydrogen, straight-chain or branched C1 to C18 alkyl, substituted or unsubstituted C6 to C9 aryl; wherein, the substituted C6 to C9 aryl is preferably a meta-substituted C6 to C9 aryl or a para-substituted C6 to C9 aryl.

[0097] At least one of R1, R2, R3 and R4 is hydrogen, preferably at least two are hydrogen; more preferably, at least one of R1 and R2 is hydrogen, and at least one of R3 and R4 is hydrogen.

[0098] In this invention, the weight-average molecular weight of the cyclic olefin polymer can be 35,000 to 65,000, for example 555329.

[0099] In this invention, the molecular weight distribution index (PDI) of the cyclic olefin polymer can be 1.5 to 4.0, for example 1.953.

[0100] In this invention, the cyclic olefin polymer can be obtained by ring-opening metathesis polymerization of monomers; the monomers include compounds as shown in formula (I'):

[0101]

[0102] In the aforementioned formula (Ⅰ'), m is as described above, and R1 to R4 are as described above.

[0103] The polymerization temperature is preferably 0–140°C, for example 25°C;

[0104] The polymerization time is preferably 0.1 to 6 hours, for example 0.5 hours;

[0105] Preferably, the polymerization pressure is 0–1.5 MPa;

[0106] The polymerization is carried out in a solvent, preferably one or more of dichloromethane, tetrahydrofuran, toluene, xylene, and chlorobenzene. The chlorobenzene is, for example, trichlorobenzene.

[0107] In this invention, the solvent used in the hydrogenation process can be one or more of the following: alkanes with not less than 6 carbon atoms, cycloalkanes with not less than 6 carbon atoms, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and tetrahydrofuran.

[0108] In this invention, the hydrogen source used in the hydrogenation process can be hydrogen (H2) or a mixture of gases containing hydrogen.

[0109] The hydrogen-containing gas mixture is, for example, H2 / N2 or H2 / Ar.

[0110] Preferably, the pressure of the hydrogen source is 0.5–4 MPa.

[0111] In this invention, the hydrogenation temperature can be 60 to 200°C, for example 80°C or 120°C.

[0112] In this invention, the hydrogenation time can be 1 to 12 hours, for example, 3 hours or 10 hours.

[0113] In this invention, after hydrogenation, the conversion rate of carbon-carbon double bonds in the cyclic olefin polymer is preferably not less than 98.5%.

[0114] The present invention also provides a hydrogenated cyclic olefin polymer, which is obtained by the hydrogenation method of the cyclic olefin polymer as described above.

[0115] In this invention, the molecular weight distribution index (PDI) of the hydrogenated cyclic olefin polymer is preferably not higher than 2.5.

[0116] The present invention also discloses the application of the catalyst as described above in the catalytic hydrogenation of cyclic olefin polymers.

[0117] In this invention, after the catalyst is used for a cumulative cycle of 1500 h under the reaction process conditions of cyclic olefin polymer hydrogenation, the loss rate of nickel in the catalyst is preferably less than 1 wt.%, where the percentage is the percentage of lost nickel to the total mass of nickel; and the reduction rate of nickel dispersion is preferably less than 5%.

[0118] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0119] The reagents and raw materials used in this invention are all commercially available.

[0120] The positive and progressive effects of this invention are as follows:

[0121] The catalyst of this invention has high activity, is easy to separate, has a long lifespan, and can be recycled. The hydrogenated cyclic olefin polymer obtained after hydrogenation can maintain the molecular weight and molecular weight distribution (PDI) of the polymer compared with the unhydrogenated polymer, avoiding the decrease in molecular weight and the broadening of molecular weight distribution (increase in PDI) during hydrogenation. Moreover, the hydrogen pressure required for the reaction is lower, and the temperature range for catalyst use is wider. Furthermore, the catalyst is low in cost and highly safe. Attached Figure Description

[0122] Figure 1 The 15 wt.% Ni / 5 wt.% CeO prepared in Example 1 x XRD pattern of SiO2 catalyst.

[0123] Figure 2 The 15 wt.% Ni / 5 wt.% CeO prepared in Example 1 x SEM image of the SiO2 catalyst.

[0124] Figure 3 Before hydrogenation of the cyclic olefin polymer PDMON 1 H-NMR spectrum.

[0125] Figure 4 The hydrogenated cyclic olefin polymer obtained by hydrogenating the cyclic olefin polymer PDMON using the catalyst of Example 1. 1 H-NMR spectrum. Detailed Implementation

[0126] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0127] Preparation Example 1: Preparation of 15 wt.% Ni / 5 wt.% CeO by impregnation method 2-x -SiO2 catalyst

[0128] S1. Dissolve 0.5g of tartaric acid in 10g of deionized water, then weigh 10g of SiO2 substrate (grade KJ-Si-1, specific surface area 187m²). 2 / g), poured into tartaric acid solution, stirred for 1h to form tartaric acid-SiO2 slurry. 1.328g of cerium nitrate hexahydrate (III) was dissolved in 10.0g of deionized water and stirred evenly to prepare Ce rare earth precursor solution. Then, the prepared Ce rare earth precursor was poured into the tartaric acid-SiO2 slurry, so that the Ce rare earth precursor solution fully wetted the substrate and uniformly impregnated the SiO2 substrate; the mouth of the impregnation container was sealed with polyethylene film, stood at 25℃ for 12h, the polyethylene film was removed, dried at 60℃ for 4h, and then heated to 110℃ for 12h; the dried solid was ground, heated to 550℃ at a heating rate of 1℃ / min, and calcined in air for 4h to obtain pale yellow CeO. 2-x -SiO2 support, 0 < x ≤ 0.1, where the obtained CeO 2-x CeO in SiO2 support 2-x The oxide content is 5 wt.%.

