CN114522736A

CN114522736A - Method for heterogeneous hydroformylation reaction of vinyl ester compound

Info

Publication number: CN114522736A
Application number: CN202111374152.4A
Authority: CN
Inventors: 丁云杰; 王国庆; 严丽; 姜淼; 马雷
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2020-11-23
Filing date: 2021-11-19
Publication date: 2022-05-24
Anticipated expiration: 2041-11-19
Also published as: CN114522739B; CN114522735B; CN114522737A; CN114522738B; CN114522740B; CN114522736B; CN114522738A; CN114522735A; CN114522739A; CN114522740A; CN114522737B

Abstract

The invention belongs to the field of heterogeneous catalytic reaction processes, and particularly relates to a method for catalyzing a hydroformylation reaction of a vinyl ester compound by using a solid heterogeneous catalyst. The method comprises reacting a vinyl ester compound and CO/H in the presence of the solid heterogeneous catalyst₂The hydroformylation reaction is carried out in a reactor to synthesize a bifunctional aldehyde product. The method uses the novel solid heterogeneous catalyst, the reaction process and the device are simple, the catalyst has excellent reaction activity and stability, the separation cost of the catalyst and reactants and products is reduced, and the economic benefit of the hydroformylation reaction process of the vinyl ester compound is effectively improved. Hydroformylation of vinyl ester compoundsThe reaction product is an important intermediate for synthesizing high-value chemical dihydric alcohol, and the high-value chemical dihydric alcohol is prepared by adopting cheap and easily available vinyl ester compounds through a multiphase hydroformylation reaction, so that the method has important research significance and industrial application prospect.

Description

Method for heterogeneous hydroformylation reaction of vinyl ester compound

Technical Field

The invention belongs to the field of heterogeneous catalytic reaction processes, and particularly relates to a method for hydroformylation of vinyl ester compounds by using a solid heterogeneous catalyst.

Background

Hydroformylation refers to a reaction process in which an olefin, carbon monoxide and hydrogen are added with a hydrogen atom and a formyl group simultaneously on an olefin double bond under the action of a catalyst to generate two isomeric aldehydes having one more carbon atom than the original olefin, and the reaction is also named as oxo synthesis or Rowland reaction, and is one of important methods for the functionalization of the olefin double bond. The most important application of hydroformylation is the conversion of propylene to butyraldehyde, which is used to produce 2-ethylhexanol. For many years, the field has primarily studied hydroformylation of terminal olefins. However, in recent years there has been increasing interest in the hydroformylation of functionalized olefins to synthesize difunctional aldehydes.

Hydroformylation of vinyl ester compounds is a very important reaction because this route has wide application for the synthesis of commercially important products. For example, the products 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde from the hydroformylation of vinyl acetate are intermediates in the production of 1, 2-propanediol and 1, 3-propanediol. 1, 2-propanediol is used as a heat transfer fluid and antifreeze in the pharmaceutical and food industries, and also as a solvent in many chemical processes. 1, 3-propanediol, in turn, is a valuable chemical in the polyurethane, adhesive and resin industries. Lactic acid is a food material and can be obtained by the oxidative hydrolysis of 2-acetoxypropionaldehyde obtained by the hydroformylation of vinyl acetate. Asymmetric hydroformylation of vinyl acetate can also be used to synthesize chiral amino acids. Most of the hydroformylation reactions of vinyl ester compounds are carried out under homogeneous conditions, and the hydroformylation reaction of a heterogeneous catalytic system is less researched, and the problems of low activity, poor chemical or regioselectivity and the like exist.

In view of the above, efforts have been made to hydroformylate vinyl esters to obtain bifunctional aldehyde products having higher added values. For the hydroformylation reaction of vinyl ester compounds applied in the actual industry, a high-efficiency recyclable catalyst is developed, so that a green and clean reaction process suitable for large-scale production is developed, and the method is a main research direction in the field.

Disclosure of Invention

In view of the disadvantages of the prior art, the present invention aims to provide a hydroformylation process of vinyl ester compounds using a solid heterogeneous catalyst having excellent reactivity and stability, which can be easily implemented industrially.

