3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst, composite catalyst, preparation method and application

Abstract

The invention discloses a 3-(3-pyridine)-5-R-group benzoic acid coordinated catalyst, a composite catalyst, a preparation method and application, the 3-(3-pyridine)-5-R-group benzoic acid coordinated catalyst has a chemical general formula shown in the specification, and the composite catalyst comprises the 3-(3-pyridine)-5-R-group benzoic acid coordinated catalyst, an auxiliary catalyst, a regulator, a protective agent and a solvent. By using the composite catalyst disclosed by the invention, the selectivity of mesitylene oxidation reaction can be improved, the reaction activity is increased, and the composite catalyst can be used repeatedly and has a relatively high utilization rate.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic catalysis, and particularly relates to a 3-(3-pyridine)-5-R group benzoic acid complex catalyst, a composite catalyst, a preparation method and application. BACKGROUND

[0002] Trimesic acid, namely 1,3,5-benzene tricarboxylic acid, is an important chemical raw material, which is used as a pharmaceutical intermediate, and is widely used in plastics, artificial fibers, water-soluble alkyl resins, antifungal agents and crosslinking agents, and is also an intermediate of special polymers and resins.

[0003] Trimesic acid is an emerging important chemical raw material, and its preparation methods have been studied at home and abroad, but none of them is ideal. At present, trimesic acid is usually synthesized by three methods: oxidation of mesitylene with potassium permanganate, oxidation of mesitylene with nitric acid and liquid phase oxygen oxidation of mesitylene. Among them, the potassium permanganate oxidation method produces a large amount of wastewater and waste residue in the reaction process, which is difficult to handle, and has low conversion rate and complex purification; the nitric acid method has high raw material cost, poor selectivity to the target product, great difficulty in product refining, serious environmental pollution and great danger in the reaction process; the oxygen oxidation method uses glacial acetic acid as a solvent, and a large amount of tar is generated in the reaction process due to the high activity of mesitylene, which has high cost, difficulty in separation and purification.

[0004] Therefore, it is particularly important to provide a catalyst for preparing trimesic acid with low cost, good quality and applicability, so that the product can be produced on a large scale, and the further development and application of trimesic acid are particularly important.

[0005] The information disclosed in this BACKGROUND section is only intended to increase an understanding of the general context in which the present application can be practiced. It is not admitted that any of the information provided in this section constitutes prior art against the present application. SUMMARY

[0006] The purpose of the present application is to provide a 3-(3-pyridine)-5-R group benzoic acid complex catalyst, a composite catalyst, a preparation method and application, which can effectively improve the selectivity of mesitylene oxidation reaction.

[0007] In order to achieve the above purpose, the technical scheme provided by an embodiment of the present application is as follows:

[0008] A 3-(3-pyridine)-5-R group benzoic acid complex catalyst, the chemical general formula of the catalyst is as formula (I):

[0009] (I)

[0010] B is an octyltributylphosphonium ion, a tetrabutylphosphonium ion, a tributylethylphosphonium ion, a tributylhexylphosphonium ion, a tetramethylammonium ion, a tetraethylammonium ion, a tetrabutylammonium ion, a benzyltrimethylammonium ion, a lithium ion, a sodium ion, a potassium ion, a magnesium ion, a calcium ion, an ammonium ion, a dodecyldimethylbenzylammonium ion, a dodecyltrimethylammonium ion, a stearyltrimethylammonium ion, a stearyldimethylbenzylammonium ion, a benzyltriphenylphosphonium ion, or a benzyltriethylammonium ion;

[0011] M is Mo;

[0012] R is a C1-C 10 alkyl group;

[0013] x is an integer between 1 and 20;

[0014] y is an integer between 1 and 40.

[0015] Another embodiment of the present application provides a technical solution as follows:

[0016] A preparation method of the above-mentioned 3- (3-pyridine) -5-R group benzoic acid coordination catalyst, comprising the following steps:

[0017] The metal compound is dissolved in deionized water, the pH of the solution is adjusted to 1-4, and then a peroxide is added to obtain a metal peroxide solution;

[0018] An alkyl-substituted 3- (3-pyridine) -5-R group benzoic acid and a salt are added to the metal peroxide solution, filtered, and dried to obtain a 3- (3-pyridine) -5-R group benzoic acid coordination catalyst.

[0019] In one or more embodiments of the present application, the metal compound is selected from sodium molybdate.

[0020] In one or more embodiments of the present application, the peroxide is selected from hydrogen peroxide, meta-chloroperoxybenzoic acid, and urea peroxide.

