A ruthenium-containing catalyst, a method for preparing the same and use thereof

Abstract

The present disclosure provides a ruthenium-containing catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The present disclosure uses 3,3'-dibromo-4,4'-diphenylol, 1,3,5-tri(p-vinylphenyl)benzene and a ruthenium salt as main raw materials to perform a polymerization reaction, so as to obtain a ruthenium-containing catalyst with nanoscale pores formed inside; the obtained ruthenium-containing catalyst has good catalytic performance, thermal stability and chemical stability; the ruthenium-containing catalyst is used to catalyze diisononyl phthalate to hydrogenation, so as to prepare diisononyl cyclohexane-1,2-dicarboxylate; the catalytic effect of the ruthenium-containing catalyst is good, and the yield of diisononyl cyclohexane-1,2-dicarboxylate is high.

Description

TECHNICAL FIELD

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

[0002] Cyclohexane-1,2-dicarboxylic acid diisononyl ester (alias: diisononyl hexahydrophthalate, for short: DINCH) is a new safe and environmentally friendly plasticizer, which has similar structure and performance to diisononyl phthalate (DINP) and dioctyl phthalate (DOP), and is mainly used in medical and pharmaceutical products, food packaging, children's toys and children's care products, and more importantly, the plasticized products can be biodegraded in the natural environment, do not cause environmental pollution, and are beneficial to human health and safety, and are good substitutes for benzoic acid ester plasticizers. Therefore, developing efficient, non-toxic and degradable plasticizer new products to replace traditional products has become a trend.

[0003] At present, the main methods for synthesizing cyclohexane-1,2-dicarboxylic acid diisononyl ester (DINCH) include direct hydrogenation method, direct esterification method and ester exchange method. The process for preparing DINCH by direct hydrogenation method mainly uses noble metal catalysts such as nickel, platinum, palladium, rhodium and ruthenium to directly hydrogenate diisononyl phthalate (DINP) into cyclohexane-1,2-dicarboxylic acid diisononyl ester (DINCH) at high temperature and high pressure. This process has a simple technical route and is clean, but requires high equipment and catalyst, and has high investment.

[0004] The catalyst used in the direct esterification method for preparing DINCH does not completely catalyze the esterification reaction, and the yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester is low. SUMMARY

[0005] The present disclosure aims 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 cyclohexane-1,2-dicarboxylic acid diisononyl ester, and the catalytic effect of the ruthenium-containing catalyst is good, and the yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester is high.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present disclosure is as follows:

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

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

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

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

[0011] The present disclosure carries out a polymerization reaction with 3,3'-dibromo-4,4'-biphenyl diol as 3,3'-dibromo-4,4'-biphenyl diol, 1,3,5-tri(p-vinylphenyl)benzene as 1,3,5-tri(p-vinylphenyl)benzene, and a ruthenium salt as raw materials. Through the reaction between different functional groups, a pore with a nanoscale is formed inside the ruthenium-containing catalyst. This pore is beneficial to improve 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 improve the catalytic performance of the ruthenium-containing catalyst. The benzene ring structure between 3,3'-dibromo-4,4'-biphenyl diol and 1,3,5-tri(p-vinylphenyl)benzene can make the ruthenium-containing catalyst have a rigid structure, improve the mechanical strength of the ruthenium-containing catalyst, and 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 long-time soaking in an organic solvent. In addition, the solid ruthenium-containing catalyst is beneficial to separation and recycling.

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

[0013] In the present disclosure, the 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 trispyridine ruthenium chloride hexahydrate, the obtained ruthenium-containing catalyst has better catalytic performance.

[0014] In one embodiment, the molar ratio of the 3,3'-dibromo-4,4'-biphenyl diol, 1,3,5-tri(p-vinylphenyl)benzene and the ruthenium salt is 3,3'-dibromo-4,4'-biphenyl diol: 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'-biphenyl-diol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt affects the specific surface area and porous structure of the ruthenium-containing catalyst; with the increase of the molar content of ruthenium salt, the specific surface area of the ruthenium-containing catalyst gradually decreases; the present disclosure selects the molar ratio of 3,3'-dibromo-4,4'-biphenyl-diol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt as 3,3'-dibromo-4,4'-biphenyl-diol: 1,3,5-tri(p-vinylphenyl)benzene: ruthenium salt = (1:1:5)-(5:5:1), the ruthenium-containing catalyst not only can obtain more nanopores, but also can introduce more functional groups, thereby improving the catalytic performance, thermal stability and chemical stability of the ruthenium-containing catalyst. Preferably, the molar ratio of 3,3'-dibromo-4,4'-biphenyl-diol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt is 3,3'-dibromo-4,4'-biphenyl-diol: 1,3,5-tri(p-vinylphenyl)benzene: ruthenium salt = (1:1:3)-(3:3:1); more preferably, the molar ratio of 3,3'-dibromo-4,4'-biphenyl-diol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium salt is 3,3'-dibromo-4,4'-biphenyl-diol: 1,3,5-tri(p-vinylphenyl)benzene: ruthenium salt = (1:1:2)-(2:2:1); the molar ratio in the preferred range can obtain a ruthenium-containing catalyst with better catalytic performance, thermal stability and chemical stability.

