Catalyst and application thereof in preparation of methyl isononanoate through carbonylation and esterification of diisobutylene

Abstract

The invention discloses a catalyst and application of the catalyst in preparation of methyl isononanoate through carbonylation esterification of diisobutylene, the catalyst is composed of a palladium compound, one or more phosphorus-containing ligands and an acid assistant, and the application of the catalyst is characterized in that diisobutylene is converted into methyl isononanoate through a carbonylation esterification reaction catalyzed by the catalyst, the method comprises the following steps of: adding a catalyst, diisobutylene and methanol into a stainless steel high-pressure kettle in a homogeneous catalytic reaction system, sealing, filling CO gas, replacing the CO gas for three times, filling the CO gas to 3-6 MPa, stirring, heating, and carrying out timing reaction at a specified reaction temperature (90-150 DEG C) and a constant CO pressure. The catalyst has good activity, selectivity and stability in the reaction of converting diisobutylene into methyl isononanoate through carbonylation esterification, and the method for preparing methyl isononanoate by taking diisobutylene as a raw material through the carbonylation esterification reaction is simple in synthetic route, mild in reaction condition, high in yield of the product methyl isononanoate and suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the chemical field of homogeneous catalysis and fine chemical synthesis, and relates to the application of a catalyst containing a noble metal palladium compound in the one-step preparation of methyl isononanoate by carbonylation esterification reaction using diisobutylene, carbon monoxide and methanol as raw materials. Background Art

[0002] Highly branched isononanoic acid is an important organic chemical raw material. Starting from isononanoic acid (for example, isononanol is prepared by hydrogenation of isononanoic acid catalyst, or isononanoic acid and polyols are prepared by esterification reaction of isononanoic acid and polyols), many high value-added fine chemical products can be synthesized. They are widely used in the manufacturing industries of plasticizers, surfactants, fragrances, high-end coatings, etc., and can replace Freon as the raw material of new refrigerants.

[0003] At present, the preparation methods of isononanoic acid are mainly through diisobutylene hydroformylation and carbonylation. Among them, the diisobutylene hydroformylation method is to use diisobutylene and synthesis gas (CO / H 2 ) as raw material, a Co or Rh compound modified with a phosphorus-containing ligand as a catalyst, and a hydroformylation reaction is used to prepare isononanal / isononanol, and the isononanal / isononanol is then oxidized to prepare isononanoic acid (CN 1900043A, CN 112794796 A, CN 114149313 A). This process not only requires the use of expensive Rh catalysts, but also the product isononanal undergoes aldol condensation reaction to generate high-boiling point by-products, which is not conducive to the separation of catalyst and product; when using Co catalyst, the product isononanal is very prone to hydrogenation side reactions, which is accompanied by the generation of a large number of isononanol by-products and the serious deactivation of Co catalysts; carbonylation carboxylation method is to use diisobutylene, CO and water as raw materials, and a phosphorus-containing ligand-modified Pd compound as a catalyst to prepare isononanoic acid by carbonylation carboxylation reaction (Angew. Chem. Int. Ed. 2019, 58, 14365-14373, Catal. Sci. Technol., 2021, 11, 2703-2707). This process requires water as raw material, resulting in the water-sensitive phosphorus-containing ligand-modified Pd catalyst being very easy to deactivate; in addition, the product isononanoic acid has strong polarity and high boiling point, which is not conducive to the separation of homogeneous Pd catalyst and product isononanoic acid. Summary of the invention

[0004] The purpose of the present invention is to provide a catalyst for preparing methyl isononanoate by carbonylation esterification of diisobutylene. The catalyst has good activity, selectivity and stability and can efficiently convert diisobutylene into methyl isononanoate by carbonylation esterification reaction.

[0005] A catalyst for preparing methyl isononanoate by carbonylation esterification of diisobutylene, wherein the catalyst can be used to convert diisobutylene into methyl isononanoate by carbonylation esterification reaction. The catalyst is composed of a palladium compound, a phosphorus-containing ligand and an acid auxiliary agent.

