Method for preparing ester through olefin carbonylation reaction

Abstract

The invention relates to the technical field of carbonylation reaction, and discloses a method for preparing ester through olefin carbonylation reaction, which comprises the following step: in the presence of a catalyst and under an acidic condition, enabling olefin, carbon monoxide and alcohol to be in contact with the catalyst for carbonylation reaction, wherein the catalyst has a structure as shown in a formula (3), and R is selected from halogen, nitryl and C1-C6 alkyl; r2 is selected from alkyl, aryl and-NR ', R' is selected from alkyl of C1-C6 and aryl of C6-C12, and M1, M2, M3 and M4 are respectively and independently selected from at least one of Fe, Al and Zr. # imgabs0 # by adopting the method disclosed by the invention, the olefin conversion rate and the ester selectivity can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of carbonylation reaction, and in particular to a method for preparing ester by carbonylation reaction of olefins. Background Art

[0002] Metal-organic frameworks (MOFs) are coordination polymers produced by the self-assembly of multidentate organic building blocks with inorganic clusters. They have applications in gas adsorption, sensing applications, drug delivery and catalysis. Due to their chemical and structural diversity, their application in catalysis has great potential. Despite the increasing number of reports related to MOFs, the study of MOF catalysts is still in its infancy. Many studies have focused on the synthesis of MOFs with catalytically active sites with well-defined structures. Many catalytic examples involve the reactivity of unsaturated sites, which are located at inorganic nodes or defect sites of the framework. Early work exploited the reactivity of transition metals for hydrogenation and isomerization reactions. Recently, the HKUST-1 and MIL101 frameworks have been used for a variety of Lewis acid-catalyzed reactions, such as the isomerization of terpene derivatives and the cyclization of citronellal to isopulegol. Many MOFs have also been used to study the catalytic properties of organic building blocks. MOFs materials have inherent advantages in heterogeneous reactions due to their metal-organic structure. Their existing metal-organic catalytic structure, coupled with their structural designability, makes their structure more diverse. Its special pore cage channel structure can play a vital role in the regioselectivity and chiral selection of organic chemical reactions. On the other hand, it participates in the reaction as a solid, and can be more easily separated from liquid and gas reactants and products after the reaction. Therefore, the research and development of MOFs materials with special functional groups is of great significance in catalytic reactions, especially in the catalytic reaction of homogeneous reactions to heterogeneous reactions.

[0003] Olefin carbonylation is an important reaction for preparing carboxylic acid esters and their derivatives. This reaction is a process in which olefins react with CO and alcohol compounds under the action of catalysts to produce carboxylic acid esters with high added value. It is currently the most important homogeneous catalytic reaction in the world. Carboxylic acid ester compounds are widely used in the organic synthesis of drugs, surfactants and fragrances. However, the low raw material conversion rate and low ester selectivity of carbonylation reactions need to be further improved. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of low raw material conversion rate and low ester selectivity in carbonylation reaction in the prior art, and to provide a method for preparing esters by carbonylation reaction of olefins.

[0005] In order to achieve the above object, the present invention provides a method for preparing esters by carbonylation of olefins, the method comprising: in the presence of a catalyst, under acidic conditions, contacting olefins, carbon monoxide and alcohol with the catalyst to carry out carbonylation reaction; wherein the catalyst has a structure shown in formula (3):

[0006]

[0007] Wherein, R is selected from halogen, nitro, C1-C6 alkyl; R2 is selected from alkyl, aryl, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl group; M1, M2, M3 and M4 are each independently selected from at least one of Fe, Al and Zr.

[0008] The present invention uses a metal organic framework material containing a specific structure and a palladium catalyst to catalyze the carbonylation reaction of olefins, which can not only obtain a higher olefin conversion rate and ester selectivity, but also the catalyst of the present invention has a stable structure, a simple preparation method, and the catalyst is easy to separate from the product and easy to recover and reuse.

[0009] Preferably, the carbonylation reaction of the present invention is particularly suitable for olefins that do not contain heteroatom functional groups (such as N, S, O, etc.). When the method of the present invention is used to cause the olefins that do not contain heteroatom functional groups to undergo carbonylation reaction, not only can the raw material conversion rate be further improved, but also the selectivity of branched esters in the product can be improved.

