[go: up one dir, main page]

CN111318308A - Catalyst composition, application thereof and method for hydroformylation of vinyl acetate - Google Patents

Catalyst composition, application thereof and method for hydroformylation of vinyl acetate Download PDF

Info

Publication number
CN111318308A
CN111318308A CN201811544467.7A CN201811544467A CN111318308A CN 111318308 A CN111318308 A CN 111318308A CN 201811544467 A CN201811544467 A CN 201811544467A CN 111318308 A CN111318308 A CN 111318308A
Authority
CN
China
Prior art keywords
vinyl acetate
catalyst composition
formula
independently selected
hydroformylation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811544467.7A
Other languages
Chinese (zh)
Inventor
徐向亚
赵思源
冯华升
姜健准
刘东兵
张明森
刘红梅
冯静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201811544467.7A priority Critical patent/CN111318308A/en
Publication of CN111318308A publication Critical patent/CN111318308A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the field of vinyl acetate hydroformylation, and discloses a catalyst composition, application thereof and a vinyl acetate hydroformylation method. The catalyst composition contains a rhodium complex and a phosphine ligand compound, wherein the phosphine ligand compound has a structure shown in a formula (1), and in the formula (1), R1、R2And R3Each independently selected from substituted or unsubstituted C1‑C20Alkyl groups of (a); and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1‑C20Alkyl, halogen, C1‑C10Alkoxy, hydroxy, carboxy and aldehyde ofAt least one of the groups; the catalyst composition provided by the invention can improve the conversion rate of vinyl acetate and the selectivity of 2-acetoxy propionaldehyde.

Description

Catalyst composition, application thereof and method for hydroformylation of vinyl acetate
Technical Field
The invention relates to the field of vinyl acetate hydroformylation, in particular to a catalyst composition and application thereof, and a method for hydroformylation of vinyl acetate.
Background
Vinyl acetate and synthesis gas (mixed gas of carbon monoxide and hydrogen) are subjected to hydroformylation reaction under the action of an olefin hydroformylation catalyst to generate 3-acetoxy propionaldehyde and 2-acetoxy propionaldehyde, products of the 3-acetoxy propionaldehyde and the 2-acetoxy propionaldehyde react with hydrogen under the action of an aldehyde group hydrogenation catalyst to generate 3-acetoxy propanol and 2-acetoxy propanol, and hydrolysis is carried out under the action of an ester hydrolysis catalyst to generate 1, 3-propylene glycol and 1, 2-propylene glycol. Or the products of 3-acetoxy propionaldehyde and 2-acetoxy propionaldehyde generate important industrial products such as lactic acid, 3-hydroxypropionic acid and the like under the action of an oxidizing agent. Regioselectivity of the product in the hydroformylation of vinyl acetate is a difficult point of investigation.
The selectivity of 2-levulinic aldehyde obtained by combining a chiral ligand with rhodium metal is 96% as published in a large body of literature, e.g. p.j.thomas, Org Lett, 2007; the metallo-organic catalyst published by Williams D B on Organometallics, the data published by Aasif a D on Catalysis Commun in 2010, etc. know that the main product of the hydroformylation of vinyl acetate catalyzed by the rhodium complex catalyst is 2-acetoxypropionaldehyde. Because 2-acetoxy propionaldehyde has a chiral center, the current research situation is that scientists all use rhodium catalyst to cooperate with some chiral ligands to catalyze vinyl acetate hydroformylation to obtain single chiral 2-acetoxy propionaldehyde, and further perform oxidative hydrolysis to generate products such as L-lactic acid.
In the prior art, in the process of vinyl acetate hydroformylation, the selectivity of singly generating 2-acetoxy propionaldehyde is poor, and how to obtain higher vinyl acetate conversion rate and higher 2-acetoxy propionaldehyde selectivity is a problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to overcome the problems of low conversion rate of vinyl acetate and low selectivity of 2-acetoxy propionaldehyde in the prior art, and provides a catalyst composition, application of the catalyst composition in catalyzing vinyl acetate hydroformylation and a method for catalyzing vinyl acetate hydroformylation.