[0021] In one or more embodiments of the present application, the alkyl-substituted 3- (3-pyridine) -5-R group benzoic acid is selected from 3- (3-pyridine) -5-methylbenzoic acid, 3- (3-pyridine) -5-ethylbenzoic acid, 3- (3-pyridine) -5-butylbenzoic acid, and 3- (3-pyridine) -5-isopropylbenzoic acid.

[0022] In one or more embodiments of the present application, the salt is selected from octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, dodecyldimethylbenzylammonium bromide, dodecyltrimethylammonium chloride, octadecyldimethylbenzylammonium bromide, octyltributylphosphonium bromide, tetrabutylphosphonium bromide, tributylethylphosphonium bromide, tributylhexylphosphonium bromide, benzyltriphenylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride.

[0023] Another embodiment of the present application provides a technical solution as follows:

[0024] A composite catalyst, comprising the 3-(3-pyridine)-5-R group benzoic acid complexing catalyst described above.

[0025] In one or more embodiments of the present application, a co-catalyst is further included, and the weight ratio of the 3-(3-pyridine)-5-R group benzoic acid complexing catalyst to the co-catalyst is 80:(1-500);

[0026] The co-catalyst is selected from cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, iron nitrate, iron sulfate, iron chloride, magnesium chloride, copper sulfate, ammonium acetate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, nickel acetate, chromium acetate, calcium acetate, and potassium sulfate.

[0027] In one or more embodiments of the present application, a regulator is further included, and the weight ratio of the 3-(3-pyridine)-5-R group benzoic acid complexing catalyst to the regulator is 100:(1-500);

[0028] The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, sodium tungstate, sodium chloride, magnesium chloride, copper chloride, and phosphomolybdovanadic acid.

[0029] In one or more embodiments of the present application, a protective agent is further included, and the weight ratio of the 3-(3-pyridine)-5-R group benzoic acid complexing catalyst to the protective agent is 100:(1-500);

[0030] The protective agent is selected from sodium acetate, ammonium bromide, sodium bromide, cetyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, ammonium molybdate, sodium sulfate, and N-hydroxyphthalimide.

[0031] In one or more embodiments of the present application, a solvent is further included, and the weight ratio of the 3-(3-pyridine)-5-R group benzoic acid complexing catalyst to the solvent is 100:(50-10000);

[0032] The solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate.

[0033] Another embodiment of the present application provides the technical solution as follows:

[0034] A preparation method of a composite catalyst comprises the following steps:

[0035] Mixing the protective agent and the solvent to obtain a solution;

[0036] Adding the 3-(3-pyridine)-5-R group benzoic acid complex catalyst of claim 1 to the solution, and stirring at 20-100 ℃ for 10-60 min;

[0037] Further adding a co-catalyst, and ultrasonicating at 20-120 ℃ for 20-60 min;

[0038] Further adding a regulator, and stirring at 20-110 ℃ for 10-60 min to obtain the composite catalyst.

[0039] Another embodiment of the present application provides the technical solution as follows:

[0040] The application of the 3-(3-pyridine)-5-R group benzoic acid complex catalyst or the composite catalyst in the preparation of trimesic acid.

[0041] Compared with the prior art, the 3-(3-pyridine)-5-R group benzoic acid complex catalyst or the composite catalyst can improve the selectivity and reactivity of the oxidation reaction of tri-methyl benzene, and can be used repeatedly, and has high utilization rate. DETAILED DESCRIPTION

[0042] In order to enable the personnel in the art to better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below, obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by the person skilled in the art without creative labor should belong to the protection scope of the present application.

[0043] One embodiment of the present application provides a 3-(3-pyridine)-5-R group benzoic acid complex catalyst, and the chemical general formula of the catalyst is shown as formula (I):

[0044] (I)

[0045] Wherein, B is octyltributylphosphonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyl dimethylbenzylammonium ion, dodecyl trimethylammonium ion, octadecyl trimethylammonium ion, octadecyl dimethylbenzylammonium ion, benzyltriphenylphosphonium ion, or benzyltriethylammonium ion; M is Mo; R is C1~C 10 Alkyl; x is an integer between 1 and 20; y is an integer between ~40.

[0046] Preferably, B is calcium ion, ammonium ion, benzyltriphenylphosphonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, lithium ion, sodium ion, potassium ion or magnesium ion, M is Mo; R is selected from C1-C5 alkyl; x is selected from integers between 1 and 5; y is selected from integers between 1 and 5.

[0047] More preferably, B is selected from octadecyltrimethylammonium ion, sodium ion, magnesium ion, ammonium ion or benzyltriphenylphosphonium ion; M is selected from Mo; R is selected from methyl, ethyl or isopropyl; x is 1; y is 1 or 2.

[0048] For example, the catalyst for coordination with 3-(3-pyridine)-5-R-ylbenzoic acid can be: , , , , , .