To this end, the invention provides a process for the hydroformylation of vinyl ester compounds, which is characterized in that a solid heterogeneous catalyst is used, the catalyst consists of a metal component and an organic ligand polymer, wherein the metal component is one or more of metal Rh, Co, Ru, Ir or Pt, the organic ligand polymer is a polymer which is generated by one or more than two monomers of phosphine nitrogen ligand or phosphine ligand containing vinyl functional group through solvent thermal polymerization and has large specific surface area and hierarchical pore structure, the metal component forms a coordination bond with a P atom or a P and N atom in the organic ligand polymer skeleton, and is highly dispersed and stably present on the organic ligand polymer carrier, the method comprises subjecting a vinyl ester compound hydroformylation reaction to the synthesis of bifunctional aldehydes in a reactor in the presence of the solid heterogeneous catalyst.

In a preferred embodiment, the functional group olefin is selected from:

m is an integer from 0 to 6, n is an integer from 0 to 6, and X is one or more of F, Cl, Br and I.

In a preferred embodiment, the molar ratio of the vinyl ester based compound feedstock to the CO feedstock is from 1:1 to 1:200, the CO feedstock to the H feedstock₂The molar ratio of the raw materials is 1:1-1: 50.

In a preferred embodiment, the vinyl ester compound raw material is conveyed into the reaction system by a high-pressure pump, and the liquid hourly space velocity is 0.01-5h^-1(ii) a CO and H₂The raw material is fed in a gas form with a diameter, and the gas space velocity is 500-10000h^-1。

In a preferred embodiment, the reactor is a trickle bed or tank reactor.

In a preferred embodiment, the hydroformylation of vinyl ester compounds is carried out continuously or batchwise.

In a preferred embodiment, the reaction temperature of the hydroformylation of the vinyl ester compound is 333-523K, and the reaction pressure is 0.05-15 MPa.

In a preferred embodiment, the metal component comprises from 0.01 to 15.0% by weight of the total solid heterogeneous catalyst.

In a preferred embodiment, the phosphine ligand containing vinyl functional groups, or phosphine nitrogen ligand, is one or more selected from the group consisting of:

in a preferred embodiment, the specific surface area of the organic ligand polymer is 500-2200m²Per g, pore volume of 0.1-4.0cm³(ii)/g, the pore size distribution is 0.1-200.0 nm.

The inert gas atmosphere is one or more than two of argon, helium, nitrogen and neon.

In a preferred embodiment, when the reactor is a trickle bed, the hydroformylation of vinyl ester compounds is carried out continuously over the solid heterogeneous catalyst, and the liquid product formed continuously flows out of the reactor and is collected by a product collection tank at a temperature of-20 to 15 ℃; when the reactor is a tank reactor, the hydroformylation reaction of the vinyl ester compound is carried out intermittently, the generated liquid product is obtained by filtering and separating from the solid heterogeneous catalyst, and the obtained liquid product is further processed by rectification or flash evaporation to obtain a high-purity bifunctional aldehyde product.

The benefits of the present invention include, but are not limited to, the following: compared with the prior art, the method uses the novel solid heterogeneous catalyst, has simple reaction process and device, has excellent reaction activity and stability, reduces the separation cost of the catalyst, reactants and products, effectively improves the economic benefit of the hydroformylation reaction process of the vinyl ester compound, and has wide industrial application prospect.

Drawings

FIG. 1 is a reaction scheme for the hydroformylation of vinyl ester compounds carried out continuously according to the invention.

Detailed Description

In order to better illustrate the preparation method of the catalyst and the application thereof in the hydroformylation of vinyl ester compounds, the following examples of the preparation of some catalyst samples and the application thereof in the reaction process are given, but the present invention is not limited to the examples. Unless otherwise specifically stated, the contents and percentages in the present application are calculated as "mass".

Example 1

10.0 g of tris (4-vinylphenyl) ylphosphine were dissolved in 100ml of tetrahydrofuran under 298K and argon, 0.25 g of azobisisobutyronitrile, a free-radical initiator, was added to the solution and the mixture was stirred for 0.5 hour. And transferring the stirred solution into a hydrothermal autoclave, and carrying out solvothermal polymerization for 24h under the protection of 373K and argon. Cooling to room temperature after the polymerization, and removing the solvent in vacuum to obtain the porous organic polymer containing the triphenylphosphine. 0.0906 g of tris (triphenylphosphine) carbonylrhodium hydride were weighed out in 50ml of tetrahydrofuran solvent under 298K and argon atmosphere, 1.0 g of the above-prepared porous organic polymer containing triphenylphosphine was added and stirred for 24 hours. Subsequently, the solvent was evacuated under 333K temperature to obtain a solid heterogeneous catalyst in which the metal component was supported by the organic ligand polymer.