[0010] After the catalyst of the present invention is reused 15 times, the olefin conversion rate and the selectivity of branched ester can still be kept basically unchanged. DETAILED DESCRIPTION

[0011] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0012] The present invention provides a method for preparing esters by carbonylation of olefins, the method comprising: in the presence of a catalyst, under acidic conditions, contacting olefins, carbon monoxide and alcohol with the catalyst to carry out carbonylation reaction; wherein the catalyst has a structure shown in formula (3):

[0013]

[0014] Wherein, R is selected from halogen, nitro, C1-C6 alkyl; R2 is selected from alkyl, aryl, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl group; M1, M2, M3 and M4 are each independently selected from at least one of Fe, Al and Zr.

[0015] In the present invention, in formula (3), the position of the R substituent may be any position on the benzene ring. Preferably, the catalyst has a structure shown in formula (3-1):

[0016]

[0017] According to the present invention, preferably, R is selected from F, Cl, Br, I, nitro, and C1-C3 alkyl.

[0018] According to the present invention, preferably, R2 is selected from C1-C6 alkyl, C6-C 15 The aryl group, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl, more preferably, R2 is selected from C1-C3 alkyl, C6-C 10 Aryl.

[0019] In the present invention, unless otherwise specified, the alkyl group may be a linear alkyl group or a branched alkyl group.

[0020] In the present invention, the C1-C6 alkyl group may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. 15 Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, propylphenyl, naphthyl, and the like.

[0021] According to the present invention, preferably, the weight ratio of the catalyst to olefin is 1:1-1000 (for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:100, 1:1000, and a range consisting of any two of the above points), more preferably 1:1-500, and further preferably 1:1-10.

[0022] According to the present invention, preferably, the olefin is C2-C 20 olefin; preferably, the olefin is an olefin that does not contain a heteroatom (such as N, S, O, etc.) functional group; further preferably, the olefin is at least one of butene, pentene, hexene, heptene and octene.

[0023] According to the present invention, preferably, the olefin is an α-olefin.

[0024] According to the present invention, preferably, relative to every gram of olefin, the consumption of described alcohol is 5-500mL (for example, 5mL, 6mL, 7mL, 8mL, 9mL, 10mL, 15mL, 20mL, 30mL, 40mL, 50mL, 100mL, 200mL, 300mL, 400mL, 500mL, and the scope of any two points above). In the present invention, a part of alcohol participates in the reaction as raw material, and the remaining alcohol plays the role of solvent. When the consumption of alcohol is within the above range, the conversion rate of raw material can be further improved.

[0025] According to the present invention, preferably, the alcohol is a monohydric alcohol, preferably a C1-C5 monohydric alcohol; more preferably methanol and / or ethanol.

[0026] According to the present invention, preferably, the amount of carbon monoxide used per gram of olefin is such that the pressure of the carbonylation reaction system is 1-7 MPa (e.g., 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, and a range consisting of any two of the above). The pressure in the present invention is a gauge pressure.

[0027] According to the present invention, preferably, the acidic condition is provided by an organic acid, and the organic acid is an organic acid having 1 to 10 carbon atoms. More preferably, the organic acid is at least one of formic acid, acetic acid and p-toluenesulfonic acid.

[0028] According to the present invention, preferably, the amount of the organic acid used per gram of olefin is 0.001-0.2 g (for example, 0.001 g, 0.01 g, 0.05 g, 0.06 g, 0.07 g, 0.08 g, 0.09 g, 0.1 g, 0.11 g, 0.12 g, 0.13 g, 0.14 g, 0.15 g, 0.2 g, and ranges consisting of any two of the above).

[0029] According to the present invention, preferably, the carbonylation reaction conditions include: temperature of 30-180° C., preferably 50-150° C., and time of 0.1-2 h.