[0049] Another specific embodiment of the present invention provides a method for preparing a catalyst coordinated with 3-(3-pyridine)-5-R-benzoic acid, comprising steps 1-2.

[0050] Step 1: Dissolve the metal compound in deionized water, adjust the pH of the solution to 1-4, and then add peroxide to obtain a metal peroxide solution. The acidic conditions inhibit the hydrolysis of metal ions, while the oxidizing properties of the peroxide (such as H₂O₂) convert the metal ions into higher valence states or metal peroxides, forming a homogeneous or stably dispersed solution.

[0051] Specifically, the metal compound is selected from sodium molybdate, the peroxide is selected from urea peroxide, m-chloroperoxybenzoic acid or a 30% hydrogen peroxide solution, and the pH of the solution is adjusted by 2 mol / L dilute hydrochloric acid or 2 mol / L dilute sulfuric acid.

[0052] Step 2, adding alkyl-substituted 3-(3-pyridine)-5-R benzene acid and salt into the metal peroxide solution, filtering, drying, and obtaining 3-(3-pyridine)-5-R benzene acid coordinated catalyst. In this step, the coordination reaction between bipyridine and metal ions in the metal peroxide solution forms metal-bipyridine complex, the alkyl-substituted group adjusts the electronic effect of the ligand, and the addition of salt promotes the crystallization of the complex. Finally, the bipyridine coordinated catalyst is obtained by solid-liquid separation.

[0053] Specifically, the alkyl-substituted 3-(3-pyridine)-5-R benzene acid is selected from 3-(3-pyridine)-5-methyl benzene acid, 3-(3-pyridine)-5-ethyl benzene acid, 3-(3-pyridine)-5-butyl benzene acid, and 3-(3-pyridine)-5-isopropyl benzene acid, and the salt is selected from octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, dodecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide, octyl tributyl phosphonium bromide, tetrabutyl phosphonium bromide, tributyl ethyl phosphonium bromide, tributyl hexyl phosphonium bromide, benzyl triphenyl phosphonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride, benzyl trimethyl ammonium chloride, or benzyl triethyl ammonium chloride.

[0054] Another specific embodiment of the present application discloses a composite catalyst, which comprises the above-mentioned 3-(3-pyridine)-5-R benzene acid coordinated catalyst, a cocatalyst, a regulator, a protective agent, and a solvent, and the weight ratio of the 3-(3-pyridine)-5-R benzene acid coordinated catalyst, the cocatalyst, the regulator, the protective agent, and the solvent is 80: (1-500): (1-500): (1-500): (50-10000).

[0055] Specifically, the cocatalyst is selected from cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, iron nitrate, iron sulfate, iron chloride, magnesium chloride, copper sulfate, ammonium acetate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, nickel acetate, chromium acetate, calcium acetate, and potassium sulfate; the regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutyl ammonium bromide, boric acid, silicotungstic acid, sodium tungstate, sodium chloride, magnesium chloride, copper chloride, and phosphomolybdovanadic acid; the protective agent is selected from sodium acetate, ammonium bromide, sodium bromide, cetyl trimethyl ammonium bromide, phenyl trimethyl ammonium bromide, sodium molybdate, ammonium molybdate, sodium sulfate, and N-hydroxy phthalimide; and the solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid, and ethyl acetate. The selection of the above-mentioned cocatalyst, regulator, protective agent, and solvent can improve the activity of the catalyst and ensure the selectivity and stability of the reaction.

[0056] Preferably, the weight ratio of the 3-(3-pyridine)-5-R group benzoic acid complex catalyst, the auxiliary catalyst, the regulator, the protective agent and the solvent is 100:(1-500):(1-500):(1-500):(50-10000); the auxiliary catalyst is selected from cerium nitrate, manganese acetate, zirconium acetate, iron nitrate, copper sulfate, magnesium sulfate, magnesium acetate, zinc sulfate and sodium molybdate; the regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdovanadic acid; the protective agent is selected from sodium acetate, ammonium bromide, cetyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide; and the solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate.

[0057] Preferably, the weight ratio of the 3-(3-pyridine)-5-R group benzoic acid complex catalyst, the auxiliary catalyst, the regulator, the protective agent and the solvent is 110:(1-60):(10-100):(10-50):(100-1000); the 3-(3-pyridine)-5-R group benzoic acid complex catalyst is a Mo-centered metal complex catalyst; the auxiliary catalyst is selected from manganese acetate, zirconium acetate, magnesium acetate and cerium acetate; the regulator is selected from phosphomolybdic acid, phosphotungstic acid and silicotungstic acid; the protective agent is selected from ammonium bromide, dodecyltrimethylammonium bromide, phenyltrimethylammonium bromide and N-hydroxyphthalimide; and the solvent is selected from methanol, ethanol and acetonitrile.