In order to achieve the above object, a first aspect of the present invention provides a catalyst composition comprising a rhodium complex and a phosphine ligand compound, wherein the phosphine ligand compound has a structure represented by formula (1):
Figure BDA0001909011960000021
wherein, in the formula (1),
R1、R2and R3Each independently selected from substituted or unsubstituted C1-C20Alkyl groups of (a);
and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C20Alkyl, halogen, C1-C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
In a second aspect, the invention provides the use of a catalyst composition as described above in the catalysis of the hydroformylation of vinyl acetate.
In a third aspect, the present invention provides a method for hydroformylation of vinyl acetate, the method comprising: in the presence of the catalyst composition, vinyl acetate and synthesis gas are subjected to contact reaction.
By adopting the technical scheme, the invention provides the catalyst composition, the application of the catalyst composition in catalyzing vinyl acetate hydroformylation and the method for catalyzing vinyl acetate hydroformylation, and the catalyst composition can improve the conversion rate of vinyl acetate to more than 85% and the selectivity of 2-acetoxy propionaldehyde to more than 95% under a mild condition.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a catalyst composition comprising a rhodium complex and a phosphine ligand compound, wherein the phosphine ligand compound has a structure represented by formula (1),
Figure BDA0001909011960000031
wherein, in the formula (1),
R1、R2and R3Each independently selected from substituted or unsubstituted C1-C20Alkyl groups of (a);
and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C20Alkyl, halogen, C1-C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
In the present invention, the term "C" is used1-C20The "alkyl group" in (1) represents an alkyl group having 1 to 20 carbon atoms in total, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, and isooctyl.
In the present invention, the term "C" is used1-C10The "alkoxy group" of (a) represents an alkoxy group having 1 to 10 carbon atoms in total, and may be, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, an n-pentyloxy group, an isopentyloxy group, or the like.
Preferably, in formula (1), R1、R2And R3Each independently selected from substituted or unsubstituted C1-C10Alkyl groups of (a); and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C10Alkyl, halogen, C1-C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde group of (A)
In the present invention, the term "C" is used1-C10The "alkyl group" in (1) represents an alkyl group having 1 to 10 carbon atoms in total, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, and isooctyl.
Preferably, in formula (1), R1、R2And R3Each independently selected from substituted or unsubstituted C1-C6Alkyl groups of (a); and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C6Alkyl, halogen, C1-C6Alkoxy and hydroxy ofAt least one of a group, a carboxyl group and an aldehyde group.
In the present invention, the term "C" is used1-C6The "alkyl group" in (1) represents an alkyl group having 1 to 6 carbon atoms in total, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, and isohexyl groups.
In the present invention, the term "C" is used1-C6The "alkoxy group" of (a) represents an alkoxy group having 1 to 6 carbon atoms in total, and may be, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, an n-pentyloxy group, an isopentyloxy group, or the like.
Preferably, in formula (1), R1、R2And R3Each independently selected from substituted or unsubstituted C1-C3Alkyl groups of (a); and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C3Alkyl, halogen, C1-C3At least one of alkoxy groups of (a).
In the present invention, the term "C" is used1-C3The "alkyl group" in (1) represents an alkyl group having 1 to 3 carbon atoms in total, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or the like.
In the present invention, the term "C" is used1-C3The "alkoxy group" of (b) represents an alkoxy group having 1 to 3 carbon atoms in total, and may be, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group or the like.
According to a preferred embodiment of the present invention, in formula (1), R1、R2And R3The same is true.
In the present invention, it is particularly preferable that the phosphine ligand compound is a compound represented by formula (2) and/or a compound represented by formula (3):
Figure BDA0001909011960000051
in the present invention, the phosphine ligand compound may be carried out according to the following methodPreparation: reacting ROH with PCl3Carrying out a contact reaction to obtain the phosphine ligand compound;
wherein R is selected from R1、R2And R3At least one of, and R1、R2And R3Are as defined as referred to in the phosphine ligand compound.