[0006] The palladium compound is selected from the group consisting of palladium dichloride, bis(acetonitrile)palladium dichloride, palladium acetate, palladium nitrate, palladium trifluoroacetate, bis(triphenylphosphine)palladium dichloride, (1,5-cyclooctadiene)palladium dichloride, allylpalladium chloride, tetrakis(triphenylphosphine)palladium, di(acetylacetone)palladium, bis(dibenzylideneacetone)palladium, or tris(dibenzylideneacetone)dipalladium;

[0007] The phosphorus-containing ligand is selected from 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,1'-bis(diphenylphosphine)ferrocene, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene, 4,6-bis(diphenylphosphine)phenazine, 1,2-bis( One or more of di-tert-butylphosphinomethyl)benzene, 1,1'-bis(di-tert-butylphosphinomethyl)ferrocene, tris(2,4-di-tert-butyl)phenyl phosphite, trimethylolpropane phosphite, 2,2'-bis[(1,1'-biphenyl-2,2'-diyl)phosphite]-3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl and a phosphorus-containing ligand containing a P,O-heterogroup (molecular structure is shown in the following formula);

[0008]

[0009] Structure of bidentate phosphorus-containing ligands containing P,O-heterogroups

[0010] The acid auxiliary agent is one or more of organic sulfonic acid, boric acid, benzoic acid, salicylic acid and Lewis acid containing trifluoromethanesulfonate; the organic sulfonic acid includes p-toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, quinoline-8-sulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and methanesulfonic acid; the Lewis acid containing trifluoromethanesulfonate includes aluminum trifluoromethanesulfonate, scandium trifluoromethanesulfonate and bismuth trifluoromethanesulfonate.

[0011] The catalyst is used in the carbonylation and esterification of diisobutylene to prepare methyl isononanoate. The specific application method of the catalyst is as follows:

[0012] The catalyst composed of the palladium compound, the phosphorus-containing ligand and the acid auxiliary agent, diisobutylene and methanol are added into a stainless steel high-pressure reactor. After the reactor is sealed, the atmosphere in the reactor is replaced with CO gas for three times, and then 3-6 MPa of CO gas is filled in, and the reaction is carried out at 90-150° C. for 3-24 hours. After the reaction is completed, the reaction liquid is cooled to room temperature and subjected to gas chromatography analysis, with n-hexadecane as an internal standard, to calculate the diisobutylene conversion rate and the chromatographic yield of methyl isononanoate, and the reaction liquid is subjected to reduced pressure distillation to separate the methyl isononanoate product and the catalyst; wherein the molar ratio of the palladium compound to diisobutylene is 1:50-20000; the molar ratio of diisobutylene to methanol is 1:1-10; the P / Pd molar ratio of the phosphorus-containing ligand to the palladium compound in the catalyst is 1-50:1, and the molar ratio of the acid auxiliary agent to the palladium compound is 1-100:1.

[0013] The application of the catalyst in the preparation of methyl isononanoate by carbonylation and esterification of diisobutylene is characterized in that the catalyst has good stability and can be reused for more than 5 times.

[0014] The present invention provides a catalyst for preparing methyl isononanoate by carbonylation of diisobutylene. The use of the catalyst can efficiently convert diisobutylene into methyl isononanoate through carbonylation esterification reaction. The method for preparing methyl isononanoate by carbonylation esterification of diisobutylene catalyzed by the catalyst has the following advantages:

[0015] (1) The catalyst has good activity, selectivity and stability;

[0016] (2) The palladium catalyst has good stability and can be recycled;

[0017] (3) Using diisobutylene, CO and methanol as raw materials, methyl isononanoate was prepared in one step. The reaction route was simple, the reaction conditions were mild, and the reaction process had 100% atom economy.

