Composition for synthesizing hydrogenated aromatic polycarboxylic acid and method for synthesizing hydrogenated aromatic polycarboxylic acid

Abstract

The invention provides a composition for synthesizing hydrogenated aromatic polycarboxylic acid and a method for synthesizing hydrogenated aromatic polycarboxylic acid. The composition for synthesizing hydrogenated aromatic polycarboxylic acid provided by the invention comprises aromatic polycarboxylic acid, polyether polyol, a catalyst and an optional solvent. The method for synthesizing hydrogenated aromatic polycarboxylic acid provided by the invention comprises the step of reacting aromatic polycarboxylic acid with hydrogen in the presence of a catalyst and polyether polyol. The polyether polyol is introduced into the synthesis of hydrogenated aromatic polycarboxylic acid such as hydrogenated benzenetetracarboxylic acid, so that the reaction selectivity can be remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical technology, and particularly relates to a composition for synthesizing hydrogenated aromatic polycarboxylic acid and a method for synthesizing hydrogenated aromatic polycarboxylic acid. BACKGROUND

[0002] PI film is a new type of high-temperature-resistant organic polymer film, which is usually prepared by polycondensation of pyromellitic dianhydride (PMDA) and diamine-based diphenyl ether (ODA) in strong polar solvent dimethylacetamide (DMAC) and then casting into film, and then imidization. The PI film has the advantages of high thermal stability, strong low-temperature resistance, high tensile strength, good radiation resistance, high recovery rate, etc., and is widely used in the fields of insulating composite materials (ordinary PI film), electronic industry (electronic-grade PI film), OLED lighting and solar cells (transparent flexible film), etc.

[0003] Among them, the transparent flexible PI film is prepared by changing the polymerization monomer of PI from PMDA to its hydrogenated compound hydrogenated pyromellitic dianhydride (HPMDA), and further reacting with ODA to obtain HPMDA-based PI. Since it does not contain aromatic groups, the prepared PI has excellent transparency, low dielectric constant and dielectric loss, high breakdown strength, low moisture absorption, and good adhesion to metal and other substrates. Based on the special physicochemical properties of HPMDA-based PI, it has a wide application prospect in the fields of integrated circuits, liquid crystal displays and other high-tech fields.

[0004] The synthesis process of HPMDA is divided into two-step method and one-step method. In the two-step method, pyromellitic acid (dianhydride) is used as the starting material, and HPMDA is prepared by esterification, hydrogenation, hydrolysis and dehydration cyclization (Japanese patents JP1996325196, JP2006045166, Chinese patent CN104926649). It is the main method of current industrial production. However, this method is complicated and has high production cost. In the one-step method, pyromellitic acid (PMA) is used as the starting material, and HPMDA is prepared by hydrogenation and dehydration cyclization (Chinese patent CN1428324). The selection of hydrogenation catalyst is the key, and the conversion rate of pyromellitic acid is required to be above 99%. Chinese patent CN1428324 uses Rh / AC catalyst to obtain good reaction results, but the selectivity of the catalyst still needs to be further improved. SUMMARY

[0005] The present application solves the problem of low selectivity of the catalyst in the prior art. Therefore, the present application provides a composition for synthesizing hydrogenated aromatic polycarboxylic acid and a method for synthesizing hydrogenated aromatic polycarboxylic acid, which solves the problem.

[0006] In a first aspect, the present application provides a composition for the synthesis of hydrogenated aromatic polycarboxylic acids comprising an aromatic polycarboxylic acid, a polyether polyol, a catalyst, and optionally a solvent.

[0007] In some embodiments, the polyether polyol has a backbone consisting of -R-O- units, wherein R is selected from C2-C10 alkylene groups. In some embodiments, R is selected from C2-C6 alkylene groups, such as ethylene, propylene, butylene, or pentylene.

[0008] In some embodiments, the polyether polyol is selected from one or more of polyethylene glycol, polypropylene glycol, and polybutylene glycol.

[0009] In some embodiments, the polyether polyol has a number average molecular weight of 200 g / mol to 5000 g / mol, such as 500 g / mol, 700 g / mol, 1000 g / mol, 1300 g / mol, 1500 g / mol, 1700 g / mol, 2000 g / mol, 2300 g / mol, 2500 g / mol, 2700 g / mol, 3000 g / mol, 3300 g / mol, 3500 g / mol, 3700 g / mol, 4000 g / mol, 4300 g / mol, 4500 g / mol, 4700 g / mol, or any value therebetween. In some embodiments, the polyether polyol has a number average molecular weight of 500 g / mol to 4000 g / mol. In some embodiments, the polyether polyol has a number average molecular weight of 600 g / mol to 1500 g / mol.

[0010] In some embodiments, the polyether polyol has a hydroxyl number of 20 mg KOH / g to 600 mg KOH / g, for example 50 mg KOH / g, 60 mg KOH / g, 70 mg KOH / g, 80 mg KOH / g, 90 mg KOH / g, 100 mg KOH / g, 110 mg KOH / g, 120 mg KOH / g, 130 mg KOH / g, 140 mg KOH / g, 150 mg KOH / g, 160 mg KOH / g, 170 mg KOH / g, 180 mg KOH / g, 190 mg KOH / g, 200 mg KOH / g, 210 mg KOH / g, 230 mg KOH / g, 250 mg KOH / g, 270 mg KOH / g, 300 mg KOH / g, 330 mg KOH / g, 350 mg KOH / g, 370 mg KOH / g, 400 mg KOH / g, 430 mg KOH / g, 450 mg KOH / g, 470 mg KOH / g, 500 mg KOH / g, 530 mg KOH / g, 550 mg KOH / g, 570 mg KOH / g, or any value therebetween. In some embodiments, the polyether polyol has a hydroxyl number of 50 mg KOH / g to 200 mg KOH / g. In some embodiments, the polyether polyol has a hydroxyl number of 100 mg KOH / g to 150 mg KOH / g.