[0129] S2. Dissolve 4.370g of nickel nitrate hexahydrate in 9.5g of deionized water and stir until homogeneous to prepare a nickel precursor solution; weigh 5.0g of the prepared 5wt.% CeO 2-x -SiO2 support was poured into the prepared nickel precursor solution and stirred for 0.5 h until 5 wt.% CeO 2-x - After the SiO2 support and nickel precursor solution are thoroughly mixed, the mouth of the impregnation container is sealed with a polyethylene film and left to stand at 25°C for 12 hours. Then, the polyethylene film is removed, and the mixture is dried at 60°C for 4 hours, and then heated to 110°C for 12 hours. The dried solid is ground and heated to 550°C at a heating rate of 1°C / min, and then calcined in air for 4 hours to obtain the catalyst precursor.

[0130] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 350℃ and atmospheric pressure for 3 hours to obtain 15wt.% Ni / 5wt.% CeO. 2-x -SiO2 catalyst, wherein 15wt.%Ni refers to the Ni element content of 15wt.% based on the total mass of the catalyst after activation.

[0131] 15 wt.% Ni / 5 wt.% CeO 2-x -High-resolution transmission electron microscopy (HR-TEM) image of SiO2 catalyst as follows Figure 1 As shown, the X-ray powder diffraction (XRD) pattern is as follows: Figure 2 As shown.

[0132] Preparation Example 2: Preparation of 15 wt.% Ni / 3 wt.% CeO by impregnation method 2-x -SiO2 catalyst

[0133] S1. Dissolve 0.5g of tartaric acid in 10g of deionized water. Then, weigh 10g of SiO2 substrate (grade KJ-Si-1, specific surface area 187m²). 2 / g), stir for 1h to form tartaric acid-SiO2 slurry. Dissolve 0.780g of cerium nitrate hexahydrate (III) in 10.0g of deionized water and stir evenly to prepare Ce rare earth precursor solution. Pour the prepared Ce rare earth precursor solution into tartaric acid-SiO2 slurry and stir for 0.5h to fully wet the substrate and evenly impregnate the SiO2 substrate; seal the mouth of the impregnation container with polyethylene film, stand at 25℃ for 12h, remove the polyethylene film, dry at 60℃ for 4h, and then heat to 110℃ for 12h; grind the dried solid, heat to 550℃ at a heating rate of 1℃ / min, and calcine in air for 4h to obtain pale yellow CeO 2-x -SiO2 support, 0 < x ≤ 0.1. Wherein, the obtained CeO 2-x CeO in SiO2 support 2-xThe oxide content is 3 wt.%.

[0134] S2. The preparation method of the catalyst precursor is the same as in Example 1.

[0135] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 350℃ and atmospheric pressure for 3 hours to obtain 15wt.% Ni / 3wt.% CeO. 2-x -SiO2 catalyst. Here, 15wt.% Ni refers to the Ni element content of 15wt.% based on the total mass of the catalyst after activation.

[0136] Preparation Example 3: Preparation of 5 wt.% Ni / 5 wt.% CeO by impregnation method 2-x -SiO2 catalyst

[0137] S1, CeO 2-x The preparation method of the SiO2 support is the same as in Example 1, where 0 < x ≤ 0.1. The obtained CeO2... 2-x CeO in SiO2 support 2-x The oxide content is 5 wt.%.

[0138] S2. Dissolve 1.304 g of nickel nitrate hexahydrate in 9.5 g of deionized water and stir until homogeneous to prepare a nickel precursor solution. Weigh 5.0 g of the prepared 5 wt.% CeO 2-x -SiO2 support was poured into the prepared nickel precursor solution and stirred for 0.5 h until 5 wt.% CeO 2-x - After the SiO2 support and nickel precursor are thoroughly mixed, the mouth of the impregnation container is sealed with a polyethylene film and left to stand at 25°C for 12 hours. The polyethylene film is then removed, and the mixture is dried at 60°C for 4 hours. The temperature is then raised to 110°C and dried for 12 hours. The dried solid is then ground and heated to 550°C at a heating rate of 1°C / min. The solid is then calcined in air for 4 hours to obtain the catalyst precursor.

[0139] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 350℃ and atmospheric pressure for 3 hours to obtain 5wt.% Ni / 5wt.% CeO. 2-x -SiO2 catalyst. Wherein, 5wt.%Ni refers to the Ni element content of 5wt.% based on the total mass of the catalyst after activation.

[0140] Preparation Example 4: Preparation of 30 wt.% Ni / 5 wt.% CeO by impregnation method 2-x -SiO2 catalyst

[0141] S1, CeO 2-x The preparation method of the SiO2 support is the same as in Example 1, where 0 < x ≤ 0.1. The obtained CeO2... 2-x CeO in SiO2 support 2-xThe oxide content is 5 wt.%.

[0142] S2. Dissolve 10.617g of nickel nitrate hexahydrate in 9.5g of deionized water and stir until homogeneous to prepare a nickel precursor solution; weigh 5.0g of the prepared 5wt.% CeO 2-x -SiO2 support was poured into the prepared nickel precursor solution and stirred for 0.5 h until 5 wt.% CeO 2-x - After the SiO2 support and nickel precursor solution are thoroughly mixed, the mouth of the impregnation container is sealed with a polyethylene film and left to stand at 25°C for 12 hours. Then the polyethylene film is removed, and the mixture is dried at 60°C for 4 hours, and then heated to 110°C for 12 hours. The dried solid is ground and heated to 550°C at a heating rate of 1°C / min, and then calcined in air for 4 hours to obtain the catalyst precursor.

[0143] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 350℃ and atmospheric pressure for 3 hours to obtain 30 wt.% Ni / 5 wt.% CeO. 2-x -SiO2 catalyst. The 30wt.% Ni refers to the Ni element content of 30wt.% based on the total mass of the catalyst after activation.

