Carbonylation reaction method

Abstract

The invention relates to the technical field of carbonylation, and discloses a carbonylation reaction method 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 R2 is selected from alkyl, aryl and halogen; m1, M2, M3 and M4 are respectively and independently selected from at least one of Zn, Co and Mg. The method provided by the invention can improve the olefin conversion rate and the ester selectivity. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of carbonylation, in particular to a carbonylation reaction method. 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 one of the most important reactions in the field of industrial catalysis: it is a carbonylation reaction between carbon monoxide (CO) and olefins, and industrially, olefin carbonylation can produce up to 10 billion tons of important chemicals such as acids, esters, and aldehydes every year. CO is an important intermediate product in chemical industry production. It can be prepared from fossil energy such as petroleum and coal, or generated from CO2 or biowaste. Although the reaction of olefin carbonylation using a homogeneous catalytic system has been discovered for 80 years, the Pd catalyst with the highest carbonylation efficiency using a homogeneous catalyst is easy to lose and difficult to recover. 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 the carbonylation reaction in the prior art, and to provide a carbonylation reaction method.

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

[0006]

[0007] Wherein, R2 is selected from alkyl, aryl, halogen; M1, M2, M3 and M4 are each independently selected from at least one of Zn, Co and Mg.

[0008] Through the above technical solution, the present invention achieves the following beneficial effects:

[0009] 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.

[0010] Preferably, the carbonylation reaction of the present invention is particularly suitable for ester-substituted olefins. When the method of the present invention is used to carbonylate ester-substituted olefins, not only the raw material conversion rate can be further improved, but also the selectivity of straight-chain esters in the product can be improved.

[0011] After the catalyst of the present invention is reused 10 times, the olefin conversion rate and the selectivity of the straight-chain ester can still be kept substantially unchanged. DETAILED DESCRIPTION

[0012] 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.

[0013] The present invention provides a carbonylation reaction method, which comprises: in the presence of a catalyst, under acidic conditions, contacting olefin, carbon monoxide and alcohol with the catalyst to carry out a carbonylation reaction; wherein the catalyst has a structure shown in formula (3):

[0014]

[0015] Wherein, R2 is selected from alkyl, aryl, halogen; M1, M2, M3 and M4 are each independently selected from at least one of Zn, Co and Mg.

[0016] According to the present invention, preferably, R2 is selected from C1-C6 alkyl, C6-C 15 Aryl, Br, Cl, I.

[0017] In the present invention, unless otherwise specified, the alkyl group may be a linear alkyl group or a branched alkyl group.

[0018] According to the present invention, preferably, R2 is selected from C1-C6 alkyl, C6-C 15 Aryl, Br, Cl, I; more preferably C1-C3 alkyl, C6-C 10 Aryl.

[0019] 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.

[0020] According to the present invention, preferably, the weight ratio of the catalyst to the 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, 1:200, 1:300, 1:500, 1:1000, and a range consisting of any two of the above points), more preferably 1:1-500, and further preferably 1:1-10.

[0021] According to the present invention, preferably, the olefin is an ester-substituted olefin; more preferably, it is an ester-substituted olefin having a total carbon atom number of 4-20; further preferably, it is an acetate-substituted olefin having a total carbon atom number of 4-20; and further preferably, it is at least one of vinyl acetate, vinyl propionate, vinyl butyrate and vinyl isobutyrate.

[0022] According to the present invention, preferably, relative to each gram of olefin, the amount of the alcohol is 5-100mL (for example, 5mL, 6mL, 7mL, 8mL, 9mL, 10mL, 15mL, 20mL, 25mL, 30mL, 40mL, 50mL, 100mL, and the range of any two points), more preferably 5-10mL. In the present invention, a part of the alcohol participates in the reaction as a raw material, and the remaining alcohol plays the role of a solvent. When the amount of alcohol is within the above range, it can be ensured that esterification is sufficient, and the alcohol plays a solvent role.

[0023] According to the present invention, preferably, the alcohol is a monohydric alcohol, preferably a C1-C5 monohydric alcohol; more preferably methanol and / or ethanol.

