Ruthenium-containing catalyst as well as preparation method and application thereof

Abstract

The invention provides a ruthenium-containing catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. According to the invention, 3, 3 '-dibromo-4, 4'-biphenol, 1, 3, 5-tri (p-vinylphenyl) benzene and ruthenium salt are used as main raw materials to carry out polymerization reaction so as to prepare a ruthenium-containing catalyst in which nano-scale pore channels are formed; the obtained ruthenium-containing catalyst is good in catalytic performance, thermal stability and chemical stability; the ruthenium-containing catalyst is used for catalyzing hydrogenation of diisononyl phthalate to prepare the cyclohexane-1, 2-diisononyl phthalate, the catalytic effect of the ruthenium-containing catalyst is good, and the yield of the cyclohexane-1, 2-diisononyl phthalate is high.

Description

Technical Field

[0001] The present disclosure relates to the field of catalyst technology, and in particular to a ruthenium-containing catalyst and a preparation method and application thereof. Background Art

[0002] Diisononyl cyclohexane-1,2-dicarboxylate (also known as diisononyl hexahydrophthalate, DINCH for short) is a new type of safe and environmentally friendly plasticizer, with similar structure and properties to diisononyl phthalate (DINP) and dioctyl phthalate (DOP), and is mainly used in: medical drugs, food packaging, children's toys and child care products. More importantly, its plasticized products can be self-biodegraded in the natural environment, without causing environmental pollution, which is beneficial to human health and safety, and is a good substitute for benzoic acid ester plasticizers. Therefore, it has become a general trend to develop new high-efficiency, non-toxic and degradable plasticizers to replace traditional varieties.

[0003] At present, the main methods for synthesizing diisononyl cyclohexane-1,2-dicarboxylate (DINCH) include direct hydrogenation, direct esterification and transesterification. The process of preparing DINCH by direct hydrogenation is mainly to directly hydrogenate diisononyl phthalate (DINP) to diisononyl cyclohexane-1,2-dicarboxylate (DINCH) under high temperature and high pressure using precious metal catalysts such as nickel, platinum, palladium, rhodium and ruthenium. The process technology route is simple and clean, but it has high requirements for equipment and catalysts and requires large investment.

[0004] The catalyst used in the direct esterification process to prepare DINCH does not catalyze the esterification reaction completely, and the yield of diisononyl cyclohexane-1,2-dicarboxylate is low. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a ruthenium-containing catalyst and a preparation method and application thereof; the ruthenium-containing catalyst is used to catalyze the hydrogenation of diisononyl phthalate to prepare diisononyl cyclohexane-1,2-dicarboxylate, the ruthenium-containing catalyst has good catalytic effect and high yield of diisononyl cyclohexane-1,2-dicarboxylate.

[0006] To achieve the above objectives, the technical solution adopted by the present disclosure is:

[0007] In a first aspect, a method for preparing a ruthenium-containing catalyst comprises the following steps:

[0008] 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene, ruthenium salt, potassium carbonate, catalyst and solvent are mixed and polymerized to obtain a ruthenium-containing catalyst; the ruthenium salt is at least one of ruthenium trichloride (III) hydrate, tri(triphenylphosphine) ruthenium dichloride, dichloro(p-methylisopropylbenzene) ruthenium (II) dimer, ruthenium trichloride, ruthenium red and terpyridine ruthenium chloride hexahydrate.

[0009] In the present disclosure, the structural formula of 3,3'-dibromo-4,4'-biphenyl is CAS number is 83909-22-2;

[0010] The structural formula of 1,3,5-tri(p-vinylphenyl)benzene is: The CAS number is 944155-02-6.

[0011] The present invention uses 3,3'-dibromo-4,4'-biphenol as 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene as 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt as raw materials for polymerization reaction. Through the reaction between different functional groups, nanometer-level channels are formed inside the ruthenium-containing catalyst. Such channels are beneficial to increasing the specific surface area of ​​the ruthenium-containing catalyst, so that the catalytic sites can be more exposed in the catalytic system, which is beneficial to improving the catalytic performance of the ruthenium-containing catalyst. The benzene ring structure between 3,3'-dibromo-4,4'-biphenol and 1,3,5-tri(p-vinylphenyl)benzene can make the ruthenium-containing catalyst have a rigid structure and improve the mechanical strength of the ruthenium-containing catalyst. The organic monomers are connected by covalent bonds. Therefore, the ruthenium-containing catalyst has excellent thermal stability and chemical stability, and the structure of the ruthenium-containing catalyst remains intact after being immersed in an organic solvent for a long time. In addition, solid ruthenium-containing catalysts are conducive to separation and recycling.