[0030] The present invention also provides a method for preparing a catalyst, which comprises: contacting a metal organic framework material with an active component precursor to carry out a complexation reaction, wherein the active component precursor is a palladium-containing substance; wherein the metal organic framework material has a structure shown in formula (1):

[0031]

[0032] wherein R is selected from halogen, nitro, C1-C6 alkyl; R1 and R2 are each independently selected from C1-C6 alkyl; R2 is selected from alkyl, aryl, -NR', R' is selected from C1-C6 alkyl, C6-C12 Aryl group; M1, M2, M3 and M4 are each independently selected from at least one of Fe, Al and Zr.

[0033] According to the present invention, preferably, R is selected from F, Cl, Br, I, nitro, and C1-C3 alkyl.

[0034] According to the metal organic framework material of the present invention, preferably, R1 and R2 are each independently selected from C1-C6 alkyl, C6-C 15 The aryl group, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl, more preferably C1-C3 alkyl, C6-C 10 Aryl.

[0035] According to the preparation method of the catalyst, preferably, the weight ratio of the active component precursor to the metal organic framework material is 1:1-10000 (for example, it can be 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 100:1, 500:1, 1000:1, 2000:1, 5000:1, 10000:1, and the range composed of any two of the above points); more preferably, it is 1:10-2000, and further preferably, it is 1:10-100.

[0036] According to the preparation method of the catalyst, preferably, the conditions of the complexation reaction include: a temperature of 15-40° C. and a time of 1-10 h. Usually, the complexation reaction is carried out at room temperature.

[0037] According to the preparation method of the catalyst, preferably, the active component precursor is a palladium salt, preferably at least one of Pd(PPh3)4, Pd(OAc)2, Pd(dba)4 and Pd(PPh3)2Cl2.

[0038] The present invention also provides a method for preparing a metal organic framework material, the method comprising: in the presence of a solvent, allowing a metal precursor to undergo a coordination reaction with a ligand, wherein the metal precursor is at least one of a zinc precursor, a cobalt precursor and a magnesium precursor, and the ligand has a structure shown in formula (2):

[0039]

[0040] wherein R is selected from halogen, nitro, C1-C6 alkyl; R1 and R2 are each independently selected from alkyl, aryl, -NR', and R' is selected from C1-C6 alkyl, C6-C 12 Aryl.

[0041] According to the present invention, preferably, R1 and R2 are each independently selected from C1-C6 alkyl, C6-C15 The aryl group, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl, more preferably C1-C3 alkyl, C6-C 10 Aryl.

[0042] According to the present invention, the iron precursor can be any substance containing an iron element that can provide a coordination with the ligand. Preferably, the iron precursor is an iron salt, more preferably a divalent metal salt of iron, further preferably at least one of iron acetate, iron nitrate and iron chloride; particularly preferably FeCl2.

[0043] According to the present invention, the aluminum precursor can be any substance containing aluminum elements that can provide coordination with the ligand. Preferably, the aluminum precursor is an aluminum salt, preferably at least one of AlO4(OH)2, aluminum acetate, aluminum nitrate and aluminum chloride.

[0044] According to the present invention, the zirconium precursor can be any substance containing zirconium elements that can provide coordination with the ligand. Preferably, the zirconium precursor is a zirconium salt, more preferably at least one of zirconium acetate, zirconium nitrate and zirconium chloride; ZrCl4 is particularly preferred.

[0045] According to the present invention, preferably, the solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylpropionamide.

[0046] According to the present invention, preferably, the molar ratio of the metal precursor to the ligand calculated as the metal element is 0.5-3:1, more preferably 0.5-2:1.

[0047] According to the present invention, preferably, the amount of solvent used per gram of ligand is 100-300 mL (for example, 100 mL, 120 mL, 140 mL, 160 mL, 180 mL, 200 mL, 250 mL, 300 mL, and ranges consisting of any two of the above points).

[0048] According to the present invention, preferably, the conditions of the coordination reaction include: temperature of 70-200° C. and time of 5-48 h.

[0049] In the present invention, the method may further include the steps of washing and drying the solid phase product obtained by the coordination reaction. The washing is usually performed using an alcohol solvent (such as ethanol). The drying may be a drying method commonly used in the art, such as oven drying, etc. The drying conditions may also be drying conditions commonly used in the art.