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

[0017] The present disclosure generates a ruthenium-containing catalyst containing a transition metal by mixing raw materials, allowing a ruthenium salt and an organic monomer to undergo a polymerization reaction; the temperature and time of the polymerization reaction, and the molar ratio of 3,3'-dibromo-4,4'-biphenyldiol and 1,3,5-tris(p-vinylphenyl)benzene have certain effects on the polymerization degree of the ruthenium-containing catalyst; for example, at least one of a decrease in the temperature of the polymerization reaction, a decrease in the monomer ratio, and a decrease in the reaction time causes the polymerization degree of the ruthenium-containing catalyst to decrease, the content of the transition metal in the pore channel 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 excessively high temperature of the polymerization reaction, an excessively high monomer ratio, and an excessively long reaction time causes the polymerization reaction to be in a boiling state, the transition metal to lose activity, and the thermal stability and catalytic performance of the ruthenium-containing catalyst to decrease; the present disclosure selects the temperature of the polymerization reaction to be 75-135°C and the time of the polymerization reaction to be 10-48h, so as 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 temperature of the polymerization reaction is 100-125°C and the time of the polymerization reaction is 30-45h; more preferably, the temperature of the polymerization reaction is 120°C and the time of the polymerization reaction is 40h; the temperature and time of the polymerization reaction in the preferred range can further improve the porosity of the ruthenium-containing catalyst, thereby making the catalytic performance of the ruthenium-containing catalyst better.

[0018] In an embodiment, the catalyst is palladium tetraphenylphosphonium and / or triphenylphosphine.

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

[0020] In an embodiment, the mass of the catalyst and the total moles of 3,3'-dibromo-4,4'-biphenyldiol and 1,3,5-tris(p-vinylphenyl)benzene are in a ratio of 0.9g:(2-5mmol).

[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 catalyst to maintain the rate of the polymerization reaction in a suitable range, so as to avoid the rate of the polymerization reaction being too fast or too slow, and to obtain a ruthenium-containing catalyst with better performance.

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

[0023] In an embodiment, after the polymerization reaction is completed, the obtained product is sequentially subjected to filtration, washing, Soxhlet extraction, and drying, so as to obtain a ruthenium-containing catalyst.

[0024] The present disclosure does not have special limitations on the specific operation mode of the filtering, and a filtering mode well known to those skilled in the art can be used.

[0025] The present disclosure does not have special limitations on the solution for washing, and a washing solution well known in the art can be used for washing, such as deionized water, ethanol, hydrochloric acid solution, etc. The present disclosure preferably uses a hydrochloric acid solution with a molar concentration of 1-2 mol / L for washing; further preferably, a hydrochloric acid solution with a molar concentration of 1.5 mol / L is used for washing.

[0026] The present disclosure does not have special limitations on the solvent for Soxhlet extraction, and a solvent well known in the art for Soxhlet extraction can be used for Soxhlet extraction. The present disclosure preferably uses dichloromethane, tetrahydrofuran and petroleum ether for Soxhlet extraction, and the specific steps are as follows: the product obtained by washing is sequentially subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran and petroleum ether.

[0027] The present disclosure does not have special limitations on the time for Soxhlet extraction, and those skilled in the art can select a suitable time according to actual needs. The present disclosure selects a time for Soxhlet extraction of 48-72 h / time, preferably 56-71 h / time, and more preferably 70 h / time.

[0028] The present disclosure does not have special limitations on the specific operation mode of the drying, and a filtering mode well known to those skilled in the art can be used.

[0029] The present disclosure does not have special limitations on the temperature and time for drying, and those skilled in the art can select a suitable temperature and time according to actual needs. The present disclosure selects a drying temperature of 50-100℃ and a drying time of 18-24 h; preferably, a drying temperature of 70-90℃ and a drying time of 20-23 h; more preferably, a drying temperature of 80℃ and a drying time of 22 h.