[0011] In some embodiments, the polyether polyol has a mass content of 0.1% to 1%, for example but not limited to 0.2%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.45%, 0.6%, 0.45%, 0.7%, 0.75%, 0.8%, 0.9%, and the like, based on the mass of the composition. In some embodiments, the polyether polyol has a mass content of 0.3% to 0.8%, based on the mass of the composition.

[0012] In some embodiments, the aromatic polycarboxylic acid is selected from one or more of C6-C8aromatic polycarboxylic acids. In some embodiments, the aromatic polycarboxylic acid is selected from one or more of phenyl polycarboxylic acids. In some embodiments, the aromatic polycarboxylic acid is selected from one or more of pyromellitic acid, mellitic acid, and mellitic propionic acid.

[0013] In some embodiments, the hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated C6-C8aromatic polycarboxylic acids. In some embodiments, the hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated phenyl polycarboxylic acids. In some embodiments, the hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated pyromellitic acid, hydrogenated mellitic acid, and hydrogenated mellitic propionic acid.

[0014] In some embodiments, the catalyst comprises an active component and a support. In some embodiments, the active component is selected from one or more of the noble metals. In some embodiments, the active component is selected from one or more of the group consisting of Rh, Ru, Pd, Pt and Au. In some embodiments, the catalyst active component comprises Rh.

[0015] In some embodiments, the support is selected from activated carbon, preferably coconut shell carbon.

[0016] In some embodiments, the activated carbon support is not particularly limited in geometry, for example it can be flake coconut shell carbon having a particle size of 10-30 mesh.

[0017] In some embodiments, the support has a specific surface area of 1000-2000 m 2 / g. By way of non-limiting example, the support can have a specific surface area of 1050 m 2 / g, 1100 m 2 / g, 1150 m 2 / g, 1200 m 2 / g, 1250 m 2 / g, 1300 m 2 / g, 1350 m 2 / g, 1400 m 2 / g, 1450 m 2 / g, 1500 m 2 / g, 1550 m 2 / g, 1600 m 2 / g, 1650 m 2 / g, 1700 m 2 / g, 1750 m 2 / g, 1800 m 2 / g, 1850 m 2 / g, 1900 m 2 / g, and 1950 m 2 / g, and so on.

[0018] In some embodiments, the support has a total pore volume of 0.2-0.8 cm 3 / g. By way of non-limiting example, the support can have a total pore volume of 0.25 cm 3 / g, 0.30 cm 3 / g, 0.35 cm 3 / g, 0.40 cm 3 / g, 0.45 cm 3 / g, 0.50 cm 3 / g, 0.55 cm 3 / g, 0.60 cm 3 / g, 0.65 cm3 / g, 0.70 cm 3 / g and 0.75 cm 3 / g, etc.

[0019] In some embodiments, the bulk density of the support is from 0.2 g / mL to 0.8 g / mL, for example, 0.25 g / mL, 0.3 g / mL, 0.35 g / mL, 0.4 g / mL, 0.45 g / mL, 0.5 g / mL, 0.55 g / mL, 0.6 g / mL, 0.65 g / mL, 0.7 g / mL, 0.75 g / mL, or any value therebetween.

[0020] In some embodiments, the concentration of the active component is from 4.0 g / L to 40.0 g / L, based on the volume of the support. As non-limiting examples, the catalyst active component content can be, but is not limited to, 8.0 g / L, 12.0 g / L, 16.0 g / L, 20.0 g / L, 24.0 g / L, 28.0 g / L, 32.0 g / L, 36.0 g / L, etc.

[0021] In some embodiments, the catalyst is obtained using a preparation method comprising the following steps:

[0022] (1) mixing a noble metal salt solution with a support, and drying to obtain a catalyst precursor;

[0023] (2) reducing the combined state noble metal in the catalyst precursor to zero valence to obtain a catalyst.

[0024] In the above technical solution, the noble metal salt in step (1) is preferably at least one of a chloride salt, a nitrate salt, and an acetate salt of Rh, Ru, Pd, Pt, and Au.

[0025] In the above technical solution, the temperature for reduction in step (2) is preferably from 200°C to 500°C. For example, but not limited to, 250°C, 300°C, 350°C, 400°C, 450°C, etc.

[0026] In the above technical solution, the reduction atmosphere in step (2) is preferably H2 atmosphere or a mixture of H2 and N2.

[0027] In some embodiments, the solvent is selected from one or more of water and C1-C6 alcohols. In some embodiments, the solvent is selected from one or more of C1-C4 alcohols. In some embodiments, the solvent is selected from one or more of water, methanol, ethanol, and propanol.

[0028] In a second aspect, the present application provides a method for synthesizing hydrogenated aromatic polycarboxylic acid, comprising reacting aromatic polycarboxylic acid and hydrogen in the presence of a catalyst and a polyether polyol, preferably, the reaction is carried out in a solvent.