[0058] Another specific embodiment of the present application provides a preparation method of the composite catalyst, comprising the following steps: preparing raw materials, including 3-(3-pyridine)-5-R group benzoic acid complex catalyst, auxiliary catalyst, regulator, protective agent and solvent;

[0059] adding the protective agent into the solvent and mixing to obtain solution 1;

[0060] adding the 3-(3-pyridine)-5-R group benzoic acid complex catalyst into the solution 1, stirring at 20-100°C for 10-60 min to obtain solution 2;

[0061] adding the auxiliary catalyst into the solution 2, ultrasonicating at 20-120°C for 20-60 min to obtain solution 3;

[0062] adding the regulator into the solution 3, stirring at 20-110°C for 10-60 min to obtain the composite catalyst.

[0063] Specifically, the co-catalyst is one or more of cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, iron nitrate, iron sulfate, iron chloride, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, and potassium sulfate; the regulator is one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, and phosphomolybdovanadic acid; the protective agent is one or more of sodium acetate, ammonium bromide, cetyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, and N-hydroxyphthalimide; and the solvent is one or more of dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid, and ethyl acetate.

[0064] Preferably, the protective agent is one or more of ammonium bromide, dodecyltrimethylammonium bromide, phenyltrimethylammonium bromide, and N-hydroxyphthalimide; the solvent is one or more of formic acid, acetic acid, and propionic acid; the 3- (3-pyridyl) -5-R- benzoic acid-coordinated catalyst is one or more of 3- (3-pyridyl) -5-R- benzoic acid-coordinated catalysts with Mo as the central metal; the co-catalyst is one or more of copper nitrate, manganese acetate, silver nitrate, iron nitrate, manganese sulfate, cerium sulfate, cerium nitrate, zirconium acetate, and magnesium sulfate; and the regulator is one or more of phosphomolybdic acid, phosphotungstic acid, and silicotungstic acid.

[0065] Another specific embodiment of the present application provides the use of the above-mentioned 3- (3-pyridyl) -5-R- benzoic acid-coordinated catalyst or the above-mentioned composite catalyst in the preparation of trimesic acid.

[0066] Specifically, the reaction conditions are as follows: the mesitylene is dissolved in a solvent, the 3- (3-pyridyl) -5-R- benzoic acid-coordinated catalyst or the composite catalyst is added, air is introduced at a speed of 1-10 mL / s, and the reaction is stirred at 50-160°C for 1-10 h.

[0067] For example, the composite catalyst is added in an amount of 0.05-6% by weight of the mesitylene.

[0068] Preferably, the composite catalyst is added in an amount of 0.1-1.5% by weight of the mesitylene, the reaction temperature is 65-100°C, the reaction time is 2-7 h, and the air introduction speed is 2-3 mL / s.

[0069] The present application is further described in detail below with reference to specific examples.

[0070] 3- (3-pyridyl) -5-R- benzoic acid-coordinated catalyst examples

[0071] Example 1

[0072] Step 1 : To sodium molybdate (41.2 g, 0.2 mol) solid, add 450 mL deionized water at room temperature, and after the solid is completely dissolved, obtain solution a. To solution a, add dilute sulfuric acid dropwise until the solution pH is 3, and obtain solution b. After continuing to stir for about 14 min, slowly add 210 mL 30% hydrogen peroxide solution to solution b, and obtain solution c. To solution c, add deionized water until the total liquid volume is 3000 mL, and obtain solution d.

[0073] Step 2: Heat solution d to 45 °C, and to solution d, add 3-(3-pyridyl)-5- ethylbenzoic acid (54.50 g, 0.24 mol) and sodium chloride (12.86 g, 0.22 mol). After stirring for about 1 h while heating, centrifuge for 10 min using a centrifuge. Filter, and after drying the solid obtained after filtering in a vacuum drying oven, obtain 62.26 g of yellow solid, which is the 3-(3-pyridyl)-5-ethylbenzoic acid coordinated catalyst YG-31-1-022. The catalyst yield is 88.33%.

[0074] Example 2

[0075] Step 1 : To sodium molybdate (20.6 g, 0.1 mol) solid, add 550 mL deionized water at room temperature, and after the solid is completely dissolved, obtain solution a. To solution a, add dilute sulfuric acid dropwise until the solution pH is 1, and obtain solution b. After continuing to stir for about 64 min, slowly add 260 mL 30% hydrogen peroxide solution to solution b, and obtain solution c. To solution c, add deionized water until the total liquid volume is 3400 mL, and obtain solution d.