[0030] In a second aspect, a ruthenium-containing catalyst is provided, which is prepared by the above-mentioned method for preparing a ruthenium-containing catalyst.

[0031] In a third aspect, the application of the ruthenium-containing catalyst in preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester is provided.

[0032] In one embodiment, the application comprises the following steps: diisononyl phthalate and a ruthenium catalyst are simultaneously added to a reaction kettle, hydrogen is introduced, the pressure is 0.5-2 MPa, heating is performed to 150-220℃, and reaction is performed for 0.5-3 h to obtain cyclohexane-1,2-dicarboxylic acid diisononyl ester; wherein the mass ratio of diisononyl phthalate to ruthenium catalyst is (1:0.01)-(1:0.05).

[0033] The diisopropyl naphthalate is hydrogenated by the ruthenium-containing catalyst of the present disclosure to prepare diisopropyl cyclohexane-1,2-dicarboxylate, and the catalytic effect of the ruthenium-containing catalyst is good.

[0034] In one embodiment, the temperature of the reaction is 160-200℃.

[0035] Compared with the prior art, the present disclosure has the following advantages:

[0036] (1) The present disclosure uses 3,3'-dibromo-4,4'-biphenyl diol, 1,3,5-tris(p-vinylphenyl) benzene and a ruthenium salt as the main raw materials for polymerization to prepare a ruthenium-containing catalyst with nanoscale pores formed inside. The nanoscale pores are beneficial to increase the specific surface area of the ruthenium-containing catalyst, so that more catalytic sites can be exposed in the catalytic system, which is beneficial to improve the catalytic performance of the catalyst. In addition, the solid ruthenium-containing catalyst is beneficial to separation and recycling. In addition, the ruthenium-containing catalyst of the present disclosure uses a monomer containing a benzene ring as a structural unit, and 3,3'-dibromo-4,4'-biphenyl diol and 1,3,5-tris(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 long-time immersion in an organic solvent;

[0037] (2) The ruthenium-containing catalyst of the present disclosure is used to catalyze the hydrogenation of diisopropyl naphthalate to prepare diisopropyl cyclohexane-1,2-dicarboxylate, and the catalytic effect of the ruthenium-containing catalyst is good, and the yield of diisopropyl cyclohexane-1,2-dicarboxylate is high. 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 combination with specific examples 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 examples obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present disclosure. The experimental reagents and instruments involved in the implementation of the present disclosure are all common ordinary reagents and instruments unless otherwise specified.

[0039] The raw materials used in the examples and comparative examples are described as follows:

[0040] 3,3'-dibromo-4,4'-biphenyl diol:

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

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

[0043] Example 1

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

[0045] In a round-bottom flask, 2 g of tetrakis(triphenylphosphine)palladium and 1 g of triphenylphosphine were added. After the flask was vacuumed, nitrogen was filled, 100 mL of tetrahydrofuran was injected, and then 3,3'-dibromo-4,4'-biphenyldiol, 1,3,5-tris(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'-biphenyldiol, 1,3,5-tris(p-vinylphenyl)benzene, and ruthenium(III) chloride hydrate was 3,3'-dibromo-4,4'-biphenyldiol: 1,3,5-tris(p-vinylphenyl)benzene: ruthenium(III) chloride hydrate = 1:1:2. Heating was performed to 120°C for 40 hours. After the reaction was completed and cooled, filtration was performed. The crude product obtained by filtration was washed with a 1.5 mol / L HCl solution. The obtained product was sequentially subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether. The product obtained by Soxhlet extraction was dried in a vacuum environment at 80°C for 22 hours to obtain a ruthenium-containing catalyst.

[0046] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by hydrogenation reaction of diisononyl phthalate using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst is as follows:

[0047] Diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added to a reaction kettle. Hydrogen was introduced, the pressure was 1 MPa, heating was performed to 170°C, and reaction was performed for 2 hours to obtain cyclohexane-1,2-dicarboxylic acid diisononyl ester. The mass ratio of diisononyl phthalate and the ruthenium-containing catalyst was 1:0.01. The yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester was 98% after calculation.

[0048] Example 2

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

[0050] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by hydrogenation reaction of diisononyl phthalate using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst is as follows:

[0051] Diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added to a reaction kettle. Hydrogen was introduced, the pressure was 1 MPa, heating was performed to 170°C, and reaction was performed for 2 hours to obtain cyclohexane-1,2-dicarboxylic acid diisononyl ester. The mass ratio of diisononyl phthalate and the ruthenium-containing catalyst was 1:0.01. The yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester was 96% after calculation.