[0029] By introducing polyether polyol additive in the synthesis of hydrogenated aromatic polycarboxylic acid, the present application can interact with catalytically active centers, accelerate the desorption of product hydrogenated aromatic polycarboxylic acid such as hydrogenated pyromellitic acid from catalytically active centers, prevent further carboxyl hydrogenation side reactions of the product on the catalytically active centers, thereby reducing the generation of by-products and improving the reaction selectivity.

[0030] In some embodiments, the polyether polyol has a backbone consisting of -R-O- units, wherein R is selected from C2-C10 alkylene groups. In some embodiments, R is selected from C2-C6 alkylene groups, such as ethylene, propylene, butylene or pentylene.

[0031] In some embodiments, the polyether polyol is selected from one or more of polyethylene glycol, polypropylene glycol and polybutylene glycol.

[0032] In some embodiments, the polyether polyol has a number average molecular weight of 200-5000 g / mol, such as 500 g / mol, 700 g / mol, 1000 g / mol, 1300 g / mol, 1500 g / mol, 1700 g / mol, 2000 g / mol, 2300 g / mol, 2500 g / mol, 2700 g / mol, 3000 g / mol, 3300 g / mol, 3500 g / mol, 3700 g / mol, 4000 g / mol, 4300 g / mol, 4500 g / mol, 4700 g / mol or any value therebetween. In the present application, the number average molecular weight of the polyether polyol within the above range can effectively optimize the catalytic reaction performance, i.e. improve the conversion rate of pyromellitic acid PMA and the selectivity of product hydrogenated pyromellitic acid HPMA; while too high or too low number average molecular weight of the polyether polyol significantly reduces the improvement of catalytic reaction performance.

[0033] In some embodiments, the polyether polyol has a number average molecular weight of 500-5000 g / mol. In some embodiments, the polyether polyol has a number average molecular weight of 600-1500 g / mol.

[0034] In some embodiments, the polyether polyol has a hydroxyl value of 20 mg KOH / g to 600 mg KOH / g, such as 50 mg KOH / g, 60 mg KOH / g, 70 mg KOH / g, 80 mg KOH / g, 90 mg KOH / g, 100 mg KOH / g, 110 mg KOH / g, 120 mg KOH / g, 130 mg KOH / g, 140 mg KOH / g, 150 mg KOH / g, 160 mg KOH / g, 170 mg KOH / g, 180 mg KOH / g, 190 mg KOH / g, 200 mg KOH / g, 210 mg KOH / g, 230 mg KOH / g, 250 mg KOH / g, 270 mg KOH / g, 300 mg KOH / g, 330 mg KOH / g, 350 mg KOH / g, 370 mg KOH / g, 400 mg KOH / g, 430 mg KOH / g, 450 mg KOH / g, 470 mg KOH / g, 500 mg KOH / g, 530 mg KOH / g, 550 mg KOH / g, 570 mg KOH / g, or any value therebetween.

[0035] In some embodiments, the polyether polyol has a hydroxyl value of 50 mg KOH / g to 200 mg KOH / g. In some embodiments, the polyether polyol has a hydroxyl value of 100 mg KOH / g to 150 mg KOH / g.

[0036] In some embodiments, the polyether polyol has a mass content of 0.1% to 1%, such as but not limited to 0.2%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.9%, and the like, based on the total mass of the catalyst, polyether polyol, aromatic polycarboxylic acid, and solvent. In some embodiments, the polyether polyol has a mass content of 0.3% to 0.8%.

[0037] In the present application, the content of the polyether polyol within the above range can effectively optimize the catalytic reaction performance, i.e., improve the PMA conversion rate and the product HPMA selectivity; and too high or too low mass content of the polyether polyol in the catalytic reaction system significantly reduces the improvement range of the catalytic reaction performance.

[0038] In some embodiments, the aromatic polycarboxylic acid is selected from one or more of C6-C8 aromatic polycarboxylic acids. In some embodiments, the aromatic polycarboxylic acid is selected from one or more of phenyl polycarboxylic acids. In some embodiments, the aromatic polycarboxylic acid is one or more of pyromellitic acid, mellitic acid, and mellitic propionic acid.

[0039] In some embodiments, the hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated C6-C8 aromatic polycarboxylic acids. In some embodiments, the hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated phenyl polycarboxylic acids. In some embodiments, the hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated pyromellitic acid, hydrogenated pyromellitic tetraacetic acid, and hydrogenated pyromellitic tetrapropionic acid.

[0040] In some embodiments, the catalyst includes an active component and a support. In some embodiments, the active component is selected from one or more noble metals. In some embodiments, the active component is selected from one or more of Rh, Ru, Pd, Pt, and Au. In some embodiments, the catalyst active component includes Rh.

[0041] In some embodiments, the carrier is selected from activated carbon, preferably coconut shell carbon.

[0042] In some embodiments, the activated carbon carrier is not particularly limited in geometry; for example, it can be flake-shaped coconut shell carbon with a particle size of 10-30 mesh.

[0043] In some embodiments, the specific surface area of ​​the carrier is 1000–2000 m². 2 / g is a non-limiting example; the specific surface area of ​​the carrier can be 1050 m². 2 / g、1100m 2 / g、1150m 2 / g、1200m 2 / g、1250m 2 / g、1300m 2 / g, 1350m 2 / g, 1400m 2 / g, 1450m 2 / g, 1500m 2 / g, 1550m 2 / g, 1600m 2 / g、1650m 2 / g, 1700m 2 / g、1750m 2 / g、1800m 2 / g、1850m 2 / g、1900m 2 / g and 1950m 2 / g etc.