[0012] In one embodiment, the ruthenium salt is at least one of ruthenium (III) chloride hydrate, ruthenium trichloride, and terpyridyl ruthenium chloride hexahydrate.

[0013] In the present disclosure, ruthenium salt affects the catalytic performance of the ruthenium-containing catalyst. When the ruthenium salt is at least one of ruthenium (III) chloride hydrate, ruthenium trichloride, and terpyridine ruthenium chloride hexahydrate, the obtained ruthenium-containing catalyst has better catalytic performance.

[0014] In one embodiment, the molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium salt=(1:1:5)-(5:5:1).

[0015] In the present disclosure, the molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt affects the specific surface area and porous structure of the ruthenium-containing catalyst; as the molar content of the ruthenium salt increases, the specific surface area of ​​the ruthenium-containing catalyst gradually decreases; the present disclosure selects the molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt as 3,3'-dibromo-4,4'-biphenol: 1,3,5-tri(p-vinylphenyl)benzene: ruthenium salt = (1:1:5)-(5:5:1), and the ruthenium-containing catalyst can not only obtain more nanopores, but also introduce more functional groups, thereby improving the catalytic performance, thermal stability and chemical stability of the ruthenium-containing catalyst. Preferably, the molar ratio of the 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and the ruthenium salt is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium salt=(1:1:3)-(3:3:1); More preferably, the molar ratio of the 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and the ruthenium salt is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium salt=(1:1:2)-(2:2:1); The molar ratio within the preferred range can obtain a ruthenium-containing catalyst with better catalytic performance, thermal stability and chemical stability.

[0016] In one embodiment, the polymerization reaction temperature is 75-135° C.; and / or, the polymerization reaction time is 10-48 h.

[0017] The present invention discloses a method for generating a ruthenium-containing catalyst containing a transition metal by mixing raw materials and subjecting a ruthenium salt and an organic monomer to a polymerization reaction; the temperature and time of the polymerization reaction, and the molar ratio of 3,3'-dibromo-4,4'-biphenol to 1,3,5-tri(p-vinylphenyl)benzene have a certain influence on the polymerization degree of the ruthenium-containing catalyst; for example, at least one of a lowering of the polymerization reaction temperature, a lowering of the monomer ratio, and a shortening of the reaction time causes the polymerization degree of the ruthenium-containing catalyst to decrease, the content of the transition metal in the pores to decrease, and the specific surface area of ​​the obtained ruthenium-containing catalyst to decrease, thereby causing the catalytic activity of the ruthenium-containing catalyst to decrease; at least one of an overly high polymerization reaction temperature, an increased monomer ratio, and an overly long reaction time causes the polymerization degree of the ruthenium-containing catalyst to decrease, and the content of the transition metal in the pores to decrease, thereby causing the specific surface area of ​​the obtained ruthenium-containing catalyst to decrease. The polymerization reaction is in a boiling state, the transition metal loses its activity, and then the thermal stability and catalytic performance of the ruthenium-containing catalyst decrease; the present invention selects the polymerization reaction temperature of 75-135°C and the polymerization reaction time of 10-48h to ensure that the polymerization reaction is in a mild preparation condition; a ruthenium-containing catalyst with high catalytic performance, thermal stability and chemical stability is obtained; preferably, the polymerization reaction temperature is 100-125°C, and the polymerization reaction time is 30-45h; more preferably, the polymerization reaction temperature is 120°C, and the polymerization reaction time is 40h; the polymerization reaction temperature and time are within the preferred range, which can further improve the porosity of the ruthenium-containing catalyst, thereby, the catalytic performance of the ruthenium-containing catalyst is better.

[0018] In one embodiment, the catalyst is tetrakistriphenylphosphine palladium and / or triphenylphosphine.

[0019] In one embodiment, the catalyst is tetrakistriphenylphosphine palladium and triphenylphosphine; the molar ratio of tetrakistriphenylphosphine palladium to triphenylphosphine is (1:4)-(4:1).

[0020] In one embodiment, the ratio of the mass of the catalyst to the total mole of 3,3'-dibromo-4,4'-biphenyldiphenol and 1,3,5-tri(p-vinylphenyl)benzene is 0.9 g:(2-5 mmol).

[0021] In the present disclosure, the type and content of the catalyst affect the rate of the polymerization reaction. The present disclosure selects the type and content of the above-mentioned catalyst to maintain the rate of the polymerization reaction within an appropriate range to avoid the polymerization reaction rate being too fast or too slow, so as to obtain a ruthenium-containing catalyst with better performance.