[0050] In the present invention, the ligand represented by formula (2) can be purchased or prepared according to the method in the literature. Preferably, the preparation method of the ligand comprises:

[0051] 1) in the presence of a first catalyst and a base, the substance represented by formula (2-1) is contacted with the substance represented by formula (2-2) to undergo a substitution reaction to obtain a substance represented by formula (2-3);

[0052] 2) Under an inert atmosphere, in the presence of a second catalyst and a reducing agent, reducing the substance represented by formula (2-3) to obtain a ligand represented by formula (2);

[0053] in,

[0054] Wherein, in formula (2-1), formula (2-2) and formula (2-3), X is a halogen (e.g., F, Cl, Br, I), and the definitions of R, R1 and R2 are the same as those of R, R1 and R2 described in the metal organic framework material.

[0055] According to the preparation method of the ligand of the present invention, the first catalyst is selected from the carrier of carbon, silicon dioxide or aluminum oxide, and the active component is Pd, Ru or Ni; preferably, the first catalyst is selected from at least one of Pd / C, Ru / C, Ni / C, Pd / SiO2 and Ru / Al2O3, more preferably at least one of Pd / C, Ru / C and Ni / C. The content of the active component in the first catalyst is 1-20% by weight.

[0056] According to the method for preparing the ligand of the present invention, the base is selected from at least one of carbonates, bicarbonates and bis(trimethylsilyl)amide salts, preferably potassium carbonate and / or potassium bis(trimethylsilyl)amide.

[0057] According to the method for preparing the ligand of the present invention, the substitution reaction in step 1) is carried out in a solvent, and the solvent includes at least one of distilled water, ethanol, methanol and butanol, preferably distilled water and / or butanol.

[0058] According to the preparation method of the ligand of the present invention, the mass ratio of the compound represented by formula (2-1), the substance represented by formula (2-2), the base, the first catalyst and the solvent is (1-8):(1.5-6):(2-18):(0.04-0.3):100.

[0059] According to the preparation method of the ligand of the present invention, the conditions of the substitution reaction include: the reaction temperature is 50-200° C., and the reaction time is 0.5-24 h.

[0060] According to the method for preparing the ligand of the present invention, the gas providing the inert atmosphere can be selected from any one of nitrogen, helium, neon, argon, krypton or xenon, preferably nitrogen.

[0061] According to the method for preparing the ligand of the present invention, the reducing agent is selected from at least one of methyldiethoxysilane, (chloromethyl)methyldiethoxysilane and diethoxyphenylsilane, preferably methyldiethoxysilane and / or (chloromethyl)methyldiethoxysilane.

[0062] According to the preparation method of the ligand of the present invention, the second catalyst is selected from at least one of diphenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate and dioctyl phosphate, preferably diphenyl phosphate and / or dibutyl phosphate.

[0063] According to the method for preparing the ligand of the present invention, the reduction reaction is carried out in a solvent, and the solvent is selected from at least one of toluene, xylene, chlorobenzene and 1,2-dichloroethane, preferably toluene.

[0064] According to the method for preparing the ligand of the present invention, the mass ratio of the substance represented by formula (2-3), the reducing agent, the second catalyst and the solvent is (3-17):(5-30):(0.3-3):(130-880).

[0065] According to the preparation method of the ligand of the present invention, the amount of the reducing agent used is 0.5-3 g per gram of the substance represented by formula (2-3).

[0066] According to the preparation method of the ligand of the present invention, the amount of the second catalyst used is 0.1-0.2 g per gram of the substance represented by formula (2-3).

[0067] According to the preparation method of the ligand of the present invention, the amount of the solvent used is 30-80 mL per gram of the substance represented by formula (2-3).

[0068] According to the preparation method of the ligand of the present invention, the conditions of the reduction reaction include: reaction temperature of 50-180° C., reaction time of 12-40 h; more preferably, reaction temperature of 70-150° C., reaction time of 18-30 h.

[0069] The present invention will be described in detail below by way of examples. In the following examples,

[0070] The room temperature is about 25°C;

[0071] The content of Pd in ​​Pd / C was 8% by weight.

[0072] Olefin conversion rate mol % = (the amount of olefin substance added to the reaction system - the amount of olefin substance remaining in the system) ÷ the amount of olefin substance added to the reaction system × 100%.