Preferably, ROH is reacted with PCl3The molar ratio of the compound (b) used is 1: (4-6).
Preferably, the conditions under which the contact reaction is carried out include: the temperature is 60-100 ℃; the time is 1-3 h.
Specifically, the preparation process of the phosphine ligand compound can be as follows: ROH was added to the reactor under nitrogen atmosphere, and then PCl was added dropwise with stirring3After the dripping is finished, the temperature is raised to 60-100 ℃ for reaction for 1-3h, wherein ROH and PCl3The molar ratio of the compound (b) used is 1: (4-6).
In the present invention, the progress of the reaction can be monitored by chromatography. After the reaction is completed, the resulting product may be subjected to a post-treatment by various post-treatment methods conventionally used in the art. Methods of such post-processing include, but are not limited to: extraction, recrystallization, washing, drying, filtration and the like. The present invention is not described in detail herein, and the post-processing methods mentioned in the embodiments are only for illustrative purposes, and do not indicate that they are necessary operations, and those skilled in the art may substitute other conventional methods.
In the present invention, the rhodium complex may be commercially available. Preferably, the rhodium complex is selected from at least one of triphenylphosphine carbonyl rhodium acetylacetonate, dicarbonyl rhodium acetylacetonate and triphenylphosphine rhodium hydride.
In order to further improve the conversion rate of vinyl acetate and the selectivity of 2-acetoxy propionaldehyde, the content molar ratio of the rhodium complex compound to the phosphine ligand compound is preferably 1 (1-10). More preferably, the content molar ratio of the rhodium complex to the phosphine ligand compound is 1 (1-5).
In a second aspect, the invention provides the use of a catalyst composition according to the invention for the catalytic hydroformylation of vinyl acetate.
The catalyst composition provided by the invention can improve the conversion rate of vinyl acetate to more than 85% and improve the selectivity of 2-acetoxy propionaldehyde to more than 95% when being applied to the catalysis of vinyl acetate hydroformylation.
In a third aspect, the present invention provides a method for hydroformylation of vinyl acetate, the method comprising: in the presence of the catalyst composition, vinyl acetate and synthesis gas are subjected to contact reaction.
Preferably, the conditions under which the contact reaction is carried out include: the temperature is 80-120 ℃; the pressure is 3-6 MPa.
Preferably, the molar ratio of vinyl acetate to the rhodium complex is 1 (0.0001-0.01).
In the present invention, CO and H in the synthesis gas2The content molar ratio of (0.1-10) is preferably 1; more preferably (0.2-5): 1.
According to a preferred embodiment of the present invention, the contact reaction is carried out in the presence of a solvent.
Preferably, the solvent is selected from C5-C20Aliphatic hydrocarbon of C6-C12Aromatic hydrocarbon of (2), C5-C20Ether of (C)5-C20At least one of the alcohols of (a). More preferably, the solvent is selected from C5-C10Aliphatic hydrocarbon of C6-C10Aromatic hydrocarbon of (2), C5-C10Ether of (C)5-C10At least one of the alcohols of (a). Further preferably, the solvent is at least one selected from the group consisting of n-hexane, cyclohexane, n-heptane, benzene, toluene, 1, 3-xylene, 1, 4-xylene, 1,3, 5-trimethylbenzene, naphthalene, methyl t-butyl ether, isopropyl ether and isoprene glycol.
Preferably, the volume ratio of the solvent to vinyl acetate is (0.01-10):1, more preferably (0.01-8): 1.
According to another preferred embodiment of the invention, the contact reaction is carried out under the solvent-free condition, so that the use and recovery of a solvent in the existing vinyl acetate hydroformylation reaction process can be omitted, and the resource waste is avoided to a certain extent.