[0024] 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, for example, 1 MPa, 2 MPa, 3 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.8 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, and a range consisting of any two of the above. The pressure of the present invention is a gauge pressure.

[0025] According to the present invention, preferably, the acidic condition is provided by an organic acid, and the organic acid is an organic acid having 1-10 carbon atoms. More preferably, the organic acid is an alkyl acid having 1-5 carbon atoms and / or an aromatic acid having 6-8 carbon atoms. Further preferably, the organic acid includes at least one of formic acid, acetic acid and p-toluenesulfonic acid.

[0026] According to the present invention, preferably, the amount of the organic acid used per gram of olefin is 0.001-0.1 g (for example, 0.001 g, 0.01 g, 0.02 g, 0.03 g, 0.04 g, 0.05 g, 0.06 g, 0.07 g, 0.08 g, 0.09 g, 0.1 g, and ranges consisting of any two of the above).

[0027] 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.

[0028] 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):

[0029]

[0030] Wherein, R1 and R2 are each independently selected from alkyl, aryl, and halogen; M1, M2, M3, and M4 are each independently selected from at least one of Zn, Co, and Mg.

[0031] In the present invention, unless otherwise specified, the alkyl group may be a linear alkyl group or a branched alkyl group.

[0032] 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 Aryl, Br, Cl, I; more preferably C1-C3 alkyl, C6-C 10 Aryl.

[0033] In the present invention, the C1-C6 alkyl group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or the like.

[0034] In the present invention, C6-C 15 Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, propylphenyl, naphthyl, and the like.

[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; more preferably 1: 200-2000, and further preferably 1: 10-100. In the present invention, the weight ratio of the active component precursor to the metal organic framework material can be 1: 1, 10: 1, 20: 1, 25: 1, 30: 1, 40: 1, 50: 1, 100: 1, 200: 1, 300: 1, 500: 1, 1000: 1, 2000: 1, 5000: 1, 10000: 1, and the range of any two of the above points.

[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, more 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, R1 and R2 are each independently selected from alkyl, aryl, and halogen.

[0041] According to the present invention, preferably, R1 and R2 are each independently selected from C1-C6 alkyl, C6-C 15 Aryl, Br, Cl, I.

[0042] According to the present invention, the zinc precursor can be any substance containing zinc elements that can provide coordination with the ligand. Preferably, the zinc precursor is a zinc salt, preferably at least one of zinc acetate, zinc nitrate and zinc chloride.

[0043] According to the present invention, the cobalt precursor may be any substance containing cobalt elements that can provide coordination with the ligand. Preferably, the cobalt precursor is a cobalt salt, preferably at least one of cobalt acetate, cobalt nitrate and cobalt chloride.

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

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

[0046] According to the present invention, preferably, the molar ratio of the metal precursor to the ligand calculated as the metal element is 0.3-3: 1. In the present invention, the molar ratio of the metal precursor to the ligand calculated as the metal element can be 0.3: 1, 0.4: 1, 0.5: 1, 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1, 0.9: 1, 1: 1, 1.1: 1, 1.2: 1, 1.5: 1, 2: 1, 2.5: 1, 3: 1, and the range of any two of the above points.

[0047] According to the present invention, preferably, the amount of the solvent is 10-500 mL relative to each gram of the ligand. In the present invention, the amount of the solvent can be 10 mL, 50 mL, 100 mL, 140 mL, 150 mL, 180 mL, 200 mL, 300 mL, 400 mL, 500 mL, and a range consisting of any two of the above points relative to each gram of the ligand.

[0048] According to the present invention, preferably, the conditions of the coordination reaction include: temperature of 50-200° C. and time of 10-48 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, Among them, formula (2-1), formula (2-2),

[0054] In formula (2-3), X is a halogen (eg, F, Cl, Br, I), and the definitions of R1 and R2 are the same as those of 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 0.5-20% 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 method for preparing the ligand of the present invention, preferably, the amount of the second catalyst used is 0.5-1 g per 6 g of the substance represented by formula (2-3).