[0076] Step 2: Heat solution d to 27 °C, and to solution d, add 3-(3-pyridyl)-5- isopropylbenzoic acid (28.95 g, 0.12 mol) and lithium chloride (8.48 g, 0.2 mol). After stirring for about 1 h while heating, centrifuge for 15 min using a centrifuge. Filter, and after drying the solid obtained after filtering in a vacuum drying oven, obtain 30.06 g of yellow solid, which is the 3-(3-pyridyl)-5-isopropylbenzoic acid coordinated catalyst YG-31-1-023. The catalyst yield is 87.46%.

[0077] Example 3

[0078] Step 1 : To sodium molybdate (41.2 g, 0.2 mol) solid, add 600 mL deionized water at room temperature, and after the solid is completely dissolved, obtain solution a. To solution a, add dilute hydrochloric acid dropwise until the solution pH is 2, and obtain solution b. Continue stirring for about 170 min, and then slowly add 250 mL 30% hydrogen peroxide solution to solution b to obtain solution c. To solution c, add deionized water until the total liquid volume is 2000 mL, and obtain solution d.

[0079] Step 2: Heat solution d to 50 °C, and to solution d, add 3-(3-pyridyl)-5- methylbenzoic acid (25.59 g, 0.12 mol) and benzyltriphenylphosphonium bromide (51.99 g, 0.12 mol) while stirring for about 1 h. Then centrifuge for 30 min using a centrifuge. Filter, and after drying the obtained solid in a vacuum drying oven, obtain 65.44 g of yellow solid, which is the 3-(3-pyridyl)-5-methylbenzoic acid coordinated catalyst YG-31-1-024. The catalyst yield reaches 91.14 %.

[0080] Example 4

[0081] Step 1 : To sodium molybdate (20.6 g, 0.1 mol) solid, add 500 mL deionized water at room temperature, and after the solid is completely dissolved, obtain solution a. To solution a, add dilute nitric acid dropwise until the solution pH is 2, and obtain solution b. Continue stirring for about 20 min, and then slowly add 290 mL 30% hydrogen peroxide solution to solution b to obtain solution c. To solution c, add deionized water until the total liquid volume is 1000 mL, and obtain solution d.

[0082] Step 2: Heat solution d to 90 °C, and to solution d, add 3-(3-pyridyl)-5- butylbenzoic acid (30.64 g, 0.12 mol) and magnesium chloride (10.47 g, 0.11 mol) while stirring for about 1 h. Then centrifuge for 20 min using a centrifuge. Filter, and after drying the obtained solid in a vacuum drying oven, obtain 59.66 g of yellow solid, which is the 3-(3-pyridyl)-5-butylbenzoic acid coordinated catalyst YG-31-1-025. The catalyst yield reaches 83.28 %.

[0083] Composite catalyst example

[0084] Example 5

[0085] Step (1): To 15.0 g of N-hydroxyphthalimide, add 23.0 g of methanol, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0086] Step (2): To the mixture A of step (1), add 1.0 g of 3-(3-pyridyl)-5-ethylbenzoic acid complexation catalyst YG-31-1-022, and stir and heat at 80°C for 36 min to obtain mixture B;

[0087] Step (3): To the mixture B formed in step (2), add 0.2 g of magnesium acetate to obtain mixture C;

[0088] Step (4): To the mixture C formed in step (3), add 0.2 g of phosphomolybdic acid, and stir at 100°C for 50 min to obtain composite catalyst 1, a total of 33.2 g.

[0089] Example 6

[0090] Step (1): To 10.0 g of sodium bromide, add 25.0 g of methanol, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0091] Step (2): To the mixture A of step (1), add 1.0 g of 3-(3-pyridyl)-5-isopropylbenzoic acid complexation catalyst YG-31-1-023, and stir and heat at 80°C for 40 min to obtain mixture B;

[0092] Step (3): To the mixture B formed in step (2), add 0.1 g of copper acetate to obtain mixture C;

[0093] Step (4): To the mixture C formed in step (3), add 0.1 g of phosphomolybdic acid, and stir at 120°C for 60 min to obtain composite catalyst 2, a total of 42.3 g.

[0094] Example 7

[0095] Step (1): To 10.0 g of dodecyltrimethylammonium bromide, add 25.0 g of methanol, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0096] Step (2): To the mixture A of step (1), add 2.0 g of 3-(3-pyridyl)-5-methylbenzoic acid complexation catalyst YG-31-1-024, and stir and heat at 80°C for 60 min to obtain mixture B;

[0097] Step (3): To the mixture B formed in step (2), add 0.1 g of ammonium acetate to obtain mixture C;

[0098] Step (4): To the mixture C formed in step (3), add 0.1 g of phosphomolybdic acid, and stir at 120°C for 60 min to obtain composite catalyst 3, a total of 31.2 g.