[0018] (4) The raw materials are cheap and readily available, and the product methyl isononanoate has high added value;

[0019] (5) The product methyl isononanoate has good chemical stability and avoids the formation of other by-products. DETAILED DESCRIPTION

[0020] The present invention is described in more detail with reference to the following examples. However, these examples are limited to illustrating the present invention and do not constitute any form of limitation to the present invention. The reagents involved in the examples are all commonly used commercial products.

[0021] Embodiment 1-47

[0022] Reaction results of carbonylation and esterification of diisobutylene to prepare methyl isononanoate under different palladium compounds and phosphorus-containing ligands

[0023] Specific experimental steps: 0.3 mmol of palladium compound, 0.6 mmol of phosphorus-containing ligand (if two phosphorus-containing ligands, namely phosphorus-containing ligand 1 and phosphorus-containing ligand 2, are used, each is 0.3 mmol), 3 mmol of methanesulfonic acid auxiliary, 100 mmol of diisobutylene and 500 mmol of methanol are added in sequence to a stainless steel high-pressure reactor. After ensuring the airtightness of the reactor device, the atmosphere in the reactor is replaced with CO gas three times, and then CO is filled to 6.0 MPa. The reactor is then heated to 130°C for 10 hours. After the reaction is completed, it is cooled to room temperature, and the reaction liquid is taken for gas chromatography analysis. Hexadecane is used as an internal standard, and the chromatographic yield of methyl isononanoate is calculated.

[0024] Table 1 Reaction results of preparing methyl isononanoate by carbonylation esterification of diisobutylene under different palladium compounds and phosphorus-containing ligands

[0025]

[0026]

[0027] Note: XANTPHOS, 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene; XANTPHOS dioxide, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene; DTBPMB, 1,2-bis(di-tert-butylphosphinomethyl)benzene; BIPHEPHOS, 2,2'-bis[(1,1'-biphenyl-2,2'-diyl)phosphite]-3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl.

[0028] Examples 48-60

[0029] Reaction results of carbonylation esterification of diisobutylene to prepare methyl isononanoate under different acid additive conditions

[0030] Specific experimental steps: 0.2mmol palladium trifluoroacetate, 0.6mmol phosphorus-containing ligand DTBPMB, 6mmol acid auxiliary, 100mmol diisobutylene and 500mmol methanol were added to a stainless steel high-pressure reactor in sequence. After ensuring the airtightness of the reactor, the atmosphere in the reactor was replaced with CO gas three times, and then CO was filled to 6.0MPa. The reactor was then heated to 130°C for 10 hours. After the reaction was completed, it was cooled to room temperature, and the reaction liquid was taken for gas chromatography analysis. Hexadecane was used as an internal standard to calculate the chromatographic yield of methyl isononanoate.

[0031] Table 2 Reaction results of preparing methyl isononanoate by carbonylation esterification of diisobutylene under different acid additive conditions Note: DTBPMB, 1,2-bis(di-tert-butylphosphinomethyl)benzene.

[0032] Embodiment 61

[0033] Catalyst service life investigation results.

[0034] The catalyst is composed of palladium trifluoroacetate, L2 and methanesulfonic acid. The catalyst is still active after being recycled 5 times in the process of preparing methyl isononanoate by carbonylation esterification of diisobutylene. The yield of methyl isononanoate gradually decreases from 93% to 73%, indicating that the catalyst has a certain degree of stability. Specific experimental steps: 0.3mmol palladium trifluoroacetate, 0.6mmol L2, 3mmol methanesulfonic acid, 100mmol diisobutylene and 500mmol methanol were placed in a stainless steel autoclave in sequence, the air tightness of the device was checked after sealing, the atmosphere in the autoclave was replaced with CO gas three times, CO was then charged to 6.0MPa, and the autoclave was heated to 130°C for reaction for 10 hours. After the reaction was completed, it was cooled to room temperature, and the reaction liquid was taken for gas chromatography analysis, with n-hexadecane as an internal standard, and the chromatographic yield of methyl isononanoate was calculated; then all the reaction liquid was removed for vacuum distillation to separate methanol, unreacted diisobutylene raw material and methyl isononanoate product, and 100mmol diisobutylene and 500mmol methanol were added to the remaining viscous material at the bottom of the autoclave (i.e., the catalyst) after vacuum distillation, and the mixture was transferred to a stainless steel autoclave, the atmosphere in the autoclave was replaced with CO gas three times, CO was charged to 6.0MPa again, and the reaction was carried out at 130°C for 10h. The addition of 100 mmol of diisobutylene and 500 mmol was repeated 5 times in total.