Adding the prepared solid heterogeneous catalyst into a trickle bed reactor, and introducing CO and H₂Gas mixture (CO: H)₂1:1, molar ratio), the vinyl acetate raw material is pumped into a reactor by a high-pressure metering pump to start reaction, and the vinyl acetate and CO/H₂The hydroformylation reaction temperature is 100 ℃, the reaction pressure is 4.1MPa, and the hourly space velocity of vinyl acetate liquid is 0.1h^-1And a CO/vinyl acetate molar ratio of 50. The liquid product was collected in a cold trap collection tank (-5 to 5 ℃). The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, using ethanol as an internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector.

The products are isomeric aldehyde 2-acetoxy propionaldehyde and normal aldehyde 3-acetoxy propionaldehyde.

The reaction process flow of the continuously performed hydroformylation reaction of the vinyl ester compound is shown in figure 1.

The reaction evaluation results are shown in Table 1.

Example 2

See example 1 for catalyst preparation except that 0.0312 grams of p-cymene ruthenium (ii) dichloride dimer was used in place of 0.0906 grams of tris (triphenylphosphine) carbonylrhodium hydride in the catalyst preparation, the catalyst preparation was otherwise identical to example 1.

Catalyst evaluation the reaction process was the same as in example 1, and the reaction evaluation results are shown in table 1.

Example 3

See example 1 for catalyst preparation except that 0.1001 grams of dicobalocatalyst were used in place of 0.0906 grams of tris (triphenylphosphine) rhodium carbonyl hydride in the catalyst preparation, the catalyst preparation was otherwise identical to example 1.

Example 4

The catalyst was prepared in the same manner as in example 1.

Adding the prepared solid heterogeneous catalyst into a trickle bed reactor, and introducing CO and H₂Gas mixture (CO: H)₂1:1), pumping vinyl acetate raw material into a reactor through a high-pressure metering pump to start reaction, and mixing vinyl acetate and CO/H₂The hydroformylation reaction temperature is 120 ℃, the reaction pressure is 4.1MPa, and the hourly space velocity of vinyl acetate liquid is 0.15h^-1The CO/vinyl acetate molar ratio was 75. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, using ethanol as an internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector, and the results of the reaction evaluations are shown in Table 1.

Example 5

The catalyst was prepared in the same manner as in example 1.

Adding the prepared solid heterogeneous catalyst into a trickle bed reactor, and introducing CO and H₂Gas mixture (CO: H)₂1:1), the vinyl acetate raw material is pumped into the reactor through a high-pressure metering pump to start the reaction, and the vinyl acetate and CO/H are mixed₂The hydroformylation reaction temperature is 140 ℃, the reaction pressure is 4.1MPa, and the hourly space velocity of vinyl acetate liquid is 0.2h^-1CO/vinyl acetate molar ratio of 75. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, using ethanol as an internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector, and the results of the reaction evaluations are shown in Table 1.

Example 6

The catalyst was prepared in the same manner as in example 1.

Adding the prepared solid heterogeneous catalyst into a trickle bed reactor, and introducing CO and H₂Gas mixture (CO: H)₂1:1), ethylene propionateEster raw material is pumped into a reactor through a high-pressure metering pump to start reaction, and vinyl propionate and CO/H₂The hydroformylation reaction temperature is 120 ℃, the reaction pressure is 4.1MPa, and the hourly space velocity of the vinyl propionate liquid is 0.1h^-1CO/vinyl propionate molar ratio of 50. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, with ethanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector, and the results of the reaction evaluations are shown in Table 1.

Example 7

The catalyst was prepared in the same manner as in example 1.

Adding the prepared solid heterogeneous catalyst into a trickle bed reactor, and introducing CO and H₂Gas mixture (CO: H)₂1:1), pumping the raw material of vinyl butyrate into a reactor through a high-pressure metering pump to start reaction, and mixing the vinyl butyrate and CO/H₂The hydroformylation reaction temperature is 120 ℃, the reaction pressure is 4.1MPa, and the hourly space velocity of vinyl butyrate liquid is 0.1h^-1CO/vinyl butyrate in a molar ratio of 50. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, using ethanol as an internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector, and the results of the reaction evaluations are shown in Table 1.

Example 8

The catalyst was prepared in the same manner as in example 1.