[0052] Example 3

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

[0054] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by using the ruthenium-containing catalyst obtained in this example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0055] Diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170℃, reaction for 2h, to obtain cyclohexane-1,2-dicarboxylic acid diisononyl ester; wherein the mass ratio of diisononyl phthalate and the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester is 94%.

[0056] Example 4

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

[0058] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by using the ruthenium-containing catalyst obtained in this example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0059] Diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170℃, reaction for 2h, to obtain cyclohexane-1,2-dicarboxylic acid diisononyl ester; wherein the mass ratio of diisononyl phthalate and the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester is 97%.

[0060] Example 5

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

[0062] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by using the ruthenium-containing catalyst obtained in this example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0063] Diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170℃, reaction for 2h, to obtain cyclohexane-1,2-dicarboxylic acid diisononyl ester; wherein the mass ratio of diisononyl phthalate and the ruthenium-containing catalyst is 1:0.01; after calculation, the yield of cyclohexane-1,2-dicarboxylic acid diisononyl ester is 99%.

[0064] Example 6

[0065] The preparation method of the ruthenium-containing catalyst of the present example is different from that of Example 1 only in that the tris-chloro-ruthenium (III) hydrate is replaced by tris-chloro-ruthenium (III) hexahydrate.

[0066] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by hydrogenation of diisononyl phthalate using the ruthenium-containing catalyst obtained in the present example as catalyst is as follows:

[0067] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, and heating is performed to 170℃, and reaction is performed for 2 h to obtain the cyclohexane-1,2-dicarboxylic acid diisononyl ester; wherein the mass ratio of the diisononyl phthalate and the ruthenium-containing catalyst is 1:0.01; and the yield of the cyclohexane-1,2-dicarboxylic acid diisononyl ester is 98% after calculation.

[0068] Example 7

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

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

[0071] The method for preparing cyclohexane-1,2-dicarboxylic acid diisononyl ester by hydrogenation of diisononyl phthalate using the ruthenium-containing catalyst obtained in the present example as catalyst is as follows:

[0072] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, and heating is performed to 170℃, and reaction is performed for 2 h to obtain the cyclohexane-1,2-dicarboxylic acid diisononyl ester; wherein the mass ratio of the diisononyl phthalate and the ruthenium-containing catalyst is 1:0.01; and the yield of the cyclohexane-1,2-dicarboxylic acid diisononyl ester is 98% after calculation.

[0073] Example 8

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

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

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

[0077] Diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heating to 170℃, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and the ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 95%.

[0078] Example 9

[0079] The difference between the preparation method of the ruthenium-containing catalyst of the example and that of example 1 is only that:

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

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

[0082] Diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heating to 170℃, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and the ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 91%.

[0083] Example 10

[0084] The difference between the preparation method of the ruthenium-containing catalyst of the example and that of example 1 is only that:

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

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

[0087] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170 ℃, reaction for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 88%.

[0088] Example 11

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

[0090] The molar ratio of 3,3'-dibromo-4,4'-biphenyldiol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenyldiol: 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 using the ruthenium-containing catalyst obtained in the present example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0092] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170 ℃, reaction for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and 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 of the present example is only different from that of Example 1 in that:

[0095] The molar ratio of 3,3'-dibromo-4,4'-biphenyldiol, 1,3,5-tri(p-vinylphenyl)benzene and ruthenium(III) chloride hydrate is 3,3'-dibromo-4,4'-biphenyldiol: 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 using the ruthenium-containing catalyst obtained in the present example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0097] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170°C, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein, the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 74%.

[0098] Example 13

[0099] The preparation method of the ruthenium-containing catalyst of the present embodiment is only different from that of Example 1 in that tris(2-aminoethyl)amine ruthenium (III) chloride hexahydrate is used instead of ruthenium (III) chloride hydrate.

[0100] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0101] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170°C, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein, the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 98%.

[0102] Example 14

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

[0104] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0105] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 170°C, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein, the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 97%.

[0106] Example 15

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

[0108] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0109] The diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heated to 170 °C, reacted for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 91%.

[0110] Example 16

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

[0112] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0113] The diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heated to 170 °C, reacted for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 98%.

[0114] Example 17

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

[0116] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0117] The diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heated to 170 °C, reacted for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 88%.

[0118] Example 18

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

[0120] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present example as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0121] The diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heated to 170 °C, reacted for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 88%.

[0122] Example 19

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

[0124] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0125] The diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heated to 170 °C, reacted for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 75%.