[0066] According to the method for preparing the ligand of the present invention, preferably, the amount of the reducing agent used is 5-15 g per 3 g of the substance represented by formula (2-3).

[0067] According to the method for preparing the ligand of the present invention, preferably, the amount of the solvent used is 100-300 mL per 3 g 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 5-40 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 and test examples,

[0070] The room temperature is 25°C.

[0071] The Ru content in Ru / C was 8 wt%.

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

[0073] Selectivity of 3-acetoxypropionate mol%=3-acetoxypropionate÷(3-acetoxypropionate+2-acetoxypropionate)×100%.

[0074] Preparation Example 1

[0075] This preparation example is used to illustrate the preparation method of 2-diphenylphosphino-terephthalic acid

[0076] (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.

[0077] (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.

[0078] Comparative Preparation Example 1

[0079] This preparation example is used to illustrate the preparation method of 5-methyl-2-diphenylphosphino-terephthalic acid

[0080] (1) 2.2 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] Example 1

[0083] This example is used to illustrate the preparation method of the catalyst

[0084] (1) 3.5 g of 2-diphenylphosphino-terephthalic acid prepared in Preparation Example 1, 2.9 g of Co(NO3)2·6H2O, 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, post-treated, filtered, washed with ethanol, and dried to obtain a white solid (metal organic framework material).

[0085] (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 to obtain a catalyst.

[0086] Example 2

[0087] (1) 3.5 g of 2-diphenylphosphino-terephthalic acid prepared in Preparation Example 1, 2.6 g of Zn(acac)2, 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, post-treated, filtered, washed with ethanol, and dried to obtain a white solid (metal organic framework material).

[0088] (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 to obtain a catalyst.

[0089] Example 3

[0090] (1) 3.5 g of 2-diphenylphosphino-terephthalic acid prepared in Preparation Example 1, 1.9 g of Mg(NO3)2·2H2O, and 500 ml of N,N-dimethylformamide were added to a hydrothermal synthesis reactor and heated at 120°C for 24 hours. The mixture was cooled to room temperature, post-treated, filtered, washed with ethanol, and dried to obtain a white solid (metal organic framework material).

[0091] (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 to obtain a catalyst.

[0092] Comparative Example 1

[0093] The method of Example 3 was followed, except that Mg(NO3)2·2H2O was replaced by an equimolar amount of ZrCl4.

[0094] Comparative Example 2

[0095] The method of Example 3 was followed, except that 2-diphenylphosphino-terephthalic acid was replaced with an equal molar amount of 5-methyl-2-diphenylphosphino-terephthalic acid prepared in Comparative Preparation Example 1.

[0096] Test Example 1-A

[0097] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate

[0098] 5.8 g of vinyl acetate, 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, nitrogen was replaced three times, carbon monoxide was replaced three times, the pressure of carbon monoxide in the reactor was controlled to be 3 MPa, and the reaction was heated to 110 ° C. 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 vinyl acetate conversion rate was 96.8 mol%, and the selectivity of methyl 3-acetoxypropionate was 97.9 mol%.

[0099] Test Example 1-B

[0100] This test example is used to illustrate the use of the recovered catalyst in the carbonylation reaction of vinyl acetate.

[0101] The catalyst used once in Test Example 1-A (about 1.0 g), 5.8 g of vinyl acetate, 500 mg of p-toluenesulfonic acid, and 40 mL of methanol were added to the 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 3 MPa, and the reactor was heated to 110°C for 0.5 h. After the reaction was completed, the temperature was lowered to room temperature, the reactor was opened, and the catalyst used twice was filtered. The solution was subjected to GC detection. The conversion rate of vinyl acetate was 95.8 mol%, and the selectivity of methyl 3-acetoxypropionate was 97.2 mol%.