[0022] In one embodiment, the solvent is at least one of chloroform, ether, benzene, methyl acetate, tetrahydrofuran, acetone, methanol, petroleum, chlorophenol, ethylene dichloride, and carbon tetrachloride; preferably, the solvent is tetrahydrofuran.

[0023] In one embodiment, after the polymerization reaction is completed, the obtained product is filtered, washed, Soxhlet extracted and dried in sequence to obtain a ruthenium-containing catalyst.

[0024] The present disclosure has no particular limitation on the specific operation method of the filtration, and a filtration method well known to those skilled in the art may be used.

[0025] The present disclosure has no special limitation on the washing solution, and washing can be performed using a washing solution well known in the art, such as deionized water, ethanol, hydrochloric acid solution, etc. The present disclosure prefers washing with hydrochloric acid having a molar concentration of 1-2 mol / L; further prefers washing with a hydrochloric acid solution having a molar concentration of 1.5 mol / L.

[0026] The present disclosure has no special limitation on the solvent for Soxhlet extraction, and the Soxhlet extraction is performed using a solvent known in the art. The present disclosure prefers dichloromethane, tetrahydrofuran and petroleum ether for Soxhlet extraction, and the specific steps are: the product obtained by washing is subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran and petroleum ether in sequence.

[0027] The present disclosure has no particular limitation on the time of Soxhlet extraction, and those skilled in the art can select a suitable time according to actual needs. The present disclosure selects a Soxhlet extraction time of 48-72 h / time, preferably 56-71 h / time, and more preferably 70 h / time.

[0028] The present disclosure does not specifically limit the specific operation mode of the drying, and a filtering method well known to those skilled in the art can be used. The preferred drying method of the present disclosure is vacuum drying.

[0029] The present disclosure does not specifically limit the drying temperature and time, and those skilled in the art can select appropriate temperature and time according to actual needs. The present disclosure selects a drying temperature of 50-100°C and a drying time of 18-24h; preferably, the drying temperature is 70-90°C and the drying time is 20-23h; more preferably, the drying temperature is 80°C and the drying time is 22h.

[0030] In a second aspect, a ruthenium-containing catalyst is provided, wherein the ruthenium-containing catalyst is prepared by the above-mentioned preparation method of the ruthenium-containing catalyst.

[0031] In a third aspect, a use of the ruthenium-containing catalyst in the preparation of diisononyl cyclohexane-1,2-dicarboxylate is provided.

[0032] In one embodiment, the application includes the following steps: adding diisononyl phthalate and a ruthenium catalyst into a reactor at the same time, introducing hydrogen at a pressure of 0.5-2MPa, heating to 150-220°C, reacting for 0.5-3h, and obtaining diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium catalyst is (1:0.01)-(1:0.05).

[0033] The ruthenium-containing catalyst disclosed in the present invention is used to catalyze the hydrogenation of diisononyl phthalate to prepare diisononyl cyclohexane-1,2-dicarboxylate, and the ruthenium-containing catalyst has a good catalytic effect.

[0034] In one embodiment, the reaction temperature is 160-200°C.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The present invention uses 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt as main raw materials for polymerization reaction to obtain a ruthenium-containing catalyst with nano-scale pores formed inside. The nano-scale pores are conducive to increasing the specific surface area of ​​the ruthenium-containing catalyst, so that the catalytic sites can be more exposed in the catalytic system, which is conducive to improving the catalytic performance of the catalyst. At the same time, the solid ruthenium-containing catalyst is conducive to separation and recycling. In addition, the ruthenium-containing catalyst of the present invention uses a monomer containing a benzene ring as a structural unit, and 3,3'-dibromo-4,4'-biphenol and 1,3,5-tri(p-vinylphenyl)benzene are connected by covalent bonds, so that the obtained ruthenium-containing catalyst has a rigid structure, which improves the mechanical strength, thermal stability and chemical stability of the ruthenium-containing catalyst; the structure of the ruthenium-containing catalyst remains intact after being immersed in an organic solvent for a long time;

[0037] (2) The ruthenium-containing catalyst disclosed in the present invention is used to catalyze the hydrogenation of diisononyl phthalate to prepare diisononyl cyclohexane-1,2-dicarboxylate. The ruthenium-containing catalyst has good catalytic effect and a high yield of diisononyl cyclohexane-1,2-dicarboxylate. DETAILED DESCRIPTION

[0038] In order to better illustrate the purpose, technical scheme and advantages of the present disclosure, the present disclosure will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present disclosure in detail, rather than to limit the present disclosure. All other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present disclosure. The experimental reagents and instruments involved in the implementation of the present disclosure are all commonly used ordinary reagents and instruments unless otherwise specified.