Adding the prepared solid heterogeneous catalyst into a trickle bed reactor, and introducing CO and H₂Gas mixture (CO: H)₂1:1), pumping the raw material of vinyl chloroformate into a reactor by a high-pressure metering pump to start reaction, and mixing the vinyl chloroformate with CO/H₂The hydroformylation reaction temperature is 120 ℃, the reaction pressure is 4.1MPa, and the hourly space velocity of the vinyl chloroformate liquid is 0.1h^-1CO/vinyl chloroformate molar ratio of 50. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, using ethanol as an internal standard. The reaction tail gas is provided with Porapak-HP-7890N gas chromatography on QS column and TCD detector was performed on-line and the results of the reaction evaluations are shown in Table 1.

Example 9

The catalyst was prepared in the same manner as in example 1.

0.043 g of the solid heterogeneous catalyst prepared in example 1 was placed in an autoclave reactor, 5mmol of vinyl acetate and 4ml of toluene solvent were added in sequence, the reactor was closed, and CO/H was charged₂Gas mixture (CO: H)₂1:1), the pressure of the autoclave system is increased to 4.1MPa, the temperature is slowly increased to 120 ℃ by a temperature controller, and the reaction is carried out for 8 h. After the reaction is finished, cooling the reaction kettle to room temperature, slowly discharging excessive reaction gas, filtering to separate out the catalyst, adding the obtained product into ethanol as an internal standard, and performing HP-7890N gas chromatography analysis by using an HP-5 capillary column and an FID detector, wherein the reaction evaluation result is shown in Table 1.

Example 10

The catalyst was prepared in the same manner as in example 1.

0.043 g of the solid heterogeneous catalyst prepared in example 1 was placed in an autoclave reactor, 5mmol of vinyl acetate and 4ml of toluene solvent were added in sequence, the reactor was closed, and CO/H was charged₂Gas mixture (CO: H)₂1:1), the pressure of the autoclave system is increased to 4.1MPa, the temperature is slowly increased to 140 ℃ by a temperature controller, and the reaction is carried out for 8 h. After the reaction is finished, cooling the reaction kettle to room temperature, slowly discharging excessive reaction gas, filtering to separate out the catalyst, adding the obtained product into ethanol as an internal standard, and performing HP-7890N gas chromatography analysis by using an HP-5 capillary column and an FID detector, wherein the reaction evaluation result is shown in Table 1.

Example 11

See example 1 for catalyst preparation except that 10 grams of L9 ligand monomer was used in place of 10 grams of tris (4-vinylphenyl) phosphine in the catalyst preparation, the catalyst preparation was otherwise identical to example 1.

Example 12

See example 1 for catalyst preparation except that 10 grams of L11 ligand monomer was used in place of 10 grams of tris (4-vinylphenyl) phosphine in the catalyst preparation, the catalyst preparation was otherwise identical to example 1.

Example 13

See example 1 for catalyst preparation except that 10 grams of L12 ligand monomer was used in place of 10 grams of tris (4-vinylphenyl) phosphine in the catalyst preparation, the catalyst preparation was otherwise identical to example 1.

Example 14

See example 1 for catalyst preparation except that 10 grams of L15 ligand monomer was used in place of 10 grams of tris (4-vinylphenyl) phosphine in the catalyst preparation, the catalyst preparation was otherwise identical to example 1.

TABLE 1 evaluation results of hydroformylation reaction of vinyl ester compounds

	Conversion/% of vinyl ester compounds	Ratio of difference to ratio
			Example 1	85	94
Example 2	<1	—
			Example 3	<1	—
Example 4	70	99
			Example 5	55	≥99
Example 6	76	97
			Example 7	73	98
Example 8	79	97
			Example 9	98	98
Example 10	99	≥99
			Example 11	87	9
Example 12	89	5
			Example 13	86	1.3
Example 14	90	0.8

The results show that: example 2 and example 3 comparative example 1 demonstrates the highest Rh activity and very low Ru and Co activity in the catalytic system. Examples 4, 5, 6, 7 and 8 all demonstrated that the polymer formed from the L1 ligand monomer produced a majority of isomeric aldehyde 2-acetoxypropionaldehyde and very little normal aldehyde 3-acetoxypropionaldehyde when the reaction was carried out. Examples 9 and 10 are comparative tests conducted in an autoclave, and the positive and negative results are similar to those of the fixed bed. The results of examples 11, 12, 13 and 14, which use L9, L11, L12 and L15 ligands, respectively, show that different ligands can significantly change the product difference ratio, and greatly improve the selectivity of normal aldehyde 3-acetoxy propionaldehyde.