[0126] Example 20

[0127] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0128] The diisononyl phthalate and the ruthenium-containing catalyst were simultaneously added into a reaction kettle, hydrogen was introduced, the pressure was 1 MPa, heated to 170 °C, reacted for 2 h to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst was 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate was 75%.

[0129] Example 21

[0130] The method for preparing diisononyl cyclohexane-1,2-dicarboxylate by using the ruthenium-containing catalyst obtained in the present embodiment as a catalyst to catalyze the hydrogenation reaction of diisononyl phthalate is as follows:

[0131] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1.5 MPa, heating to 170°C, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 94%.

[0132] Example 22

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

[0134] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 2 MPa, heating to 170°C, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 99%.

[0135] Example 23

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

[0137] The diisononyl phthalate and the ruthenium-containing catalyst are simultaneously added into a reaction kettle, hydrogen is introduced, the pressure is 1 MPa, heating to 150°C, reaction for 2h, to obtain diisononyl cyclohexane-1,2-dicarboxylate; wherein the mass ratio of diisononyl phthalate and ruthenium-containing catalyst is 1:0.01; after calculation, the yield of diisononyl cyclohexane-1,2-dicarboxylate is 93%.

[0138] Example 24

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

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

[0141] Acid and alkali stability: 10 mg of the catalyst is respectively soaked in 100 mL of 1 mol / L sulfuric acid and 1 mol / L sodium hydroxide solution for 2 hours, taken out, washed with water, dried, and then tested by DZ-TGA105 high temperature thermal gravimetric analyzer.

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

[0143] Table 1

[0144]

[0145]

[0146] From the test data in Table 1, it can be seen that the ruthenium-containing catalyst prepared in the embodiments has excellent thermal stability and acid-base stability.

[0147] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present disclosure, rather than 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 solutions of the present disclosure can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present disclosure.

Claims

1. A method for preparing a ruthenium-containing catalyst, characterized in that, The process includes the following steps: mixing 3,3'-dibromo-4,4'-biphenylhydrazine, 1,3,5-tris(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; wherein the ruthenium salt is at least one selected from ruthenium(III) chloride hydrate, tris(triphenylphosphine) dichloride, dichloro(p-methylisopropylbenzene) ruthenium(II) dimer, ruthenium trichloride, ruthenium red, and terpyridine ruthenium chloride hexahydrate; wherein the catalyst is tetratetraphenylphosphine palladium and / or triphenylphosphine; The ruthenium salt is at least one of ruthenium(III) chloride hydrate, ruthenium trichloride, and ruthenium tripyridine chloride hexahydrate; The molar ratio of 3,3'-dibromo-4,4'-biphenyl, 1,3,5-tris(p-vinylphenyl)benzene and ruthenium salt is 3,3'-dibromo-4,4'-biphenyl: 1,3,5-tris(p-vinylphenyl)benzene: ruthenium salt = (1:1:5) - (5:5:1); The polymerization reaction is carried out at a temperature of 75-135℃ and for a duration of 10-48 hours. The catalyst is tetraphenylphosphine palladium and triphenylphosphine; The molar ratio of the tetraphenylphosphine palladium and triphenylphosphine is (1:4)-(4:1). The ratio of tetratriphenylphosphine palladium to potassium carbonate is (1:1) to (1:2). The mass of the catalyst and the total molar ratio of 3,3'-dibromo-4,4'-biphenyl to 1,3,5-tris(p-vinylphenyl)benzene is 0.9 g:(2-5 mmol).

2. The preparation method according to claim 1, characterized in that, The solvent is at least one of chloroform, ether, benzene, methyl acetate, tetrahydrofuran, acetone, methanol, petroleum, chlorophenol, dichloroethylene, and carbon tetrachloride; And / or, after the polymerization reaction is completed, the resulting product is sequentially filtered, washed, Soxhlet extracted and dried to obtain a ruthenium-containing catalyst.

3. A ruthenium-containing catalyst, characterized in that, The ruthenium-containing catalyst is prepared by the method described in any one of claims 1-2.

4. The application of the ruthenium-containing catalyst as described in claim 3 in the preparation of diisononyl cyclohexane-1,2-dicarboxylate.

5. The application as described in claim 4, characterized in that, The application includes the following steps: diisononyl phthalate and a ruthenium-containing catalyst are simultaneously added to a reaction vessel, hydrogen gas is introduced, the pressure is 0.5-2 MPa, the mixture is heated to 150-220℃, and the reaction is carried out for 0.5-3 hours to obtain 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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