[0039] The raw materials used in the embodiments and comparative examples are described below:

[0040] 3,3'-Dibromo-4,4'-biphenylene glycol:

[0041] 1,3,5-Tri(p-vinylphenyl)benzene:

[0042] Other raw materials are conventional commercially available products.

[0043] Example 1

[0044] The preparation method of the ruthenium-containing catalyst of this embodiment is as follows:

[0045] 2 g of tetrakistriphenylphosphine palladium and 1 g of triphenylphosphine were added to a round-bottom flask; the flask was evacuated, filled with nitrogen, and then 100 mL of tetrahydrofuran was injected, and then 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium (III) chloride hydrate were added to the round-bottom flask, wherein the molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium (III) chloride hydrate was 3,3'-dibromo-4,4'-biphenol: 1,3,5-tri(p-vinylphenyl)benzene: ruthenium (III) chloride hydrate = 1:1:2, and the mixture was heated to 120°C for 40 hours; after the reaction was completed and cooled, the mixture was filtered, and the crude product obtained by filtration was eluted with 1.5 mol / L The product was washed with HCl solution, and the washed product was extracted with dichloromethane, tetrahydrofuran and petroleum ether in sequence. The product obtained by Soxhlet extraction was heated to 80° C. and dried for 22 hours under a vacuum environment to obtain a ruthenium-containing catalyst.

[0046] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0047] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 98%.

[0048] Example 2

[0049] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the ruthenium salt is tris(triphenylphosphine)ruthenium dichloride.

[0050] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0051] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 96%.

[0052] Example 3

[0053] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the ruthenium salt is dichloro(p-methylisopropylbenzene)ruthenium(II) dimer.

[0054] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0055] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 94%.

[0056] Example 4

[0057] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the ruthenium salt is ruthenium trichloride.

[0058] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0059] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 97%.

[0060] Example 5

[0061] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the ruthenium salt is bipyridyl ruthenium chloride.

[0062] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0063] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 99%.

[0064] Example 6

[0065] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that terpyridine ruthenium chloride hexahydrate is used to replace ruthenium (III) chloride hydrate.

[0066] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0067] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 98%.

[0068] Example 7

[0069] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Example 1 only in that:

[0070] The molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium(III) chloride hydrate=2:2:1.

[0071] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0072] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 98%.

[0073] Example 8

[0074] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Example 1 only in that:

[0075] The molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium(III) chloride hydrate=3:3:1.

[0076] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0077] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 95%.

[0078] Example 9

[0079] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Example 1 only in that:

[0080] The molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium(III) chloride hydrate=1:1:3.

[0081] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0082] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 91%.

[0083] Example 10

[0084] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Example 1 only in that:

[0085] The molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium(III) chloride hydrate=5:5:1.

[0086] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0087] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 88%.

[0088] Embodiment 11

[0089] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Example 1 only in that:

[0090] The molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium(III) chloride hydrate=1:1:5.

[0091] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0092] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 86%.

[0093] Example 12

[0094] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Example 1 only in that:

[0095] The molar ratio of 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium(III) chloride hydrate=6:6:1.

[0096] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0097] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 74%.

[0098] Embodiment 13

[0099] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that terpyridine ruthenium chloride hexahydrate is used to replace ruthenium (III) chloride hydrate.

[0100] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0101] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 98%.

[0102] Embodiment 14

[0103] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the polymerization reaction temperature is 95°C.

[0104] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0105] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 97%.

[0106] Embodiment 15

[0107] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the polymerization reaction temperature is 100°C.

[0108] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0109] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 91%.

[0110] Example 16

[0111] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the polymerization reaction temperature is 125°C.

[0112] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0113] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 98%.

[0114] Embodiment 17

[0115] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the polymerization reaction temperature is 75°C.

[0116] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0117] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 88%.

[0118] Embodiment 18

[0119] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the polymerization reaction temperature is 135°C.

[0120] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0121] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 88%.

[0122] Embodiment 19

[0123] The preparation method of the ruthenium-containing catalyst in this embodiment is different from that in Embodiment 1 only in that the polymerization reaction temperature is 65°C.

[0124] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0125] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 75%.

[0126] Embodiment 20

[0127] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0128] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 0.5 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 91%.

[0129] Embodiment 21

[0130] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0131] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1.5 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 94%.