The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims

1. A method for hydroformylation of vinyl ester compounds is characterized in that:

reacting a vinyl ester compound with CO and H in the presence of the solid heterogeneous catalyst₂Performing the hydroformylation reaction in a reactor to synthesize a bifunctional aldehyde product;

the vinyl ester compound is selected from one or more than two of the following compounds:

m is an integer of 0 to 6, n is an integer of 0 to 6, and X is one or more of F, Cl, Br and I.

2. The method as claimed in claim 1, wherein the hydroformylation reaction temperature of the vinyl ester compound is 333-.

3. The process according to claim 1 or 2, wherein the vinyl ester feedstock is fed into the reactor at a liquid hourly space velocity of from 0.01 to 5h^-1(preferably 0.5-2 h)^-1More preferably 0.7-1.7h^-1) (ii) a CO and H₂The mixed gas raw material is fed in a gas form with a diameter, and the gas space velocity is 500-10000h^-1(preferably 1000-5000 h)^-1More preferably 1500-^-1)。

4. The process according to claim 1 or 3, wherein the molar ratio of the vinyl ester based compound feedstock to the CO feedstock is from 1:1 to 1:200 (preferably from 1:10 to 1:150, more preferably from 1:30 to 1:120), and the CO feedstock to the H feedstock is₂The molar ratio of the starting materials is from 1:0.1 to 1:50 (preferably from 1:0.2 to 1:10, more preferably from 1:0.5 to 1: 7).

5. The process according to claim 1 or 3, wherein the reactor is a batch reactor or a trickle bed reactor in a continuous mode;

when the reactor is a trickle bed, the hydroformylation of vinyl ester compounds is continuously carried out on the solid heterogeneous catalyst, and the generated liquid product continuously flows out of the reactor and is collected by a product collecting tank at the temperature of-20-15 ℃;

when the reactor is a kettle reactor, the hydroformylation reaction of the vinyl ester compound is carried out intermittently, the generated liquid product is obtained by filtering and separating from the solid heterogeneous catalyst, and the obtained liquid product is further processed by rectification or flash evaporation to obtain the high-purity bifunctional aldehyde product.

6. The method according to claim 1, wherein the solid heterogeneous catalyst used consists of a metal component and an organic ligand polymer, wherein the metal component is one or more than two of metals Rh, Co, Ru, Ir or Pt, and the organic ligand polymer is a porous polymer generated by solvent thermal polymerization of one or more than two monomers containing vinyl functionalized phosphine nitrogen ligands or phosphine ligands; the metal component is present in an amount of 0.01 to 15.0% (preferably 0.01 to 5.0%, more preferably 0.05 to 3.0%) by weight based on the total weight of the solid heterogeneous catalyst.

7. The method of claim 6, wherein: the phosphine nitrogen ligand or the phosphine ligand containing vinyl functional groups is one or more than two of the following components:

8. the method according to claim 6 or 7, characterized in that the solvent thermal polymerization process:

a) adding one or more of phosphine nitrogen ligand or phosphine ligand, adding or not adding a cross-linking agent, and then adding a free radical initiator into an organic solvent under 273-333K (preferably 298-323K) and inert gas atmosphere, mixing, and stirring the mixture for 0.1-96 h (preferably 0.1-5 h);

b) transferring the mixed solution prepared in the step a) into a synthesis high-pressure autoclave, standing for 1-100h (preferably 6-48h) for polymerization reaction by adopting a solvent thermal polymerization method under the atmosphere of inert gas at 333K-473K (preferably 373-423K), and obtaining a phosphine nitrogen-containing porous organic polymer;

c) vacuum-pumping the solvent from the polymer obtained in the step b) at room temperature to obtain an organic polymer containing naked P or organic polymers containing naked P and N, which has a hierarchical pore structure, namely the carrier of the heterogeneous catalyst;

d) placing the organic ligand polymer in a solvent containing an active metal component, stirring for 0.5-100h (preferably 6-48h) under the protection of 273-;

the organic solvent in the step a) is one or more than two of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or trichloromethane; the cross-linking agent is one or more than two of styrene, ethylene, propylene, divinyl benzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3, 5-triethylalkynyl benzene; the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile;

in the case of adding the crosslinking agent to the ligand in the step a), the molar ratio of the ligand to the crosslinking agent is 0.01: 1-10:1 (preferably 1:1-5:1), the molar ratio of the ligand to the radical initiator is 250: 1-10:1 (preferably 80:1-10:1), and the concentration of the ligand in the organic solvent before polymerization into the organic polymer is in the range of 0.01-500g/L (preferably 10-200 g/L).