[0144] Preparation Example 5: Preparation of 10 wt.% Ni / 5 wt.% La2O3-Al2O3 catalyst by impregnation method

[0145] S1. Dissolve 0.5g of tartaric acid in 10g of deionized water. Weigh 10g of γ-Al2O3 substrate (specific surface area 153m2 / g) and pour it into the tartaric acid solution. Stir for 2h to form a tartaric acid-Al2O3 slurry. Dissolve 0.699g of lanthanum nitrate hexahydrate in 5.0g of deionized water and stir evenly to prepare a La rare earth precursor solution. Pour the prepared La rare earth precursor solution into the slurry and stir for 0.5h to fully wet the substrate and uniformly impregnate the γ-Al2O3 substrate. Seal the mouth of the impregnation container with polyethylene film and let it stand at 30℃ for 6h. Then remove the polyethylene film, dry at 60℃ for 2h, and then heat to 110℃ for 6h. Grind the dried solid and heat it to 500℃ at a heating rate of 1℃ / min. Calcinate it in air for 3h to obtain a white La2O3-Al2O3 support. The La2O3 content in the obtained La2O3-Al2O3 support was 5 wt.%.

[0146] S2. Dissolve 2.774g of nickel nitrate hexahydrate in 5.0g of deionized water and stir until homogeneous to prepare a nickel precursor solution. Weigh 5.0g of the prepared 5wt.% La2O3-Al2O3 support and pour it into the prepared nickel precursor solution. Stir for 0.5h. After the 5wt.% La2O3-Al2O3 support and the nickel precursor solution are thoroughly mixed, seal the mouth of the impregnation container with polyethylene film and let it stand at 30℃ for 6h. Then remove the polyethylene film, dry at 60℃ for 2h, and then heat to 110℃ for 6h. Grind the dried solid and heat it to 500℃ at a heating rate of 1℃ / min. Calcinate it in air for 3h to obtain the catalyst precursor.

[0147] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 400℃ and atmospheric pressure for 3 hours to obtain a 10wt.% Ni / 5wt.% La2O3-Al2O3 catalyst. Here, 10wt.% Ni refers to the Ni element content of 10wt.% based on the total mass of the catalyst after activation.

[0148] Preparation Example 6: Preparation of 15 wt.% Ni / 7.5 wt.% La2O3-diatomite catalyst by precipitation-impregnation method

[0149] S1. 10.0g of diatomaceous earth substrate (specific surface area 115m²) 2 Lanthanum nitrate hexahydrate (LnO3) was dispersed in 200 mL of deionized water, and 0.5 g of tartaric acid was added. After stirring for 0.5 h, 1.078 g of LnO3 hexahydrate was dissolved in the diatomaceous earth dispersion, and stirring was continued for 1 h. A 10 wt% NaOH-NaHCO3 mixed alkali solution (molar ratio 1:1) was added dropwise until the pH of the dispersion reached 11.5. After the pH stabilized at 11.5, the container was sealed with polyethylene film, and stirring was continued for 12 h. The solid in the dispersion was then filtered out by suction filtration, and the filter cake was washed with deionized water until the pH of the filtrate reached 7. The filter cake was first dried at 60 °C for 2 h, and then dried at 110 °C for 6 h. The dried solid was ground, heated to 550 °C at a rate of 1 °C / min, and calcined in air for 3 h to obtain a white La2O3-diatomaceous earth carrier. The mass content of La2O3 in the obtained La2O3-diatomaceous earth carrier was 7.5 wt.%.

[0150] S2. Dissolve 4.370g of nickel nitrate hexahydrate in 5.0g of deionized water and stir until homogeneous to prepare a nickel precursor solution. Weigh 5.0g of the prepared 5wt.% La2O3-diatomaceous earth support and pour it into the prepared nickel precursor solution. Stir for 0.5h. After the 5wt.% La2O3-diatomaceous earth support and the nickel precursor solution are fully mixed, seal the mouth of the impregnation container with polyethylene film and let it stand at 30℃ for 6h. Then remove the polyethylene film, dry at 60℃ for 2h, and then heat to 110℃ for 6h. Grind the dried solid and heat it to 500℃ at a heating rate of 1℃ / min. Calcinate it in air for 3h to obtain the catalyst precursor.

[0151] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 400℃ and atmospheric pressure for 3 hours to obtain a 15wt.% Ni / 7.5wt.% La2O3-diatomite catalyst. Here, 15wt.% Ni refers to the Ni element content of 15wt.% based on the total mass of the catalyst after activation.

[0152] Preparation Example 7: Preparation of 5wt.% Ni / 5wt.% La2O3-SiO2 catalyst by impregnation method

[0153] S1. Dissolve 0.5g of tartaric acid in 10g of deionized water. Weigh 10g of SiO2 substrate (grade KJ-Si-1, specific surface area 187m²). 2 / g), poured into the prepared tartaric acid solution, stirred for 0.5h to obtain tartaric acid-SiO2 slurry. 0.699g of lanthanum nitrate hexahydrate was dissolved in 10.0g of deionized water and stirred evenly to prepare a La rare earth precursor solution. The prepared La rare earth precursor solution was poured into the tartaric acid-SiO2 slurry and stirred for another 0.5h to ensure that the La rare earth precursor solution fully wetted the substrate and uniformly impregnated the SiO2 substrate. The mouth of the impregnation container was sealed with polyethylene film, and the container was left to stand at 25℃ for 12h. The polyethylene film was then removed, and the container was dried at 60℃ for 4h, followed by drying at 110℃ for 12h. The dried solid was ground and heated to 550℃ at a rate of 1℃ / min, and calcined in air for 4h to obtain a white La2O3-SiO2 support. The mass content of La2O3 in the obtained La2O3-SiO2 support was 5wt.%.

[0154] S2. Dissolve 1.304g of nickel nitrate hexahydrate in 9.5g of deionized water and stir until homogeneous to prepare a nickel precursor solution. Weigh 5.0g of the prepared 5wt.% La2O3-SiO2 support and pour it into the prepared nickel precursor solution. Stir for 0.5h. After the 5wt.% La2O3-SiO2 support and the nickel precursor solution are fully mixed, seal the mouth of the impregnation container with polyethylene film and let it stand at 25℃ for 12h. Then, remove the polyethylene film, dry at 60℃ for 4h, and then heat to 110℃ for 12h. Grind the dried solid and heat it to 550℃ at a heating rate of 1℃ / min. Calcinate it in air for 4h to obtain the catalyst precursor.