[0044] In some embodiments, the total pore volume of the carrier adsorbed is 0.2–0.8 cm³. 3 / g, as a non-limiting example, the total pore volume of the carrier adsorbed can be 0.25 cm³. 3 / g, 0.30cm3 / g, 0.35 cm 3 / g, 0.40 cm 3 / g, 0.45 cm 3 / g, 0.50 cm 3 / g, 0.55 cm 3 / g, 0.60 cm 3 / g, 0.65 cm 3 / g, 0.70 cm 3 / g and 0.75 cm 3 / g, and so on.

[0045] In some embodiments, the bulk density of the support is 0.2 g / mL-0.8 g / mL, for example 0.25 g / mL, 0.3 g / mL, 0.35 g / mL, 0.4 g / mL, 0.45 g / mL, 0.5 g / mL, 0.55 g / mL, 0.6 g / mL, 0.65 g / mL, 0.7 g / mL, 0.75 g / mL, or any value therebetween.

[0046] In some embodiments, the concentration of the active component is 4.0 g / L-40.0 g / L, based on the volume of the support. As non-limiting examples, the catalyst active component content can be, but is not limited to, 8.0 g / L, 12.0 g / L, 16.0 g / L, 20.0 g / L, 24.0 g / L, 28.0 g / L, 32.0 g / L, 36.0 g / L, and so on.

[0047] In some embodiments, the catalyst is obtained using a preparation method comprising the following steps:

[0048] (1) mixing a noble metal salt solution with a support, and drying to obtain a catalyst precursor;

[0049] (2) reducing the chemical state noble metal in the catalyst precursor to zero valence to obtain the catalyst.

[0050] In the above technical solution, the noble metal salt in step (1) is preferably at least one of the hydrochloride, nitrate, and acetate of Rh, Ru, Pd, Pt, and Au.

[0051] In the above technical solution, the temperature for reduction in step (2) is preferably 200°C-500°C. For example, but not limited to, 250°C, 300°C, 350°C, 400°C, 450°C, and so on.

[0052] In the above technical solution, the reduction atmosphere in step (2) is preferably H2 atmosphere or H2 and N2 mixed gas.

[0053] In some embodiments, the solvent is selected from one or more of water and C1-C6 alcohols. In some embodiments, the solvent is selected from one or more of C1-C4 alcohols. In some embodiments, the solvent is selected from one or more of water, methanol, ethanol, and propanol.

[0054] In some embodiments, the temperature of the reaction is from 60°C to 200°C, such as, but not limited to, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and the like.

[0055] In some embodiments, the time of the reaction is from 1 h to 10 h, such as, but not limited to, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, and the like.

[0056] In some embodiments, the partial pressure of hydrogen in the reaction is from 5.0 MPaG to 12.0 MPaG, such as, but not limited to, 5.5 MPaG, 6.0 MPaG, 6.5 MPaG, 7.0 MPaG, 7.5 MPaG, 8.0 MPaG, 8.5 MPaG, 9.0 MPaG, 9.5 MPaG, 10.0 MPaG, 10.5 MPaG, 11.0 MPaG, 11.5 MPaG, and the like.

[0057] Compared to the prior art, the present application can significantly improve the selectivity of the reaction by introducing a polyether polyol in the synthesis of hydrogenated aromatic polycarboxylic acids, such as hydrogenated pyromellitic acid. DETAILED DESCRIPTION

[0058] In order to make the objectives, technical solutions, and advantages of the present application clearer, the following further describes the present application in conjunction with examples. The specific examples described herein are only used to explain the present application and do not constitute any limitation on the present application. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessarily confusing the concept of the present disclosure. Such structures and technologies are also described in many publications.

[0059] The reaction pressures described in the present application are all gauge pressures.

[0060] The conversion rate of pyromellitic acid in the present application is calculated by the following formula:

[0061] Pyromellitic acid conversion rate (a) = (m (PMA,in) -m (PMA,out) ) / m (PMA,in) x 100%;

[0062] Hydrogenated pyromellitic acid selectivity (S) = m (HPMA) / M (HPMA) / ((m (PMA,in) -m (PMA,out) ) / M (PMA) )×100%;

[0063] PMA: pyromellitic acid;

[0064] HPMA: hydrogenated pyromellitic acid;

[0065] m (PMA,in) : mass of PMA put in before reaction;

[0066] m (PMA,out) : mass of PMA remained after reaction;

[0067] m (HPMA) : mass of HPMA produced in reaction;

[0068] M (HPMA) : molecular weight of HPMA;

[0069] M (PMA) : molecular weight of PMA.

[0070] The present application will be described in detail by way of examples.

[0071] Example 1

[0072] (I) Catalyst preparation

[0073] (1) Rhodium chloride trihydrate (RhCl3-3H2O) was mixed with pure water to prepare a 100.0 mL RhCl3 aqueous solution containing 2.0 g of Rh, with a Rh concentration of 20.0 g / L. 100.0 mL of coconut shell activated carbon AC (specific surface area: 1200 m 2 / g, pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) was mixed with the impregnation solution, and impregnated on a rotary evaporator at 60°C for 2 hours. After the solvent was evaporated under reduced pressure, the wet catalyst precursor was placed in a blast drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor.