[0073] Selectivity of target ester mol%=amount of β-position-inserted ester substance÷(amount of α-position-inserted ester substance+amount of β-position-inserted ester substance)×100%.

[0074] Preparation Example 1

[0075] Preparation method of 5-bromo-2-diphenylphosphinoyl-terephthalic acid:

[0076] (1) 3.6 g of 2,5-dibromoterephthalic acid, 2.9 g of diphenylphosphine oxide, 6.10 g of potassium carbonate, 120 mg of Pd / C and 100 ml of distilled water were placed in a hydrothermal synthesis reactor and heated at 150°C for 3 hours. The mixture was cooled to room temperature and filtered. The liquid was neutralized with 10 wt% hydrochloric acid to pH = 1. A white solid precipitated. The mixture was filtered and washed with distilled water to obtain a white solid 5-bromo-2-diphenylphosphineoxy-terephthalic acid, which was evaporated to dryness at 105°C.

[0077] (2) 8.5 g of 5-bromo-2-diphenylphosphino-terephthalic acid, 11.4 g of methyldiethoxysilane, 1.5 g of diphenyl phosphate and 500 ml of toluene were added under nitrogen protection at 110° C. for 24 h. After the reaction, a 3N aqueous solution of NaOH was added to the reaction system to adjust the pH to greater than 10, and the mixture was extracted three times with 300 ml of ethyl acetate, the aqueous phase was collected, and the mixture was neutralized with a 10 wt % aqueous solution of hydrochloric acid to a pH of less than 3, and a white solid was precipitated. The collected white solid was 5-bromo-2-diphenylphosphino-terephthalic acid, which was then dried at 105° C.

[0078] Preparation Example 2

[0079] Preparation method of 5-methyl-2-diphenylphosphino-terephthalic acid:

[0080] (1) 3.2 g of 5-methyl-terephthalic acid, 3.5 g of diphenylphosphine oxide, 5.6 g of sodium carbonate, 100 mg of Ru / C and 200 ml of distilled water were placed in a hydrothermal synthesis reactor and heated at 180° C. for 3 hours by microwave. The mixture was cooled to room temperature and filtered. The liquid was neutralized with 10 wt % dilute hydrochloric acid to pH=1. A white solid precipitated. The mixture was filtered and washed with distilled water to obtain a white solid 5-methyl-2-diphenylphosphino-terephthalic acid, which was evaporated to dryness at 120° C.

[0081] (2) 5.0 g of 5-methyl-2-diphenylphosphino-terephthalic acid, 10 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 200 ml of toluene were added under nitrogen protection and refluxed at 105° C. for 24 h. After the reaction, a 3N aqueous solution of NaOH was added to the reaction system to adjust the pH to greater than 10, and the mixture was extracted three times with 200 ml of ethyl acetate, the aqueous phase was collected, and the mixture was neutralized with a 10 wt % aqueous solution of hydrochloric acid to a pH of less than 2, and a white solid was precipitated. The white solid was filtered to obtain 5-methyl-2-diphenylphosphino-terephthalic acid, and then dried at 120° C.

[0082] Preparation Example 3

[0083] Preparation method of 5-isopropyl-2-diphenylphosphino-terephthalic acid:

[0084] (1) 3.5 g of 5-isopropyl-terephthalic acid, 3.9 g of diphenylphosphine oxide, 5.0 g of sodium carbonate, 100 mg of Pd / C and 200 ml of distilled water were placed in a hydrothermal synthesis reactor and heated in a microwave at 180° C. for 7 hours. The mixture was cooled to room temperature and filtered. The liquid was neutralized with 10 wt % dilute hydrochloric acid to pH=1. A white solid precipitated. The mixture was filtered and washed with distilled water to obtain a white solid 5-isopropyl-2-diphenylphosphino-terephthalic acid, which was then dried at 120° C.