[0155] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 400℃ and atmospheric pressure for 3 hours to obtain a 5wt.% Ni / 5wt.% La2O3-SiO2 catalyst. Here, 5wt.% Ni refers to the Ni element content of 5wt.% based on the total mass of the catalyst after activation.

[0156] Preparation of Comparative Example 1: Preparation of 15 wt.% Ni / SiO2 catalyst by impregnation method

[0157] S1. Dissolve 4.370g of nickel nitrate hexahydrate in 10.0g of deionized water and stir until homogeneous to prepare a nickel precursor solution; weigh 5.0g of substrate SiO2 (grade KJ-Si-1) and pour it into the prepared nickel precursor solution, stir for 0.5h, and after the substrate and nickel precursor solution are fully mixed, seal the mouth of the impregnation container with polyethylene film and let it stand at 25℃ for 12h; then remove the polyethylene film, dry at 60℃ for 4h, and then heat to 110℃ for 12h. Grind the dried solid, heat it to 500℃ at a heating rate of 1℃ / min, and calcine it in air for 3h to obtain the catalyst precursor.

[0158] S2. The catalyst precursor was activated and reduced in high-purity hydrogen at 400℃ and atmospheric pressure for 3 hours to obtain a 15 wt.% Ni / SiO2 catalyst. Here, 15 wt.% Ni refers to the Ni element content of 15 wt.% based on the total mass of the catalyst after activation.

[0159] Preparation of Comparative Example 2: Preparation of 10 wt.% Ni / γ-Al2O3 catalyst by impregnation method

[0160] S1. Dissolve 2.774g of nickel nitrate hexahydrate in 5.0g of deionized water and stir until homogeneous to prepare a nickel precursor solution. Weigh 5.0g of substrate γ-Al2O3 and pour it into the prepared nickel precursor solution. Stir for 0.5h. After the substrate and nickel precursor solution are thoroughly mixed, seal the mouth of the impregnation container with polyethylene film and let it stand at 30℃ for 6h. Then remove the polyethylene film, dry at 60℃ for 2h, and then heat to 110℃ for 6h. Grind the dried solid and heat it to 500℃ at a heating rate of 1℃ / min. Calcinate it in air for 3h to obtain the catalyst precursor.

[0161] S2. The catalyst precursor was activated and reduced in high-purity hydrogen at 400℃ and atmospheric pressure for 3 hours to obtain a 10 wt.% Ni / γ-Al2O3 catalyst. Here, 10 wt.% Ni refers to the Ni element content of 10 wt.% based on the total mass of the catalyst after activation.

[0162] Preparation of Comparative Example 3

[0163] Commercial Raney nickel catalyst, purchased from Maclean's reagent.

[0164] Preparation of Comparative Example 4: Precipitation method for preparing 15 wt.% Ni / 5 wt.% CeO 2-x -SiO2 catalyst

[0165] S1. 1.328 g of cerium nitrate hexahydrate (III), 50 g of 20% silica sol (purchased from Sigma-Aldrich) and 4.370 g of nickel nitrate hexahydrate were thoroughly mixed and stirred at 25 °C for 1 h to ensure uniform dispersion of the components. Then, 10% NaOH-NaHCO3 mixed alkaline solution was added dropwise to the system to gradually control the pH value of the system to 11.5. After stirring for 12 h, the resulting catalyst dispersion was allowed to stand for precipitation for 12 h. The catalyst solid filter cake was then obtained by filtration and dried in an oven at 110 °C for 12 h. The dried solid was ground and heated to 550 °C at a heating rate of 1 °C / min, and calcined in air for 4 h to obtain the unreduced catalyst precursor.

[0166] S2. The catalyst precursor was activated and reduced in high-purity hydrogen at 350℃ and atmospheric pressure for 3 hours to obtain 15% Ni / 5wt.% CeO. 2-x -SiO2 catalyst. Wherein, 15wt.% Ni refers to the Ni element content of 15wt.% based on the total mass of the catalyst after activation; 5wt.% CeO 2-x -SiO2 refers to CeO 2-x CeO in SiO2 support 2-x The mass content of the oxide is 5 wt.%, where 0 < x ≤ 0.1.

[0167] Preparation of 15 wt.% Ni / 5 wt.% MgO-SiO2 catalyst by impregnation method (Comparative Example 5)

[0168] S1. Dissolve 0.5g of tartaric acid in 10g of deionized water. Weigh 10g of SiO2 substrate (grade KJ-Si-1, specific surface area 187m²). 2 / g) was poured into tartaric acid solution and stirred for 1 hour to obtain tartaric acid-SiO2 slurry; 3.348g of magnesium nitrate hexahydrate was dissolved in 10.0g of deionized water and stirred evenly to prepare Mg metal precursor solution. The prepared Mg metal precursor solution was poured into tartaric acid-SiO2 slurry and stirred for 2 hours to fully wet the substrate and uniformly impregnate the SiO2 substrate; the mouth of the impregnation container was sealed with polyethylene film and left to stand at 25℃ for 12 hours, then the polyethylene film was removed, dried at 60℃ for 4 hours, and then heated to 110℃ for 12 hours. The dried solid was ground and heated to 550℃ at a heating rate of 1℃ / min and calcined in air for 4 hours to obtain white MgO-SiO2 support, wherein the mass content of MgO in the obtained MgO-SiO2 support was 5wt.%.

[0169] S2. The preparation method of the catalyst precursor is the same as in Example 1.

[0170] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 400℃ and atmospheric pressure for 3 hours to obtain a 15wt.% Ni / 5wt.% MgO-SiO2 catalyst. Here, 15wt.% Ni refers to the Ni element content of 15wt.% based on the total mass of the catalyst after activation.