The present invention will be described in detail below by way of examples. In the following examples, various materials used are commercially available without specific mention.
Rhodium acetylacetonate dicarbonyl and rhodium acetylacetonate triphenylphosphine carbonyl are available from carbofuran corporation.
The reaction solution is analyzed by gas chromatography, and is quantified by an internal standard method, and the conversion rate of the vinyl acetate and the selectivity of the 3-acetoxy propionaldehyde and the 2-acetoxy propionaldehyde are calculated.
The vinyl acetate conversion was calculated according to the following formula:
Figure BDA0001909011960000071
the selectivity to aldehyde is calculated as follows:
Figure BDA0001909011960000072
the selectivity to 3-acetoxypropionaldehyde was calculated as follows:
Figure BDA0001909011960000073
the selectivity to 2-acetoxypropionaldehyde was calculated as follows:
Figure BDA0001909011960000074
preparation example 1
A process for producing a compound represented by the formula (2):
Figure BDA0001909011960000075
vacuumizing a 50L reaction kettle, introducing nitrogen for three times, adding 24.2mol of methanol, stirring, dropwise adding 114.7mol of phosphorus trichloride into the reaction kettle from a head tank, heating to 80 ℃ after 1 hour of addition, and carrying out reflux reaction for 2 hours. The reaction produced about 1800L of HCl gas, which was absorbed in a hydrochloric acid absorber. After the reaction is finished, the temperature is reduced to 40 ℃, phosphorus trichloride is decompressed and steamed to a phosphorus trichloride elevated tank, the phosphorus trichloride elevated tank is recycled, the distillation loss is estimated to be 0.5 liter, and a product is separated to obtain the compound shown in the formula (2).
Yield: 53 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 3.42(s, 9H, 3CH 3).
Mass spectrum: [ M + ] 124.7612.
Preparation example 2
A process for producing a compound represented by the formula (3):
Figure BDA0001909011960000081
the procedure of preparation example 1 was followed, except that methanol was replaced with an equimolar amount of ethanol, to obtain a compound represented by formula (3).
Yield: 66 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 1.25(t, J ═ 6.2Hz, 9H, 3CH3)3.42(q, J ═ 4.7Hz, 6H, 3CH 2).
Mass spectrum: [ M + ] 166.0912.
Example 1
64.88mmol of vinyl acetate as a raw material for hydroformylation, 44mL of cyclohexane as a solvent, 0.025mmol of dicarbonylrhodium acetylacetonate and 0.063mmol of a compound represented by the formula (2) as a catalyst were charged in a 100mL autoclave, and the autoclave was sealed. Replacement with nitrogen three times, with syngas (CO: H)2The volume ratio is 1: 1) replacing for three times, pressurizing to 4MPa by using synthesis gas, heating to the reaction temperature of 100 ℃, and starting hydroformylation. The consumption of synthesis gas by the reaction is indicated by the change in pressure in the gas storage tank until no more gas is consumed as the end of the reaction. The reaction vessel was cooled to room temperature (25 ℃ C.), unreacted gas was discharged, and after 3 times of replacement with nitrogen, the reaction vessel was opened, and the composition of the reaction product was analyzed by gas chromatography, and quantitative determination was carried out by an internal standard method, the results being shown in Table 1.
Example 2
In a 100mL autoclave, 6 was added4.88mmol of vinyl acetate as a raw material for hydroformylation, 44mL of toluene as a solvent, 0.025mmol of acetylacetonatocarbonyltriphenylphosphine rhodium and 0.05mmol of the compound represented by the formula (2) as a catalyst, and sealing the reaction vessel. Replacement with nitrogen three times, with syngas (CO: H)2The volume ratio is 1: 1) replacing for three times, pressurizing to 5MPa by using synthesis gas, heating to the reaction temperature of 120 ℃, and starting hydroformylation. The consumption of synthesis gas by the reaction is indicated by the change in pressure in the gas storage tank until no more gas is consumed as the end of the reaction. The reaction kettle was cooled to room temperature, unreacted gas was discharged, and after 3 times of replacement with nitrogen, the reaction kettle was opened, and the composition of the reaction product was analyzed by gas chromatography, and the internal standard method was used for quantification, and the results are shown in table 1.