[0085] (2) 6.0 g of 5-isopropyl-2-diphenylphosphino-terephthalic acid, 12 g of methyldiethoxysilane, 800 mg of diphenyl phosphate and 200 ml of toluene were added under nitrogen protection and refluxed at 115° C. for 24 h. After the reaction, a 3N aqueous solution of NaOH was added to the reaction system to adjust the pH to greater than 10, and the mixture was extracted three times with 200 ml of ethyl acetate, the aqueous phase was collected, and the mixture was neutralized with a 10 wt % aqueous solution of hydrochloric acid to a pH of less than 2, and a white solid was precipitated. The white solid was filtered to obtain 5-isopropyl-2-diphenylphosphino-terephthalic acid, and then dried at 120° C.

[0086] Comparative Preparation Example 1

[0087] Preparation method of 2-diphenylphosphino-terephthalic acid:

[0088] (1) 3.0 g of 2-bromoterephthalic acid, 3.3 g of diphenylphosphine oxide, 5.08 g of sodium carbonate, 100 mg of Ru / C and 200 ml of distilled water were placed in a hydrothermal synthesis reactor and heated in a microwave at 180° C. for 2 hours. The mixture was cooled to room temperature and filtered. The liquid was neutralized with 10 wt % dilute hydrochloric acid to pH=1. A white solid precipitated. The mixture was filtered and washed with distilled water to obtain a white solid 2-diphenylphosphineoxy-terephthalic acid, which was evaporated to dryness at 105° C.

[0089] (2) 6.0 g of 2-diphenylphosphino-terephthalic acid, 10 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 200 ml of toluene were added under nitrogen protection and refluxed at 105° C. for 8 h. After the reaction was completed, a 3N aqueous solution of NaOH was added to the reaction system to adjust the pH to greater than 10, and the mixture was extracted three times with 200 ml of ethyl acetate, the aqueous phase was collected, and the mixture was neutralized with a 10 wt % aqueous solution of hydrochloric acid to a pH of less than 2, and a white solid was precipitated. The white solid was filtered to obtain 2-diphenylphosphino-terephthalic acid, and then dried at 120° C.

[0090] Example 1

[0091] (1) Preparation Example 1 4.3 g of 5-bromo-2-diphenylphosphino-terephthalic acid, 3.0 g of ZrCl4, and 500 ml of N,N-dimethylformamide were added to a hydrothermal synthesis reactor and heated at 95° C. for 24 hours. The mixture was cooled to room temperature, filtered, washed with ethanol, and dried to obtain a white solid (metal organic framework material).

[0092] (2) 5 g of the metal organic framework material obtained in step (1), 200 mg of Pd(dba)4 and 100 ml of toluene were added into a reactor and stirred at room temperature for 8 hours, filtered, washed with toluene and dried at 120°C.

[0093] Example 2

[0094] (1) 3.7 g of 5-methyl-2-diphenylphosphino-terephthalic acid prepared in Preparation Example 2, 1.5 g of FeCl2, and 500 ml of N,N-dimethylformamide were added to a hydrothermal synthesis reactor and heated at 100° C. for 24 hours. The mixture was cooled to room temperature, filtered, washed with ethanol, and dried to obtain a white solid (metal organic framework material).

[0095] (2) 5 g of the metal organic framework material obtained in step (1), 230 mg of Pd(PPh3)4 and 100 ml of toluene were added into a reactor and stirred at room temperature for 8 hours, filtered, washed with toluene and dried at 110°C.

[0096] Example 3

[0097] (1) 4.0 g of 5-isopropyl-2-diphenylphosphino-terephthalic acid prepared in Preparation Example 3, 1.9 g of AlO4(OH)2, and 500 ml of N,N-dimethylformamide were added into a hydrothermal synthesis reactor and heated at 120° C. for 24 hours. The mixture was cooled to room temperature, filtered, washed with ethanol, and dried to obtain a white solid (metal organic framework material).

[0098] (4) 5 g of the metal organic framework material obtained in step (1), 230 mg of Pd(PPh3)4 and 100 ml of toluene were added into a reactor and stirred at room temperature for 8 hours, filtered, washed with toluene and dried at 110°C.

[0099] Comparative Example 1

[0100] The method of Example 1 was followed, except that 5-bromo-2-diphenylphosphino-terephthalic acid was replaced with an equal mole of 2-diphenylphosphino-terephthalic acid prepared in Comparative Preparation Example 1.