[0171] Preparation of Comparative Example 6: Preparation of 15 wt.% Ni / 5 wt.% CoO by Impregnation Method x -SiO2 catalyst

[0172] S1. Dissolve 0.5g of tartaric acid in 10g of deionized water. Weigh 10g of SiO2 substrate (grade KJ-Si-1, specific surface area 187m²). 2 / g) was poured into tartaric acid solution and stirred for 1 hour to obtain tartaric acid-SiO2 slurry; 4.088g of cobalt nitrate hexahydrate was dissolved in 10.0g of deionized water and stirred evenly to prepare a Co metal precursor solution. The prepared Co metal precursor solution was poured into the tartaric acid-SiO2 slurry and stirred for 2 hours to ensure that the Co metal precursor solution fully wetted the substrate and uniformly impregnated the SiO2 substrate; the mouth of the impregnation container was sealed with polyethylene film and left to stand at 25°C for 12 hours, then the polyethylene film was removed, and the substrate was dried at 60°C for 4 hours, and then heated to 110°C for 12 hours. The dried solid was ground and then heated to 550°C at a heating rate of 1°C / min and calcined in air for 4 hours to obtain black CoO.x -SiO2 support, 1≤x≤1.5, wherein the obtained CoO x -CoO in SiO2 support x The mass content is 5 wt.%.

[0173] S2. The preparation method of the catalyst precursor is the same as in Example 1.

[0174] S3. The catalyst precursor was activated and reduced in high-purity hydrogen at 350℃ and atmospheric pressure for 3 hours to obtain 15wt.% Ni / 5wt.% CoO. x -SiO2 catalyst. Here, 15wt.% Ni refers to the Ni element content of 15wt.% based on the total mass of the catalyst after activation.

[0175] Application Example 1

[0176] (1) Preparation of cyclic olefin polymer PDMON

[0177] The monomer (DMON) shown in formula (I”) was used for polymerization, and solution polymerization was carried out using Grubbs 2nd catalyst (CAS: 301224-40-8) in the solvent of tetrahydrofuran.

[0178] The preparation steps included: first, dissolving 1 g of DMON in 10 mL of tetrahydrofuran, then adding Grubbs 2nd catalyst (G2), wherein the molar ratio of DMON to G2 was 10000:1. The reaction was then carried out under N2 protection at 25 °C for 0.5 h. After the reaction was completed, vinyl ether and methanol were added to the solution to quench the reaction, and then the polymer solid was filtered out and dried under vacuum at 60 °C for 12 h to obtain the polymer precursor PDMON, with a weight-average molecular weight Mw = 555329 and PDI = 1.953.

[0179]

[0180] (2) Hydrogenation of the cyclic olefin polymer PDMON

[0181] The catalyst prepared in Example 1 was used for the hydrogenation of the above-mentioned cyclic olefin polymer PDMON. The specific steps included: the reaction solution and the catalyst were added to the reactor for reaction. After the reaction was completed, the hydrogen valve was closed. After cooling to room temperature, the catalyst was centrifuged and separated. Sufficient methanol was added to the reaction solution to precipitate the polymer. After filtration, washing, and vacuum drying, the corresponding product was obtained.

[0182] The reaction was carried out in a 316L stainless steel reactor with a maximum volume of 1L. The reaction solution was prepared with p-xylene as solvent to contain 6 wt.% PDMON. The hydrogen pressure in the system was kept constant at 2.9 MPa, the mass of the reaction solution was 550 g, the amount of catalyst added was 5.0 g, the reaction temperature was 120℃, and the reaction time was 3 h.

[0183] Application Examples 2-7, Comparative Examples 1-2, and Comparative Examples 4-6

[0184] The catalysts used in Application Examples 2-7, Comparative Examples 1-2, and Comparative Examples 4-6 were the catalysts prepared in Application Examples 2-7, Comparative Examples 1-2, and Comparative Examples 4-6, respectively. The preparation and hydrogenation of the cyclic olefin polymer PDMON were the same as in Application Example 1.

[0185] Application Comparative Example 3

[0186] The catalyst prepared in Comparative Example 3 was used for the hydrogenation of PDMON synthesized by ring-opening metathesis polymerization of DMON monomer, specifically including the following steps:

[0187] The Raney nickel catalyst from Comparative Example 3 and a reactor containing 550 g of 6 wt.% PDMON-tetrahydrofuran solution were placed in a nitrogen bag filled with N2. 1.0 g of the water-sealed Raney nickel catalyst was filtered through a funnel and quickly poured into the reactor. The reactor was then sealed and the nitrogen bag removed, and a hydrogenation reaction was carried out under the following conditions: constant hydrogen pressure of 4.0 MPa, reaction temperature of 150 °C, and reaction time of 3 h. After the reaction was complete, the hydrogen valve was closed, and the mixture was allowed to cool to room temperature. The catalyst was then centrifuged, and sufficient methanol was added to the reaction solution to precipitate the polymer. The polymer was then filtered, washed, and vacuum dried to obtain the product.

[0188] Example 1

[0189] The specific surface area, Ni content, and Ni dispersion of the catalysts prepared in Examples 1-7 and Comparative Examples 1-6 were tested, and the test results are summarized in Table 1.

[0190] (1) Specific surface area test method:

[0191] The specific surface area and pore size were determined using a Micromeritics ASAP 2020Plus analyzer. The test procedure was as follows: 0.5 g of solid powder was weighed into a quartz sample tube, degassed under vacuum at 120 °C for 6 h, and after cooling, the sample tube was transferred to the analysis port. The nitrogen adsorption-desorption curve of the sample was collected at -196 °C to obtain the specific surface area of ​​the catalyst.

[0192] (2) Ni content testing method:

[0193] Inductively coupled plasma atomic emission spectrometry (ICP-OES) was used for determination. The test steps were as follows: ① Sample preparation: A certain amount of sample was placed in a polytetrafluoroethylene digestion bottle, and sufficient aqua regia and hydrogen peroxide were added. The sample was weighed, and then the digestion vessel containing the sample was placed in a dedicated microwave digester to dissolve the sample; ② Test: The dissolved sample solution was pumped into the ICP-OES instrument for quantitative analysis to obtain the Ni content.