[0132] Embodiment 22

[0133] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0134] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 2 MPa, heat to 170°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 99%.

[0135] Embodiment 23

[0136] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by hydrogenating diisononyl phthalate using the ruthenium-containing catalyst obtained in this example as a catalyst is as follows:

[0137] Add diisononyl phthalate and a ruthenium-containing catalyst into a reactor at the same time, introduce hydrogen at a pressure of 1 MPa, heat to 150°C, and react for 2 hours to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 93%.

[0138] Embodiment 24

[0139] The thermal stability and chemical stability of the ruthenium-containing catalysts obtained in each embodiment and comparative example were tested; the testing method is as follows:

[0140] Thermal stability: DZ-TGA105 high temperature thermogravimetric analyzer was used to test the thermal stability of the catalyst.

[0141] Acid-base stability: 10 mg of the catalyst was immersed in 100 mL of 1 mol / L sulfuric acid and 1 mol / L sodium hydroxide solution for 2 hours respectively. After being taken out, it was washed with clean water, dried, and tested with a DZ-TGA105 high temperature thermogravimetric analyzer.

[0142] The test results are shown in Table 1.

[0143] Table 1

[0144]

[0145]

[0146] It can be seen from the experimental data in Table 1 that the ruthenium-containing catalyst prepared in the examples of the present application has excellent thermal stability and acid-base stability.

[0147] Finally, it should be noted that the above embodiments are used to illustrate the technical solution of the present disclosure rather than to limit the protection scope of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present disclosure can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present disclosure.

Claims

1. A method for preparing a ruthenium-containing catalyst, characterized in that: The method comprises the following steps: mixing 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene, a ruthenium salt, potassium carbonate, a catalyst and a solvent, and carrying out a polymerization reaction to obtain a ruthenium-containing catalyst; the ruthenium salt is at least one of ruthenium trichloride (III) hydrate, tri(triphenylphosphine) ruthenium dichloride, dichloro(p-methylisopropylbenzene) ruthenium (II) dimer, ruthenium trichloride, ruthenium red and terpyridine ruthenium chloride hexahydrate; and the catalyst is tetrakistriphenylphosphine palladium and / or triphenylphosphine.

2. The preparation method according to claim 1, characterized in that The ruthenium salt is at least one of ruthenium (III) chloride hydrate, ruthenium trichloride, and terpyridyl ruthenium chloride hexahydrate.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the 3,3'-dibromo-4,4'-biphenol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt is 3,3'-dibromo-4,4'-biphenol:1,3,5-tri(p-vinylphenyl)benzene:ruthenium salt=(1:1:5)-(5:5:1).

4. The preparation method according to claim 1, characterized in that: The polymerization reaction temperature is 75-135° C.; and / or the polymerization reaction time is 10-48 hours.

5. The preparation method according to claim 1, characterized in that: The catalyst is tetrakistriphenylphosphine palladium and triphenylphosphine.

6. The preparation method according to claim 5, characterized in that: The molar ratio of tetrakistriphenylphosphine palladium to triphenylphosphine is (1:4)-(4:1).

7. The preparation method according to claim 1, characterized in that: The ratio of tetrakistriphenylphosphine palladium to potassium carbonate is (1:1)-(1:2).

8. The preparation method according to claim 1, characterized in that: The ratio of the mass of the catalyst to the total mole of 3,3'-dibromo-4,4'-biphenyldiphenol and 1,3,5-tri(p-vinylphenyl)benzene is 0.9 g:(2-5 mmol); and / or, the solvent is at least one of chloroform, ether, benzene, methyl acetate, tetrahydrofuran, acetone, methanol, petroleum, chlorophenol, ethylene dichloride, and carbon tetrachloride; And / or, after the polymerization reaction is completed, the obtained product is filtered, washed, Soxhlet extracted and dried in sequence to obtain a ruthenium-containing catalyst.

9. A ruthenium-containing catalyst, characterized in that The ruthenium-containing catalyst is prepared by the preparation method of the ruthenium-containing catalyst according to any one of claims 1-7.

10. Use of the ruthenium-containing catalyst as claimed in claim 9 in the preparation of diisononyl cyclohexane-1,2-dicarboxylate.

11. The use according to claim 10, characterized in that The application comprises the following steps: adding diisononyl phthalate and a ruthenium-containing catalyst into a reaction kettle at the same time, introducing hydrogen at a pressure of 0.5-2MPa, heating to 150-220°C, reacting for 0.5-3h, and obtaining diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate to the ruthenium-containing catalyst is (1:0.01)-(1:0.05).

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