[0102] Test Example 2-A

[0103] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate

[0104] 5.8 g of vinyl acetate, 1.0 g of the catalyst of Example 2, 40 mL of ethanol, and 400 mg of formic acid 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 3.5 MPa, and the reaction was heated to 110 ° C for 1 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 GC detection, and the conversion rate of vinyl acetate was calculated to be 98.2 mol%, and the selectivity of ethyl 3-acetoxypropionate was 96.4 mol%.

[0105] Test Example 2-B

[0106] This test example is used to illustrate the use of the recovered catalyst in the carbonylation reaction of vinyl acetate.

[0107] The catalyst used once in Test Example 2-A (about 1 g), 5.8 g of vinyl acetate, 40 mL of ethanol, and 400 mg of formic acid were added into a reactor, and the reactor was sealed. The atmosphere was replaced with nitrogen three times, and with carbon monoxide three times. The pressure of carbon monoxide in the reactor was controlled to be 3.5 MPa. The reactor was heated to 110°C for 1 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 tested by GC. The conversion rate of vinyl acetate was 98.8 mol%, and the selectivity of ethyl 3-acetoxypropionate was 95.6 mol%.

[0108] Test Example 3-A

[0109] This test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate

[0110] 5.8 g of vinyl acetate, 1.0 g of the catalyst of Example 3, 40 mL of methanol, and 400 mg of acetic acid 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 4.0 MPa, and the reaction was heated to 110 ° C for 1 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 GC detection, and the conversion rate of vinyl acetate was calculated to be 97.2 mol%, and the selectivity of methyl 3-acetoxypropionate was 98.4 mol%.

[0111] Test Example 3-B

[0112] This test example is used to illustrate the use of the recovered catalyst in the carbonylation reaction of vinyl acetate.

[0113] The catalyst used once in Test Example 3-A (about 1 g), 5.8 g of vinyl acetate, 40 mL of methanol, and 400 mg of acetic acid were added into 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 4.0 MPa, and the reactor was heated to 110°C for 1 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 vinyl acetate was 96.8 mol%, and the selectivity of methyl 3-acetoxypropionate was 97.4 mol%.

[0114] Comparative Test Example 1-A

[0115] This comparative test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate.

[0116] The method of Test Example 3-A was followed, except that the catalyst of Example 3 was replaced by the catalyst of Comparative Example 1. The vinyl acetate conversion was 84.4 mol%, and the selectivity of methyl 3-acetoxypropionate was 83.7 mol%.

[0117] Comparative Test Example 1-B

[0118] This comparative test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate.

[0119] The method of Test Example 3-B was followed, except that the catalyst used once in Test Example 3-A was replaced with the catalyst used once in Comparative Test Example 1-A. The vinyl acetate conversion was 63.1 mol%, and the selectivity of methyl 3-acetoxypropionate was 54.2 mol%.

[0120] Comparative Test Example 2-A

[0121] This comparative test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate.

[0122] The method of Test Example 3-A was followed, except that the catalyst of Example 3 was replaced by the catalyst of Comparative Example 2. The vinyl acetate conversion was 82.4 mol%, and the selectivity of methyl 3-acetoxypropionate was 79.6 mol%.

[0123] Comparative Test Example 2-B

[0124] This comparative test example is used to illustrate the use of the catalyst in the carbonylation reaction of vinyl acetate.

[0125] The method of Test Example 3-B was followed, except that the catalyst used once in Test Example 3-A was replaced with the catalyst used once in Comparative Test Example 2-A. The vinyl acetate conversion was 56.3 mol%, and the selectivity of methyl 3-acetoxypropionate was 58.6 mol%.

[0126] 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 carbonylation reaction, 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, R2 is selected from alkyl, aryl, halogen; M1, M2, M3 and M4 are each independently selected from at least one of Zn, Co and Mg.

2. The method according to claim 1, wherein: R2 is selected from C1-C6 alkyl, C6-C 15 Aryl, Br, Cl, I.

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 an ester-substituted olefin; preferably at least one of vinyl acetate, vinyl propionate, vinyl butyrate and vinyl isobutyrate.

5. The method according to claim 1, wherein: The amount of the alcohol used is 5-100 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 0.001-0.1 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.

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