[0194] (3) Ni dispersion test method:

[0195] The Ni dispersion was determined using a Micrometritics Autochem III chemisorption analyzer. The test procedure was as follows: a certain amount of 60-mesh unreduced catalyst powder was accurately weighed and filled into a U-shaped quartz glass tube, which was then connected to the gas path of the instrument. The sample was pretreated by reducing the catalyst with high-purity hydrogen at 350℃ for 3 hours, then switching to high-purity nitrogen, purging at 500℃ for 1 hour, and then cooling to 25℃. During sample testing, at 25℃, a 0.5% H2 / Ar mixture was pulsed through the metered gas loop using an automatically controlled system until the sample was saturated with H2 adsorption, thus obtaining the Ni dispersion. The test data are summarized in Table 1.

[0196] Table 1. Specific surface area, Ni content, and Ni dispersion of the catalyst.

[0197]

[0198] As shown in Table 1, the specific surface areas of the catalysts prepared in Examples 1-7 range from 90 to 170 m². 2 / g, the nickel element has a high degree of dispersion on the catalyst surface, with the Ni dispersion ranging from 24.1% to 42.2%.

[0199] Comparing preparation examples 1 and 5 with preparation comparative examples 1 and 2, it can be seen that using a support loaded with light rare earth oxides is beneficial to improving the dispersion of nickel on the catalyst surface and enhancing the catalytic activity of the catalyst.

[0200] The composition of Preparation Example 1 and Preparation Comparative Example 4 is the same, but the catalyst used in Preparation Comparative Example 4 is prepared by simultaneously mixing the raw materials and precipitating them. The specific surface area, Ni content and Ni dispersion of the catalyst in Preparation Comparative Example 4 are all lower than those in Example 1.

[0201] The substrate on which the catalyst of Comparative Example 5 was prepared was supported was MgO, while the substrate on which the catalyst of Comparative Example 6 was prepared was supported was CoO. xEverything else was the same as in Example 1. The specific surface area and Ni dispersion of the catalyst prepared in Comparative Example 5 were both lower than those in Example 1, and the specific surface area and Ni dispersion of the catalyst prepared in Comparative Example 6 were also lower than those in Example 1.

[0202] Example 2

[0203] The hydrogenation reaction products of Application Examples 1-7 and Application Comparative Examples 1-6 were analyzed by 1H-NMR and gel size exclusion chromatography (GPC). 1H-NMR was used to quantify the conversion rate of C=C in the polymer, and GPC was used to determine the molecular weight and distribution PDI of the polymer. The reaction data are summarized in Table 2.

[0204] in, 1 For H-NMR testing, deuterated chloroform is used as the solvent for testing cyclic olefin polymers, while deuterated benzene is used as the solvent for testing hydrogenated cyclic olefin polymer products obtained by hydrogenation of cyclic olefin polymers. 1 H-NMR spectrum as shown Figure 3 and Figure 4 As shown.

[0205] The GPC test used the high-temperature GPC method, with an Agilent 1260 Infinity chromatographic column, 1,2,4-trichlorobenzene mobile phase, and a PLgel Olexis column.

[0206] Table 2

[0207] Requesting Numbers Catalyst number used Conversion rate (%) Mw <![CDATA[PDI(M w / M n )]]> Application Example 1 Preparation Example 1 99.4 55322 2.099 Application Example 2 Preparation Example 2 99.2 54219 2.129 Application Example 3 Preparation Example 3 98.6 55329 2.057 Application Example 4 Preparation Example 4 98.8 53578 2.202 Application Example 5 Preparation Example 5 99.0 54018 2.113 Application Example 6 Preparation Example 6 98.5 55506 2.031 Application Example 7 Preparation Example 7 96.3 55141 2.066 Application Comparative Example 1 Preparation of Comparative Example 1 92.0 48991 3.402 Application Comparative Example 2 Preparation of Comparative Example 2 95.6 46996 3.577 Application Comparative Example 3 Preparation of Comparative Example 3 99.0 50997 2.562 Application Comparative Example 4 Preparation of Comparative Example 4 97.8 49199 2.602 Application Comparative Example 5 Preparation of Comparative Example 5 78.3 54118 1.998 Application Comparative Example 6 Preparation of Comparative Example 6 70.6 47117 3.476

[0208] As shown in Table 2, the catalysts prepared in Examples 1 to 7 exhibit high activity in the catalytic hydrogenation of ring-opening heterotopic polymers. The conversion rate of C=C during the hydrogenation of cyclic olefin polymers is 96% or higher, and the molecular weight distribution (PDI) of the hydrogenated cyclic olefin polymers obtained after hydrogenation is narrow, below 2.3.

[0209] Comparing Application Example 3 and Application Example 7, it can be seen that the C=C conversion rate of Application Example 3 is higher than that of Application Example 7; and the molecular weight distribution PDI of the hydrogenated cyclic olefin polymer obtained after hydrogenation is lower than that of Application Example 7.

[0210] Comparing application examples 1 and 5 with application comparative examples 1 and 2, it can be seen that using a support loaded with light rare earth oxides can improve the catalytic activity of the catalyst, and the hydrogenated cyclic olefin polymers obtained by hydrogenating the cyclic olefin polymers using the catalyst have a narrower molecular weight distribution.

[0211] Comparing application examples 1-6 with application comparative example 3, it can be seen that the nickel catalyst of the present invention is more convenient to use than the conventional Raney nickel, the reaction conditions are milder, and the molecular weight distribution of the hydrogenated cyclic olefin polymer obtained by hydrogenation is narrower.

[0212] Comparing Application Example 1 and Application Comparative Example 4, it can be seen that the conversion rate of C=C in Application Comparative Example 4 is lower than that in Application Example 1, and the molecular weight distribution (PDI) of the hydrogenated cyclic olefin polymer is wider than that in Application Example 1.