[0074] (2) The catalyst precursor was placed in a tube furnace and programmed to 350°C at a temperature rising rate of 10°C / min under a mixed gas containing 10% H2(H2 and N2), and kept at 350°C for 2 hours. The temperature was then naturally lowered to room temperature (25°C) to obtain the catalyst, with a Rh content of 20.0 g / L.

[0075] The preparation conditions of the catalyst and the composition of the catalyst are listed in Table 1.

[0076] (II) Synthesis of hydrogenated pyromellitic acid

[0077] Into a 300 mL 316L stainless steel autoclave-type reactor, pyromellitic acid, an additive, a catalyst, and a solvent were charged. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out while stirring and raising the temperature to a reaction temperature. The specific conditions were as follows:

[0078] Catalyst: 2.5 g;

[0079] Raw material: pyromellitic acid = 10 g;

[0080] Solvent: ethanol = 90 g;

[0081] Additive: polybutylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 108 mgKOH / g) = 0.5% (based on the total weight of the catalyst + raw material + solvent + additive, the same as in the following examples and comparative examples);

[0082] Reaction pressure (H2partial pressure): 8.0 MPa;

[0083] Reaction temperature: 120°C;

[0084] Reaction time: 5.0 h.

[0085] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0086] For ease of comparison, the hydrogenated pyromellitic acid synthesis conditions are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0087] Example 2

[0088] (I) Catalyst preparation

[0089] (1) RhCl3.3H2O was mixed with pure water to prepare a 100.0 mL RhCl3aqueous solution containing 2.0 g of Rh as an impregnation solution, wherein the Rh concentration was 20.0 g / L. 100.0 mL of activated carbon AC (specific surface area: 1200 m 2 / g, pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) was mixed with the impregnation solution, and impregnated on a rotary evaporator at 60°C for 2 hours. After the solvent was evaporated under reduced pressure, the wet catalyst precursor was placed in a blast drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor.

[0090] (2) The catalyst precursor was placed in a tube furnace, and was programmed to a temperature of 350°C at a heating rate of 10°C / min under a mixed gas containing 10% H2(H2and N2), and was kept at 350°C for 2 hours, and then naturally cooled to room temperature of 25°C to obtain the catalyst, wherein the Rh content was 20.0 g / L.

[0091] The preparation conditions and catalyst composition of the catalysts are listed in Table 1.

[0092] (II) Synthesis of hydrogenated pyromellitic acid

[0093] Into a 300 mL 316L stainless steel autoclave reactor, pyromellitic acid, additive, catalyst and solvent were charged. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out under stirring and heating to the reaction temperature. The specific conditions are as follows:

[0094] Catalyst: 2.5 g;

[0095] Raw material: pyromellitic acid = 10 g;

[0096] Solvent: ethanol = 90 g;

[0097] Additive: polypropylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 113 mgKOH / g) = 0.5%;

[0098] Reaction pressure (H2partial pressure): 8.0 MPa;

[0099] Reaction temperature: 120°C;

[0100] Reaction time: 5.0 h.

[0101] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0102] For ease of comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0103] Example 3

[0104] (I) Catalyst preparation

[0105] (1) Rhodium chloride trihydrate (RhCl3·3H2O) was mixed with pure water to prepare a 100.0 mL RhCl3aqueous solution containing 2.0 g of Rh as the impregnation solution, wherein the Rh concentration was 20.0 g / L. 100.0 mL of activated carbon AC (specific surface area: 1200 m 2 / g, pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) was mixed with the impregnation solution, and impregnated on a rotary evaporator at 60°C for 2 hours. After the solvent was evaporated under reduced pressure, the wet catalyst precursor was placed in a blast drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor.

[0106] (2) The catalyst precursor was placed in a tube furnace, and was programmed to increase in temperature to 350°C at a rate of 10°C / min under a mixed gas of H2and N2containing 10% H2, and was kept at 350°C for 2 hours, and was naturally cooled to room temperature of 25°C to obtain a catalyst, wherein the content of Rh was 20.0 g / L.

[0107] The preparation conditions and catalyst composition of the catalysts are listed in Table 1.

[0108] (II) Synthesis of hydrogenated pyromellitic acid

[0109] In a 300 mL 316L stainless steel autoclave reactor, pyromellitic acid, an additive, a catalyst, and a solvent were added. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out under stirring and at a reaction temperature. The specific conditions were as follows:

[0110] Catalyst: 2.5 g;

[0111] Raw material: pyromellitic acid = 10 g;

[0112] Solvent: ethanol = 90 g;

[0113] Additive: polyethylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 110 mgKOH / g) = 0.5%;

[0114] Reaction pressure (H2partial pressure): 8.0 MPa;

[0115] Reaction temperature: 120°C;

[0116] Reaction time: 5.0 h.

[0117] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0118] For ease of comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0119] Example 4

[0120] (I) Catalyst preparation

[0121] (1) RhCl3·3H2O was mixed with pure water to prepare a 100.0 mL RhCl3aqueous solution containing 0.4 g of Rh as an impregnation liquid, wherein the Rh concentration was 4.0 g / L. 100.0 mL of activated carbon AC (specific surface area: 1200 m 2The catalyst precursor was obtained by mixing the support (pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) with the impregnation solution and impregnating in a rotary evaporator at 60°C for 2 hours. After evaporating the solvent under reduced pressure, the wet catalyst precursor was dried in a blast drying oven at 120°C for 3 hours.