[0101] Test Example 1-A

[0102] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of n-butene

[0103] 3.8 g of n-butene, 1.0 g of the catalyst of Example 1, 500 mg of p-toluenesulfonic acid, and 40 mL of methanol were added to a 100 mL reactor. The reactor was closed and replaced with nitrogen three times and carbon monoxide three times. The pressure of carbon monoxide in the reactor was controlled to be 4 MPa. The reactor was heated to 110 ° C and reacted for 0.5 h. After the reaction was completed, the temperature was lowered to room temperature, the reactor was opened, and the catalyst used once was filtered. The solution was subjected to gas chromatography (GC) detection. The conversion of n-butene was 97.4 mol%, and the selectivity of 2-methyl-butyric acid methyl ester was 96.9 mol%.

[0104] Test Example 1-B

[0105] This test example is used to illustrate the use of the recovered catalyst in the carbonylation reaction of n-butene

[0106] The catalyst used once in Test Example 1-A (about 1 g), 3.8 g of n-butene, 500 mg of p-toluenesulfonic acid, and 40 mL of methanol were added to a reactor, which was sealed and replaced with nitrogen three times, carbon monoxide three times, and replaced three times. The pressure of carbon monoxide in the reactor was controlled to be 4 MPa, and the reactor was heated to 110°C for reaction for 0.5 h. After the reaction was completed, the reactor was cooled to room temperature, the reactor was opened, and the catalyst used twice was obtained by filtration. The solution was subjected to gas chromatography (GC) detection, and the n-butene conversion rate was 97.1 mol%, and the selectivity of 2-methyl-butyric acid methyl ester was 96.5 mol%.

[0107] Test Example 2-A

[0108] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of n-pentene

[0109] A 100mL reactor was added with 4.7g of n-pentene, 1.0g of the catalyst of Example 2, 40mL of ethanol, and 500mg of p-toluenesulfonic acid. The reactor was closed, replaced with nitrogen three times, and replaced with carbon monoxide three times. The pressure of carbon monoxide in the reactor was controlled to be 5MPa. The reactor was heated to 110°C. After the reaction was completed, the reaction was allowed to react for 1h. The reactor was cooled to room temperature, the reactor was opened, and the catalyst for one use was obtained by filtration. The solution was subjected to GC detection. The conversion rate of n-pentene was 98.2mol%, and the selectivity of 2-methyl-ethyl pentanoate was 97.4mol%.

[0110] Test Example 2-B

[0111] This test example is used to illustrate the use of the recovered catalyst in the carbonylation reaction of n-pentene

[0112] The catalyst used once in Test Example 2-A (about 1 g), 4.7 g of n-pentene, 40 mL of ethanol, and 500 mg of p-toluenesulfonic acid were added to the reactor, and the reactor was closed. The nitrogen and carbon monoxide were replaced three times, and the pressure of carbon monoxide in the reactor was controlled to be 5 MPa. The reactor was heated to 110°C for 1 hour. After the reaction was completed, the temperature was lowered to room temperature, the reactor was opened, and the catalyst used twice was obtained by filtration. The solution was subjected to GC detection. The conversion rate of n-pentene was 98.5 mol%, and the selectivity of 2-methyl-ethyl pentanoate was 97.1 mol%.

[0113] Test Example 3-A

[0114] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of n-octene

[0115] 7.6 g of n-octene, 1.0 g of the catalyst of Example 3, 40 mL of methanol, and 500 mg of p-toluenesulfonic acid were added to a 100 mL reactor. The reactor was closed, replaced with nitrogen three times, and replaced with carbon monoxide three times. The pressure of carbon monoxide in the reactor was controlled to be 5 MPa. The reactor was heated to 110° C. and reacted for 1.5 h. After the reaction was completed, the reactor was cooled to room temperature, the reactor was opened, and the catalyst used once was filtered. The solution was subjected to GC detection. The conversion of n-octene was 97.2 mol%, and the selectivity of 2-methyl-nonanoic acid methyl ester was 96.4 mol%.