[0213] Comparative Example 5 used the catalyst prepared in Comparative Example 5, whose substrate was supported on MgO. Comparative Example 6 used the catalyst prepared in Comparative Example 6, whose substrate was supported on CoO. x Everything else was the same as the catalyst in Preparation Example 1. Comparing Application Example 1 and Application Comparative Examples 5-6, it can be seen that the C=C conversion rate of Application Comparative Example 5 was lower than that of Application Example 1, the C=C conversion rate of Application Comparative Example 6 was lower than that of Application Example 1, and the molecular weight distribution PDI of the hydrogenated cyclic olefin polymer was wider than that of Application Example 1.

[0214] Example 3

[0215] 1500h Cyclic Application Test of Catalyst for PDMON Hydrogenation

[0216] The catalysts prepared in Preparation Example 1, Preparation Example 5, Comparative Example 1, and Comparative Example 2 were subjected to catalyst recycling tests, specifically including the following steps:

[0217] The test used a 316L stainless steel mechanically stirred reactor with a maximum volume of 1L as the reactor. The reactor adopted a bottom discharge design, and a 25μm pore size filter was installed above the discharge port to trap the catalyst inside the reactor. The reaction solution and catalyst were added to the reactor for reaction. In the initial test, the C=C conversion rate of the cyclic olefin polymer was controlled at 98%. After the reaction, after the material cooled to room temperature, the hydrogen in the reactor was replaced with nitrogen, and then the reactor was sealed for discharge. The catalyst remained in the reactor due to the filter screen. Then, the next batch of substrate solution was pumped into the reactor for the next test. The catalyst cycle stability test was carried out for a total of 1500 hours. After the reaction evaluation, the catalyst was removed, soaked and washed with tetrahydrofuran, and vacuum dried. The nickel content and Ni dispersion of the catalyst were analyzed, and the C=C conversion rate of PDMON was tested. The method for testing the nickel content and Ni dispersion of the catalyst was the same as in Example 1, and the method for testing the C=C conversion rate of PDMON was the same as in Example 2.

[0218] The reaction solution was prepared using a mixed solution of 80 wt.% toluene and 20% n-octane as a solvent to form a polymer solution with a mass fraction of 6 wt.%. The hydrogen pressure in the system was kept constant at 1.5 MPa during the reaction. The mass of the reaction solution was 550 g, the amount of catalyst added was 5.0 g, the reaction temperature was 80 °C, and the reaction time was 10 h.

[0219] The test results are summarized in Table 3.

[0220] Table 3 applies data to the 1500h hydrogenation cycle of PDMON.

[0221]

[0222] Table 2 shows that after 1500 h of cycling, the catalysts of Preparation Example 1 and Preparation Example 5 still maintained a C=C conversion rate of over 98% during the hydrogenation of cyclic olefin polymers. However, after 500 h of cycling, the catalysts of Comparative Example 1 and Comparative Example 2 showed that the C=C conversion rates during the hydrogenation of cyclic olefin polymers decreased to 49.6% and 37.1%, respectively, indicating severe deactivation. This demonstrates that the catalyst of the present invention exhibits good stability and a long service life. The presence of light rare earth elements effectively reduces the loss of supported nickel and prevents the agglomeration of metallic nickel in a hydrogen atmosphere, maintaining a high degree of dispersion.

[0223] The above embodiments are preferred embodiments of the invention, but the embodiments of the present invention are not limited to the above examples. Any changes, modifications, substitutions, combinations and simplifications made without departing from the spirit and principle of the present invention are equivalent.

Claims

1. A method for hydrogenating a cyclic olefin polymer, characterized in that, It uses a catalyst to catalytically hydrogenate cyclic olefin polymers to obtain hydrogenated cyclic olefin polymers; The catalyst includes a support and nickel element supported on the support; The carrier comprises a substrate and light rare earth elements; the substrate is SiO2 and / or Al2O3. Based on the total mass of the catalyst, the proportion of nickel is 5 wt.% to 30 wt.%; the proportion of light rare earth elements is 0.5 wt.% to 10 wt.%; and the proportion of the substrate is 60 wt.% to 94.5 wt.%. The specific surface area of ​​the catalyst is not less than 80 m². 2 / g; The cyclic olefin polymer comprises structural units as shown in formula (I); Equation (I); In equation (Ⅰ), m is 0, 1, 2 or 3; R1 to R4 are each independently hydrogen, straight-chain or branched C1 to C18 alkyl, substituted or unsubstituted C6 to C9 aryl; At least one of R1, R2, R3 and R4 is hydrogen; The weight-average molecular weight of the cyclic olefin polymer is 35,000 to 65,000. The molecular weight distribution index of the cyclic olefin polymer is 1.5 to 4.

0.

2. The hydrogenation method for cyclic olefin polymers as described in claim 1, characterized in that, The nickel element exists in the form of metallic nickel and / or nickel oxide; And / or, the proportion of nickel is 5 wt.% to 24 wt.%; And / or, the light rare earth elements are distributed on the surface of the substrate; And / or, the light rare earth element is La and / or Ce; And / or, the proportion of the light rare earth elements is 0.5 wt.% to 7.5 wt.%; And / or, the substrate comprises 65 wt.% to 90 wt.%; And / or, the specific surface area of ​​the catalyst is 96~179 m². 2 / g.

3. The hydrogenation method for cyclic olefin polymers as described in claim 2, characterized in that, The mass percentage of nickel element present in metallic nickel form shall not be less than 80%; And / or, the proportion of nickel is 10 wt.% or 15 wt.%; And / or, the La exists in the form of La2O3; And / or, the Ce is CeO 2-x It exists in the form of , where 0 < x ≤ 0.5; And / or, the proportion of the light rare earth elements is 0.5~5 wt.%; And / or, the substrate comprises 80 wt.%, 82 wt.%, or 85 wt.%; And / or, the catalyst has a specific surface area of ​​137 m². 2 / g、142 m 2 / g、153 m 2 / g or 161 m 2 / g.