[0122] (2) The catalyst precursor was placed in a tube furnace and programmed to 350°C at a rate of 10°C / min in a mixed gas (H2and N2) containing 10% H2, and kept at 350°C for 2 hours, and then naturally cooled to room temperature (25°C) to obtain the catalyst, wherein the Rh content was 4.0 g / L.

[0123] The preparation conditions and catalyst composition are listed in Table 1.

[0124] (II) Synthesis of hydrogenated pyromellitic acid

[0125] A 300 mL 316L stainless steel autoclave reactor was charged with pyromellitic acid, additive, catalyst and solvent. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out under stirring and heating to the reaction temperature. The specific conditions were as follows:

[0126] Catalyst: 2.5 g;

[0127] Raw material: pyromellitic acid = 10 g;

[0128] Solvent: ethanol = 90 g;

[0129] Additive: polyethylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 110 mgKOH / g) = 0.1%

[0130] Reaction pressure (H2partial pressure): 5.0 MPa;

[0131] Reaction temperature: 60°C;

[0132] Reaction time: 1.0 h.

[0133] After the reaction, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0134] For easy comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0135] Example 5

[0136] (I) Catalyst preparation

[0137] (1) Rhodium chloride trihydrate (RhCl3·3H2O) was mixed with pure water to prepare 100.0 mL of RhCl3 aqueous solution containing 4.0 g Rh, with an Rh concentration of 40.0 g / L. This solution was then mixed with 100.0 mL of activated carbon AC (specific surface area: 1200 m² / L). 2 The catalyst precursor (with a pore volume of 0.6 mL / g and a bulk density of 0.42 g / mL) was mixed with the impregnation solution and impregnated for 2 hours at 60°C using a rotary evaporator. After evaporating the solvent under reduced pressure, the wet catalyst precursor was placed in a forced-air drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor.

[0138] (2) The catalyst precursor was placed in a tubular atmosphere furnace and heated to 350°C at a heating rate of 10°C / min under the condition of a mixed gas containing 10% H2 (H2 and N2). The temperature was kept constant for 2 hours and then naturally cooled to room temperature of 25°C to obtain the catalyst, wherein the Rh content was 40.0 g / L.

[0139] The preparation conditions and composition of the catalyst are listed in Table 1.

[0140] (II) Catalyst Performance Evaluation

[0141] Pyromellitic acid, additives, catalyst, and solvent were added to a 300 mL 316 L stainless steel high-pressure reactor. After nitrogen purging, hydrogen was added to pressurize the reactor to a certain pressure. The reactor was stirred and heated to the reaction temperature. Specific conditions were as follows:

[0142] Catalyst: 2.5g;

[0143] Raw material: Pyromellitic acid = 10g;

[0144] Solvent: Ethanol = 90g;

[0145] Additive: Polyethylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 110 mg KOH / g) = 1.0%;

[0146] Reaction pressure (H2 partial pressure): 12.0 MPa;

[0147] Reaction temperature: 200℃;

[0148] Reaction time: 10.0h.

[0149] After the reaction was completed, the reaction products were qualitatively analyzed by LC-MS and quantitatively analyzed by HPLC. The conversion rate of the raw materials and the selectivity of the products were calculated.

[0150] For ease of comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0151] Example 6

[0152] (I) Catalyst preparation

[0153] (1) Rhodium chloride trihydrate (RhCl3-3H2O) was mixed with pure water to prepare a 100.0 mL aqueous solution of RhCl3containing 2.0 g of Rh as the impregnation solution, wherein the Rh concentration was 20.0 g / L. 100.0 mL of activated carbon AC (specific surface area: 1200 m2 / g, pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) was mixed with the impregnation solution, and impregnated on a rotary evaporator at 60°C for 2 hours. After the solvent was evaporated under reduced pressure, the wet catalyst precursor was placed in a blast drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor. 2

[0154] (2) The catalyst precursor was placed in a tube furnace and programmed to 300°C at a heating rate of 10°C / min under a mixed gas containing 10% H2(H2and N2), and held at 300°C for 2 hours. The temperature was then naturally lowered to room temperature (25°C) to obtain the catalyst, wherein the Rh content was 20.0 g / L.

[0155] The preparation conditions and catalyst composition are listed in Table 1.

[0156] (II) Synthesis of hydrogenated pyromellitic acid

[0157] Pyromellitic acid, additive, catalyst and solvent were added to a 300 mL 316L stainless steel autoclave reactor. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out under stirring and heating to the reaction temperature. The specific conditions were as follows:

[0158] Catalyst: 2.5 g;

[0159] Raw material: pyromellitic acid = 10 g;

[0160] Solvent: H2O = 90 g;

[0161] Additive: polyethylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 110 mgKOH / g) = 0.5%;

[0162] Reaction pressure (H2partial pressure): 8.0 MPa;

[0163] Reaction temperature: 120°C;

[0164] Reaction time: 5.0 h.

[0165] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity. ​

[0166] The conditions for the synthesis of hydrogenated pyromellitic acid are listed in Table 1, and the results of the reaction and product analysis are listed in Table 2.