[0035] Table 3 Catalyst service life investigation results (Example 61)

[0036]

Claims

1. A catalyst, It is characterized in that The catalyst is composed of a palladium compound, a phosphorus-containing ligand and an acid auxiliary agent; the P / Pd molar ratio of the phosphorus-containing ligand to the palladium compound is 1-50:1; the molar ratio of the acid auxiliary agent to the palladium compound is 1-100:1; The palladium compound is selected from the group consisting of palladium dichloride, bis(acetonitrile)palladium dichloride, palladium acetate, palladium nitrate, palladium trifluoroacetate, bis(triphenylphosphine)palladium dichloride, (1,5-cyclooctadiene)palladium dichloride, allylpalladium chloride, tetrakis(triphenylphosphine)palladium, di(acetylacetone)palladium, bis(dibenzylideneacetone)palladium and tris(dibenzylideneacetone)dipalladium; The phosphorus-containing ligand is selected from 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,1'-bis(diphenylphosphine)ferrocene, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene, 4,6-bis(diphenylphosphine)phenazine, 1 , 2-bis(di-tert-butylphosphinomethyl)benzene, 1,1'-bis(di-tert-butylphosphinomethyl)ferrocene, tris(2,4-di-tert-butyl)phenyl phosphite, trimethylolpropane phosphite, 2,2'-bis[(1,1'-biphenyl-2,2'-diyl)phosphite]-3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl and phosphorus-containing ligands containing P,O-heterogroups or a combination thereof; The acid auxiliary agent is one or more of organic sulfonic acid, boric acid, benzoic acid, salicylic acid and Lewis acid containing trifluoromethanesulfonate; the organic sulfonic acid includes p-toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, quinoline-8-sulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and methanesulfonic acid; the Lewis acid containing trifluoromethanesulfonate includes aluminum trifluoromethanesulfonate, scandium trifluoromethanesulfonate and bismuth trifluoromethanesulfonate.

2. Use of the catalyst according to claim 1 in the preparation of methyl isononanoate by carbonylation esterification of diisobutylene, It is characterized in that Specifically include: The catalyst composed of the palladium compound, the phosphorus-containing ligand and the acid auxiliary agent, diisobutylene and methanol are added to a stainless steel high-pressure reactor. After the reactor is sealed, the atmosphere in the reactor is replaced with CO gas three times, and then 3-6 MPa of CO gas is filled in, and the reaction is carried out at 90-150° C. for 3-24 hours. After the reaction is completed, the reaction liquid is cooled to room temperature and subjected to gas chromatography analysis, with n-hexadecane as an internal standard, to calculate the diisobutylene conversion rate and the chromatographic yield of methyl isononanoate, and the reaction liquid is subjected to reduced pressure distillation to separate the methyl isononanoate product and the catalyst; the molar ratio of the palladium compound to diisobutylene is 1: 50-20000; the molar ratio of diisobutylene to methanol is 1: 1-10; the P / Pd molar ratio of the phosphorus-containing ligand to the palladium compound in the catalyst is 1-50: 1, and the molar ratio of the acid auxiliary agent to the palladium compound is 1-100: 1.

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