[0099] Example 8

[0100] Step (1): To the mixture of 5.0 g of ammonium bromide and 5.0 g of octadecyl trimethyl ammonium bromide, 30.0 g of ethanol was added and stirred at room temperature until the solid was completely dissolved to obtain mixture A;

[0101] Step (2): To the mixture A of step (1), 1.0 g of 3-(3-pyridine)-5-butyl benzoic acid complex catalyst YG-31-1-025 was added, and after stirring and heating at 120°C for 30 min, mixture B was obtained;

[0102] Step (3): To the mixture B formed in step (2), 0.1 g of cerium acetate was added to obtain mixture C;

[0103] Step (4): To the mixture C formed in step (3), 0.1 g of phosphotungstic acid was added, and after stirring at 110°C for 120 min, a total of 41.2 g of composite catalyst 5 was obtained.

[0104] Application Example

[0105] Example 9

[0106] Into a 250 mL titanium high-pressure reaction kettle, N-hydroxyphthalimide (0.25 g), 3-(3-pyridine)-5-ethyl benzoic acid complex catalyst YG-31-1-022 (0.1 g), manganese acetate (0.01 g), sodium tungstate (0.04 g), ethanol (2.0 g) solvent, acetic acid (20 g), mesitylene (100 g) were sequentially added. After the high-pressure reaction kettle was installed, nitrogen was filled to a pressure of 0.5 MPa in the kettle for 15 min, and the pressure was reduced by no more than 5% to consider that the reaction kettle was airtight. After the nitrogen was discharged, the temperature was increased to 60°C, and air was passed into the reaction kettle to a pressure of 0.3 MPa. The air was continuously passed, and the flow rate was controlled at 400-500 mL / min. After three hours of reaction, the reaction was stopped. The reaction liquid was dark brown, and the total weight of the reaction liquid was 220.14 g. 0.1 g of the reaction liquid was taken, toluene was used as an internal standard, 0.1 g of toluene was taken, and after dilution with 30 g of acetonitrile, the sample was tested. The test data was substituted into the internal standard curve to calculate that the mesitylene remaining was 4.04 g, and the trimesic acid was 193.47 g. The conversion rate of mesitylene was 95.96%, and the selectivity of trimesic acid reached 95.41%.

[0107] Example 10

[0108] Into a 250 mL titanium high-pressure reaction kettle, ammonium bromide (0.05 g), 3- (3-pyridine) -5-methyl benzoic acid complex catalyst YG-31-1-024 (0.2 g), manganese acetate (0.01 g), sodium tungstate (0.04 g), ethanol (2.0 g), propionic acid (20 g), mesitylene (100 g) were sequentially added. After the high-pressure reaction kettle was installed, nitrogen was filled into the kettle to a pressure of 0.5 MPa for 15 minutes, and the reaction kettle was considered to have good airtightness if the pressure decreased by no more than 5%. After the nitrogen was discharged, the temperature was raised to 60°C, air was introduced into the kettle to a pressure of 0.6 MPa, and the air flow was continuously controlled at 400-500 mL / min. The reaction was stopped after three hours. The reaction liquid was dark brown, and the total weight of the reaction liquid was 221.34 g. 0.1 g of the reaction liquid was taken, toluene was used as an internal standard, 0.1 g of toluene was taken, and 30 g of acetonitrile was added for dilution, and then the sample was tested. The test data was substituted into the internal standard curve to calculate that the mesitylene remaining was 3.96 g, the trimesic acid was 190.09 g, the conversion rate of mesitylene was 96.04%, and the selectivity of trimesic acid was 94.21%.

[0109] Example 11

[0110] Into a 250 mL titanium high-pressure reaction kettle, ammonium bromide (0.05 g), 3- (3-pyridine) -5-methyl benzoic acid complex catalyst YG-31-1-024 (0.2 g), manganese acetate (0.01 g), sodium tungstate (0.04 g), ethanol (2.0 g), propionic acid (20 g), mesitylene (100 g) were sequentially added. After the high-pressure reaction kettle was installed, nitrogen was filled into the kettle to a pressure of 0.5 MPa for 15 minutes, and the reaction kettle was considered to have good airtightness if the pressure decreased by no more than 5%. After the nitrogen was discharged, the temperature was raised to 60°C, air was introduced into the kettle to a pressure of 0.6 MPa, and the air flow was continuously controlled at 400-500 mL / min. The reaction was stopped after three hours. The reaction liquid was dark brown, and the total weight of the reaction liquid was 221.34 g. 0.1 g of the reaction liquid was taken, toluene was used as an internal standard, 0.1 g of toluene was taken, and 30 g of acetonitrile was added for dilution, and then the sample was tested. The test data was substituted into the internal standard curve to calculate that the mesitylene remaining was 3.96 g, the trimesic acid was 190.09 g, the conversion rate of mesitylene was 96.04%, and the selectivity of trimesic acid was 94.21%.