[0167] Example 7

[0168] (I) Catalyst preparation

[0169] (1) Rhodium chloride trihydrate (RhCl3-3H2O) was mixed with pure water to prepare a 100.0 mL RhCl3aqueous solution containing 2.0 g of Rh as the impregnation liquid, with a Rh concentration of 20.0 g / L. 100.0 mL of activated carbon AC (specific surface area: 1200 m2 / g, pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) was mixed with the impregnation liquid, and impregnated on a rotary evaporator at 60°C for 2 hours. After the solvent was evaporated under reduced pressure, the wet catalyst precursor was placed in a blast drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor. 2

[0170] (2) The catalyst precursor was placed in a tube furnace and programmed to 300°C at a heating rate of 10°C / min under a mixed gas containing 10% H2(H2and N2), and held at 300°C for 2 hours. The temperature was then naturally lowered to room temperature (25°C) to obtain the catalyst, with a Rh content of 20.0 g / L.

[0171] The preparation conditions and catalyst composition are listed in Table 1.

[0172] (II) Synthesis of hydrogenated pyromellitic acid

[0173] A 300 mL 316L stainless steel high-pressure reaction kettle type reactor was charged with pyromellitic acid, an additive, a catalyst, and a solvent. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out under stirring and heating to the reaction temperature. The specific conditions were as follows:

[0174] Catalyst: 2.5 g;

[0175] Raw material: pyromellitic acid = 10 g;

[0176] Solvent: methanol = 90 g;

[0177] Additive: polyethylene glycol (number average molecular weight Mn: 1000 g / mol, hydroxyl value: 110 mgKOH / g) = 0.5%;

[0178] Reaction pressure (H2partial pressure): 8.0 MPa;

[0179] Reaction temperature: 120°C;

[0180] Reaction time: 5.0 h.

[0181] ​After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0182] For comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0183] Example 8

[0184] (I) Catalyst preparation

[0185] The same as Example 3.

[0186] (II) Synthesis of hydrogenated pyromellitic acid

[0187] The difference from Example 3 is that the number average molecular weight of the additive polyethylene glycol is 200 g / mol, and the hydroxyl value is 552 mgKOH / g.

[0188] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0189] For comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0190] Example 9

[0191] (I) Catalyst preparation

[0192] The same as Example 3.

[0193] (II) Synthesis of hydrogenated pyromellitic acid

[0194] The difference from Example 3 is that the number average molecular weight of the additive polyethylene glycol is 1500 g / mol, and the hydroxyl value is 73 mgKOH / g.

[0195] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0196] For comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0197] Example 10

[0198] (I) Catalyst preparation

[0199] The same as Example 3.

[0200] (II) Synthesis of hydrogenated pyromellitic acid

[0201] The difference from Example 3 is that the additive polyethylene glycol has a number average molecular weight of 3000 g / mol and a hydroxyl value of 45 mg KOH / g.

[0202] After the reaction, the reaction product is qualitatively analyzed by LC-MS and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0203] For comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0204] Example 11

[0205] (I) Catalyst preparation

[0206] The same as Example 3.

[0207] (II) Synthesis of hydrogenated pyromellitic acid

[0208] The difference from Example 3 is that the additive polyethylene glycol has a number average molecular weight of 4000 g / mol and a hydroxyl value of 28 mg KOH / g.

[0209] After the reaction, the reaction product is qualitatively analyzed by LC-MS and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0210] For comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0211] Comparative Example 1

[0212] (I) Catalyst preparation

[0213] (1) Rhodium chloride trihydrate (RhCl3·3H2O) was mixed with pure water to prepare a 100.0 mL RhCl3 aqueous solution containing 2.0 g of Rh as an impregnation solution, wherein the Rh concentration was 20.0 g / L. 100.0 mL of activated carbon AC (specific surface area: 1200 m 2 / g, pore volume: 0.6 mL / g, bulk density: 0.42 g / mL) was mixed with the impregnation solution, and impregnated on a rotary evaporator at 60°C for 2 hours. After the solvent was evaporated under reduced pressure, the wet catalyst precursor was placed in a blast drying oven and dried at 120°C for 3 hours to obtain the catalyst precursor.

[0214] (2) The catalyst precursor was placed in a tube furnace and programmed to 300°C at a temperature rising rate of 10°C / min under a mixed gas containing 10% H2(H2 and N2), and kept at 300°C for 2 hours, and then naturally cooled to room temperature 25°C to obtain the catalyst, wherein the Rh content was 20.0 g / L.

[0215] The preparation conditions and catalyst composition of the catalysts are listed in Table 1.

[0216] (II) Synthesis of hydrogenated pyromellitic acid

[0217] Into a 300 mL 316L stainless steel autoclave reactor, pyromellitic acid, catalyst and solvent were charged. After nitrogen replacement, hydrogen was pressurized to a certain pressure. The reaction was carried out under stirring and heating to the reaction temperature. The specific conditions were as follows:

[0218] Catalyst: 2.5 g;

[0219] Raw material: pyromellitic acid = 10 g;

[0220] Solvent: H2O = 90 g;

[0221] Reaction pressure (H2partial pressure): 8.0 MPa;

[0222] Reaction temperature: 120°C;

[0223] Reaction time: 5.0 h.

[0224] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0225] For ease of comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0226] Comparative Example 2

[0227] (I) Catalyst preparation

[0228] The same as Example 3.