[0116] Test Example 3-B

[0117] This test example is used to illustrate the use of the recovered catalyst in the carbonylation reaction of n-octene

[0118] The catalyst used once in Test Example 3-A (about 1 g), 7.6 g of n-octene, 40 mL of methanol, and 500 mg of p-toluenesulfonic acid were added to a reactor, which was sealed and replaced with nitrogen three times and carbon monoxide three times. The pressure of carbon monoxide in the reactor was controlled to be 5 MPa. The reactor was heated to 110°C for 1.5 h. After the reaction was completed, the reactor was cooled to room temperature, the reactor was opened, and the catalyst used twice was obtained by filtration. The solution was subjected to GC detection, and the conversion rate of n-octene was 97.4 mol%, and the selectivity of 2-methyl-nonanoic acid methyl ester was 96.1 mol%.

[0119] Comparative Test Example 1-A

[0120] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of n-butene

[0121] 3.8 g of n-butene, 1.0 g of the catalyst of Comparative Example 1, 500 mg of p-toluenesulfonic acid, and 40 mL of methanol were added to a 100 mL reactor, the reactor was closed, nitrogen was replaced three times, carbon monoxide was replaced three times, the pressure of carbon monoxide in the reactor was controlled to be 4 MPa, and the reaction was heated to 110 ° C for 0.5 h. After the reaction was completed, the temperature was cooled to room temperature, the reactor was opened, and the catalyst used once was filtered. The solution was subjected to GC detection. The n-butene conversion rate was 90.2 mol%, and the selectivity of 2-methyl-butyric acid methyl ester was 83.7 mol%.

[0122] Comparative Test Example 1-B

[0123] This test example is used to illustrate the use of recycled catalyst for the carbonylation reaction of n-butene

[0124] The catalyst used once in comparative test example 1-A (about 1g), 3.8g of n-butene, 500mg of p-toluenesulfonic acid, and 40mL of methanol were added into the reactor, and the reactor was closed. The nitrogen and carbon monoxide were replaced three times, and the pressure of carbon monoxide in the reactor was controlled to be 4MPa. The reactor was heated to 110°C for reaction for 0.5h. After the reaction was completed, the temperature was lowered to room temperature, the reactor was opened, and the used catalyst was filtered. The solution was subjected to GC detection. The conversion rate of n-butene was 70.4mol%, and the selectivity of 2-methyl-butyric acid methyl ester was 62.1mol%.

[0125] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing esters by carbonylation of olefins, characterized in that: The method comprises: in the presence of a catalyst, under acidic conditions, contacting olefins, carbon monoxide and alcohol with the catalyst to carry out a carbonylation reaction; wherein the catalyst has a structure shown in formula (3): Wherein, R is selected from halogen, nitro, C1-C6 alkyl; R2 is selected from alkyl, aryl, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl group; M1, M2, M3 and M4 are each independently selected from at least one of Fe, Al and Zr.

2. The method according to claim 1, wherein: R is selected from F, Cl, Br, I, nitro, C1-C3 alkyl; R2 is selected from C1-C6 alkyl, C6-C 15 The aryl group, -NR', R' is selected from C1-C6 alkyl, C6-C 12 Aryl.

3. The method according to claim 1, wherein: The weight ratio of the catalyst to the olefin is 1:1-1000, preferably 1:1-500.

4. The method according to claim 1, wherein: The olefin is C2-C 20 Olefins; preferably at least one of butene, pentene, hexene, heptene and octene.

5. The method according to claim 1, wherein: The amount of the alcohol used is 5-500 mL per gram of olefin.

6. The method according to claim 1, wherein: The alcohol is a monohydric alcohol, preferably a C1-C5 monohydric alcohol; more preferably methanol and / or ethanol.

7. The method according to claim 1, wherein: The amount of carbon monoxide used per gram of olefin is such that the pressure of the carbonylation reaction system is 1-7 MPa.

8. The method according to claim 1, wherein: The acidic condition is provided by an organic acid, and the organic acid is at least one of formic acid, acetic acid and p-toluenesulfonic acid.

9. The method according to claim 8, wherein: The amount of the organic acid used is 0.001-0.2 g per gram of olefin.

10. The method according to claim 1, wherein: The carbonylation reaction conditions include: temperature of 30-180° C., preferably 50-150° C., and time of 0.1-2 h.

Images