[0111] Example 12

[0112] Into a 250 mL titanium high-pressure reactor, N-hydroxyphthalimide (0.05 g), octadecyl trimethylammonium bromide (0.05 g), 3-(3-pyridyl)-5- isopropyl benzoic acid complex catalyst YG-31-1-023 (0.2 g), calcium acetate (0.01 g), ammonium molybdate (0.03 g), methanol (2.0 g), acetic acid (20 g), mesitylene (100 g) were sequentially added. After the high-pressure reactor was installed, nitrogen was filled into the reactor to a pressure of 0.5 MPa for 15 minutes. If the pressure decreased by no more than 5%, it was considered that the reactor had good airtightness. After the nitrogen was discharged, the temperature was raised to 60°C, and air was introduced into the reactor to a pressure of 0.5 MPa. The air flow was continuously controlled at 400-500 mL / min, and the reaction was stopped after three hours. The reaction liquid was dark brown, and the total weight of the reaction liquid was 219.43 g. 0.1 g of the reaction liquid was taken, toluene was used as an internal standard, 0.1 g of toluene was taken, and 30 g of acetonitrile was added for dilution, and then the sample was tested. The test data was substituted into the internal standard curve to calculate that the residual mesitylene was 4.69 g, and the trimellitic acid was 183.29 g. The conversion rate of mesitylene was 95.31%, and the selectivity of trimellitic acid was 91.53%.

[0113] Example 13

[0114] Into a 250 mL titanium high-pressure reactor, N-hydroxyphthalimide (0.05 g), octadecyl trimethylammonium bromide (0.05 g), 3-(3-pyridyl)-5- isopropyl benzoic acid complex catalyst YG-31-1-023 (0.2 g), calcium acetate (0.01 g), ammonium molybdate (0.03 g), methanol (2.0 g), acetic acid (20 g), mesitylene (100 g) were sequentially added. After the high-pressure reactor was installed, nitrogen was filled into the reactor to a pressure of 0.5 MPa for 15 minutes. If the pressure decreased by no more than 5%, it was considered that the reactor had good airtightness. After the nitrogen was discharged, the temperature was raised to 60°C, and air was introduced into the reactor to a pressure of 0.5 MPa. The air flow was continuously controlled at 400-500 mL / min, and the reaction was stopped after three hours. The reaction liquid was dark brown, and the total weight of the reaction liquid was 219.43 g. 0.1 g of the reaction liquid was taken, toluene was used as an internal standard, 0.1 g of toluene was taken, and 30 g of acetonitrile was added for dilution, and then the sample was tested. The test data was substituted into the internal standard curve to calculate that the residual mesitylene was 4.69 g, and the trimellitic acid was 183.29 g. The conversion rate of mesitylene was 95.31%, and the selectivity of trimellitic acid was 91.53%.

[0115] Comparative Example

[0116] The experimental operation methods of the comparative examples were consistent with those of Example 9, except that the amount of the materials added was different. The amount of the materials added and the experimental results are shown in Table 1.

[0117]

[0118] As can be seen from Table 1, compared with the catalyst without 3-(3-pyridine)-5-ethylbenzoic acid coordination in Comparative Example 8, Example 9 has the optimal reaction effect of conversion rate and selectivity, indicating that the 3-(3-pyridine)-5-R group benzoic acid coordination catalyst disclosed in the present application can improve the selectivity and activity of the oxidation reaction of mesitylene.

[0119] In combination with Comparative Examples 1-7, the conversion rate of mesitylene and the selectivity of trimesic acid are reduced to different degrees by selectively removing one or more of the auxiliary catalyst, the regulator, the protective agent and the solvent, indicating that the 3-(3-pyridine)-5-R group benzoic acid coordination catalyst, the auxiliary catalyst, the regulator, the protective agent and the solvent are used in combination, which can better promote the oxidation of mesitylene to form trimesic acid.

[0120] It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be regarded as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application.

[0121] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A 3-(3-pyridyl)-5-R-phenyl acid ligated catalyst characterized by, The catalyst has a chemical formula as shown in formula (I): （Ⅰ） B is an octyl tributyl phosphonium ion, a tetrabutyl phosphonium ion, a tributyl ethyl phosphonium ion, a tributyl hexyl phosphonium ion, a tetramethyl ammonium ion, a tetraethyl ammonium ion, a tetrabutyl ammonium ion, a benzyl trimethyl ammonium ion, a lithium ion, a sodium ion, a potassium ion, a magnesium ion, a calcium ion, an ammonium ion, a dodecyl dimethyl benzyl ammonium ion, a dodecyl trimethyl ammonium ion, a octadecyl trimethyl ammonium ion, a octadecyl dimethyl benzyl ammonium ion, a benzyl triphenyl phosphonium ion or a benzyl triethyl ammonium ion; M is Mo; R is C1-C 10 alkyl; x is an integer between 1 and 20; y is an integer between 1 and 40.