[0229] (II) Synthesis of hydrogenated pyromellitic acid

[0230] The difference from Example 3 is only that the additive is polyphenyl ether, and the number average molecular weight of the polyphenyl ether is 20,000 g / mol.

[0231] After the reaction was completed, the reaction product was qualitatively analyzed by LC-MS, and quantitatively analyzed by HPLC to calculate the raw material conversion rate and product selectivity.

[0232] For ease of comparison, the synthesis conditions of hydrogenated pyromellitic acid are listed in Table 1, and the reaction results and product analysis are listed in Table 2.

[0233] Table 1 Pyromellitic acid hydrogenation reaction conditions

[0234]

[0235]

[0236] Table 2. Reaction results of pyromellitic acid hydrogenation

[0237]

[0238] The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A composition for synthesizing hydrogenated aromatic polycarboxylic acids, comprising an aromatic polycarboxylic acid, a polyether polyol, a catalyst, and optionally a solvent.

2. The composition according to claim 1, characterized in that, The polyether polyol has a main chain composed of -RO- units, wherein R is selected from C2-C10 alkylene groups, preferably from C2-C6 alkylene groups; Preferably, the polyether polyol is selected from one or more of polyethylene glycol, polypropylene glycol, and polybutanediol.

3. The composition according to claim 1 or 2, characterized in that, The polyether polyol has a number average molecular weight of 200 g / mol to 5000 g / mol, preferably 500 g / mol to 4000 g / mol, and more preferably 600 g / mol to 1500 g / mol; and / or The hydroxyl value of the polyether polyol is 20mgKOH / g-600mgKOH / g, preferably 50mgKOH / g-200mgKOH / g, and more preferably 100mgKOH / g-150mgKOH / g.

4. The composition according to any one of claims 1-3, characterized in that, Based on the mass of the composition, the mass content of the polyether polyol is 0.1%-1.0%, preferably 0.3%-0.8%.

5. The composition according to any one of claims 1-4, characterized in that, The aromatic polycarboxylic acid is selected from one or more of C6-C8 aromatic polycarboxylic acids, preferably from one or more of phenyl polycarboxylic acids, more preferably from one or more of pyromellitic acid, pyromellitic tetraacetic acid and pyromellitic tetrapropionic acid; and / or The hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated C6-C8 aromatic polycarboxylic acids, preferably from one or more of hydrogenated phenyl polycarboxylic acids, more preferably from one or more of hydrogenated pyromellitic acid, hydrogenated pyromellitic tetraacetic acid, and hydrogenated pyromellitic tetrapropionic acid; and / or The catalyst comprises an active component and a support. The active component is selected from one or more noble metals, preferably one or more of Rh, Ru, Pd, Pt, and Au. The support is selected from activated carbon. Preferably, based on the volume of the support, the concentration of the active component is 4.0 g / L to 40.0 g / L; and / or The solvent is selected from one or more of water and C1-C6 alcohols, preferably one or more of water, methanol, ethanol and propanol.

6. A method for synthesizing hydrogenated aromatic polycarboxylic acids, comprising reacting an aromatic polycarboxylic acid with hydrogen in the presence of a catalyst and a polyether polyol, preferably, the reaction being carried out in a solvent.

7. The method according to claim 6, characterized in that, The polyether polyol has a main chain composed of -RO- units, wherein R is selected from C2-C10 alkylene groups, preferably from C2-C6 alkylene groups; Preferably, the polyether polyol is selected from one or more of polyethylene glycol, polypropylene glycol, and polybutanediol.

8. The method according to claim 6 or 7, characterized in that, The polyether polyol has a number-average molecular weight of 200 g / mol to 5000 g / mol, preferably 500 g / mol to 4000 g / mol, and more preferably 600 g / mol to 1500 g / mol; and / or The hydroxyl value of the polyether polyol is 20-600, preferably 50-200, more preferably 100-150; and / or Based on the total mass of the catalyst, polyether polyol, aromatic polycarboxylic acid, and solvent, the mass content of the polyether polyol is 0.1%-1.0%, preferably 0.3%-0.8%.

9. The method according to any one of claims 6-8, characterized in that, The aromatic polycarboxylic acid is selected from one or more of C6-C8 aromatic polycarboxylic acids, preferably from one or more of phenyl polycarboxylic acids, more preferably from one or more of pyromellitic acid, pyromellitic tetraacetic acid and pyromellitic tetrapropionic acid; and / or The hydrogenated aromatic polycarboxylic acid is selected from one or more of hydrogenated C6-C8 aromatic polycarboxylic acids, preferably from one or more of hydrogenated phenyl polycarboxylic acids, more preferably from one or more of hydrogenated pyromellitic acid, hydrogenated pyromellitic tetraacetic acid, and hydrogenated pyromellitic tetrapropionic acid; and / or The catalyst comprises an active component and a support. The active component is selected from one or more noble metals, preferably one or more of Rh, Ru, Pd, Pt, and Au. The support is selected from activated carbon. Preferably, based on the volume of the support, the concentration of the active component is 4.0 g / L to 40.0 g / L; and / or The solvent is selected from one or more of water and C1-C6 alcohols, preferably one or more of water, methanol, ethanol and propanol.

10. The method according to any one of claims 6-9, characterized in that, The reaction temperature is 60℃-200℃; and / or The reaction time is 1 h to 10 h; and / or The partial pressure of hydrogen in the reaction is 5.0 MPaG-12.0 MPaG.

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