4. The hydrogenation method for cyclic olefin polymers as described in claim 3, characterized in that, 0＜x≤0.1； And / or, the proportion of the light rare earth elements is 3 wt.% or 5 wt.%.

5. The hydrogenation method for cyclic olefin polymers as described in claim 1, characterized in that, The preparation method of the catalyst includes the following steps: S1. The carrier raw material composition is impregnated or precipitated, and then subjected to a first calcination to obtain the carrier; the carrier raw material composition includes a substrate, a light rare earth element source, and a solvent; the substrate includes SiO2 and / or Al2O3; S2. The support is impregnated in a nickel source solution and then calcined a second time to obtain the catalyst precursor; S3. The catalyst precursor is activated and reduced to obtain the catalyst.

6. The hydrogenation method for the cyclic olefin polymer as described in claim 5, characterized in that, The nickel source in the nickel source solution is a nickel salt and / or a derivative of a nickel salt; And / or, the light rare earth element source is a light rare earth metal salt and / or a derivative of a light rare earth metal salt; And / or, the specific surface area of ​​the substrate is not less than 100 m². 2 / g; And / or, the temperature of the first calcination is 350~600℃; And / or, the temperature of the second calcination is 350~600℃.

7. The hydrogenation method for the cyclic olefin polymer as described in claim 6, characterized in that, The nickel salt is one or more of nickel nitrate, nickel chloride, and nickel acetate; And / or, the nickel salt derivative is one or more of the following: nickel nitrate derivative, nickel chloride derivative, and nickel acetate derivative; And / or, the light rare earth metal salt is one or more of lanthanum nitrate, lanthanum acetate, lanthanum chloride, cerium nitrate, cerium ammonium nitrate, and cerium trichloride or their derivatives; And / or, the derivative of the light rare earth metal salt is one or more of the following: a derivative of lanthanum nitrate, a derivative of lanthanum acetate, a derivative of lanthanum chloride, a derivative of cerium nitrate, a derivative of cerium ammonium nitrate, and a derivative of cerium trichloride. And / or, the specific surface area of ​​the substrate is 115 m². 2 / g、153 m 2 / g or 187 m 2 / g; And / or, the temperature of the first calcination is 500°C or 550°C; And / or, the temperature of the second calcination is 500°C or 550°C.

8. The hydrogenation method for the cyclic olefin polymer as described in claim 7, characterized in that, The light rare earth metal salts are lanthanum nitrate and cerium (III) nitrate or their derivatives; And / or, the derivatives of the light rare earth metal salts are derivatives of lanthanum nitrate and cerium nitrate.

9. The hydrogenation method for cyclic olefin polymers as described in claim 5, characterized in that, The activation and reduction temperature is 300~400℃; And / or, the activation and reduction time is 1~6 h; And / or, after the activation and reduction, the specific surface area of ​​the catalyst is not less than 80 m². 2 / g.

10. The hydrogenation method for the cyclic olefin polymer as described in claim 9, characterized in that, The activation and reduction temperature is 350℃; And / or, the activation and reduction time is 3 h.

11. The hydrogenation method for the cyclic olefin polymer as described in claim 1, characterized in that, The substituted C6-C9 aryl group is a meta-substituted C6-C9 aryl group or a para-substituted C6-C9 aryl group; At least two of R1, R2, R3 and R4 are hydrogen; And / or, the weight-average molecular weight of the cyclic olefin polymer is 555,329; And / or, the molecular weight distribution index of the cyclic olefin polymer is 1.

953.

12. The hydrogenation method for the cyclic olefin polymer as described in claim 11, characterized in that, At least one of R1 and R2 is a hydrogen atom, and at least one of R3 and R4 is a hydrogen atom.

13. The hydrogenation method for the cyclic olefin polymer as described in claim 1, characterized in that, The cyclic olefin polymer is formed by ring-opening metathesis polymerization of monomers; the monomers include compounds represented by formula (I'): Equation (Ⅰ'); Wherein, in the formula (Ⅰ'), m and R1~R4 are as described in any one of claims 1, 11-12; The polymerization is carried out in a solvent.

14. The hydrogenation method for the cyclic olefin polymer as described in claim 13, characterized in that, The polymerization temperature is 0~140℃; And / or, the polymerization time is 0.1~6 h; And / or, the polymerization pressure is 0~1.5 MPa; And / or, the solvent is one or more of dichloromethane, tetrahydrofuran, toluene, xylene, and chlorobenzene.

15. The hydrogenation method for the cyclic olefin polymer as described in claim 14, characterized in that, The polymerization temperature is 25°C; And / or, the polymerization time is 0.5 h; And / or, the chlorobenzene is trichlorobenzene.

16. The hydrogenation method for the cyclic olefin polymer as described in claim 1, characterized in that, It satisfies one or more of the following (a) to (e): (a) In the hydrogenation process, the solvent used is one or more of the following: alkanes with not less than 6 carbon atoms, cycloalkanes with not less than 6 carbon atoms, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and tetrahydrofuran; (b) The hydrogen source used in the hydrogenation process is hydrogen or a mixture of gases containing hydrogen; (c) The hydrogenation temperature is 60~200℃; (d) The hydrogenation time is 1~12 h; and, (e) After hydrogenation, the conversion rate of carbon-carbon double bonds in the cyclic olefin polymer is not less than 98.5%.

17. The hydrogenation method for the cyclic olefin polymer as described in claim 16, characterized in that, It satisfies one or more of the following (a) to (c): (a) The pressure of the hydrogen source is 0.5~4 MPa; (b) The hydrogenation temperature is 80°C or 120°C; and, (c) The hydrogenation time is 3 h or 10 h.

18. A hydrogenated cyclic olefin polymer, characterized in that, It is obtained by hydrogenation of the cyclic olefin polymer as described in any one of claims 1 to 17.

19. The hydrogenated cyclic olefin polymer according to claim 18, characterized in that, The molecular weight distribution index of the hydrogenated cyclic olefin polymer is not higher than 2.5.

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