2. A process for the preparation of a catalyst for the complexation of 3-(3-pyridyl)-5-R- benzoic acids according to claim 1, characterized in that The method comprises the following steps: dissolving the metal compound in deionized water, adjusting the pH of the solution to 1-4, and then adding a peroxide to obtain a metal peroxide solution; adding an alkyl-substituted 3-(3-pyridine)-5-R benzene acid and a salt to the metal peroxide solution, filtering, and drying to obtain a 3-(3-pyridine)-5-R benzene acid complex catalyst.

3. The process for the preparation of 3-(3-pyridyl)-5-R-phenyl acid ligand catalyst according to claim 2, characterized in that, The metal compound is selected from sodium molybdate.

4. The process for the preparation of 3-(3-pyridyl)-5-R-phenyl acid ligated catalyst according to claim 2, characterized in that, The peroxide is selected from hydrogen peroxide, m-chloroperbenzoic acid and urea peroxide.

5. The process for the preparation of 3-(3-pyridyl)-5-R- benzoic acid complexed catalyst according to claim 2, characterized by that, The alkyl-substituted 3-(3-pyridine)-5-R benzene acid is selected from 3-(3-pyridine)-5-methyl benzene acid, 3-(3-pyridine)-5-ethyl benzene acid, 3-(3-pyridine)-5-butyl benzene acid and 3-(3-pyridine)-5-isopropyl benzene acid.

6. The process for the preparation of 3-(3-pyridyl)-5-R- benzoic acid complexed catalyst according to claim 2, characterized by that, The salt is selected from octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, dodecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide, octyl tributyl phosphonium bromide, tetrabutyl phosphonium bromide, tributyl ethyl phosphonium bromide, tributyl hexyl phosphonium bromide, benzyl triphenyl phosphonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride, benzyl trimethyl ammonium chloride or benzyl triethyl ammonium chloride.

7. A composite catalyst characterized by comprising: The 3-(3-pyridine)-5-R benzene acid complex catalyst of claim 1.

8. The composite catalyst according to claim 7, characterized in that, The 3-(3-pyridine)-5-R benzene acid complex catalyst is further combined with a cocatalyst, and the weight ratio of the 3-(3-pyridine)-5-R benzene acid complex catalyst to the cocatalyst is 80:(1-500); The cocatalyst is selected from cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, iron nitrate, iron sulfate, iron chloride, magnesium chloride, copper sulfate, ammonium acetate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, nickel acetate, chromium acetate, calcium acetate and potassium sulfate.

9. The composite catalyst according to claim 7, wherein The 3-(3-pyridine)-5-R benzene acid complex catalyst is further combined with a regulator, and the weight ratio of the 3-(3-pyridine)-5-R benzene acid complex catalyst to the regulator is 100:(1-500); The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutyl ammonium bromide, boric acid, silicotungstic acid, sodium tungstate, sodium chloride, magnesium chloride, copper chloride and phosphomolybdovanadic acid.

10. The composite catalyst according to claim 7, wherein The 3-(3-pyridine)-5-R benzene acid complex catalyst is further combined with a protective agent, and the weight ratio of the 3-(3-pyridine)-5-R benzene acid complex catalyst to the protective agent is 100:(1-500); The protective agent is selected from sodium acetate, ammonium bromide, sodium bromide, cetyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, ammonium molybdate, sodium sulfate, and N-hydroxyphthalimide.

11. The composite catalyst according to claim 7, wherein The solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid, and ethyl acetate. The solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid, and ethyl acetate.

12. A method for preparing a composite catalyst, characterized by, The method comprises the following steps: Mixing the protective agent and the solvent to obtain a solution; Adding the 3-(3-pyridyl)-5-R-substituted benzoic acid acid-coordinating catalyst of claim 1 to the solution, stirring at 20-100°C for 10-60 min; Then adding a co-catalyst, and ultrasonicating at 20-120°C for 20-60 min; Then adding a regulator, and stirring at 20-110°C for 10-60 min to obtain a composite catalyst.

13. Use of the 3-(3-pyridyl)-5-R-substituted benzoic acid acid-coordinating catalyst of claim 1 or the composite catalyst of any one of claims 7-11 in the preparation of a trimesic acid reaction.

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