Example 3
519mmol of vinyl acetate as a raw material for hydroformylation, 0.2mmol of rhodium acetylacetonate dicarbonyl and 0.5mmol of a compound represented by the formula (2) as a catalyst were charged in a 100mL autoclave, and the autoclave was sealed. Replacement with nitrogen three times, with syngas (CO: H)2The volume ratio is 1: 1) replacing for three times, pressurizing to 4.5MPa by using synthesis gas, heating to the reaction temperature of 100 ℃, and starting hydroformylation. The consumption of synthesis gas by the reaction is indicated by the change in pressure in the gas storage tank until no more gas is consumed as the end of the reaction. The reaction kettle was cooled to room temperature, unreacted gas was discharged, and after 3 times of replacement with nitrogen, the reaction kettle was opened, and the composition of the reaction product was analyzed by gas chromatography, and the internal standard method was used for quantification, and the results are shown in table 1.
Example 4
An experiment was performed in the same manner as in example 1, except that the compound represented by formula (2) was replaced with an equimolar amount of the compound represented by formula (3). The results are shown in Table 1.
Example 5
An experiment was conducted in the same manner as in example 1 except that the compound represented by the formula (2) was added in an amount of 0.01 mmol. The results are shown in Table 1.
Example 6
An experiment was conducted in the same manner as in example 1 except that the compound represented by the formula (2) was added in an amount of 0.143 mmol. The results are shown in Table 1.
Comparative example 1
An experiment was carried out in the same manner as in example 1 except that the compound represented by the formula (2) was not added during the experiment. The results are shown in Table 1.
Comparative example 2
An experiment was carried out in the same manner as in example 1 except that the compound represented by the formula (2) was replaced with tributylphosphine in an equimolar amount. The results are shown in Table 1.
TABLE 1
Figure BDA0001909011960000101
The results in table 1 show that the catalyst composition provided by the present invention can improve the conversion rate of vinyl acetate to 85% or more and the selectivity of 2-acetoxypropionaldehyde to 95% or more when used for the hydroformylation of vinyl acetate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A catalyst composition comprising a rhodium complex and a phosphine ligand compound, wherein the phosphine ligand compound has a structure represented by the formula (1),
Figure FDA0001909011950000011
wherein, in the formula (1),
R1、R2and R3Each independently selected from substituted or unsubstituted C1-C20Alkyl groups of (a);
and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C20Alkyl, halogen, C1-C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
2. The catalyst composition according to claim 1, wherein, in formula (1), R1、R2And R3Each independently selected from substituted or unsubstituted C1-C6Alkyl groups of (a); and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C6Alkyl, halogen, C1-C6At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups;
preferably, in formula (1), R1、R2And R3Each independently selected from substituted or unsubstituted C1-C3Alkyl groups of (a); and R is1、R2And R3Wherein the substituents optionally present are each independently selected from C1-C3Alkyl, halogen, C1-C3At least one of alkoxy groups of (a).
3. The catalyst composition according to claim 1 or 2, wherein, in formula (1), R1、R2And R3The same is true.
4. The catalyst composition according to any one of claims 1-3, wherein the phosphine ligand compound is a compound of formula (2) and/or a compound of formula (3):
Figure FDA0001909011950000021
5. the catalyst composition of any one of claims 1-4, wherein the rhodium complex is selected from at least one of triphenylphosphine carbonyl rhodium acetylacetonate, dicarbonyl rhodium acetylacetonate, and triphenylphosphine rhodium hydride;
preferably, the content molar ratio of the rhodium complex to the phosphine ligand compound is 1 (1-10), preferably 1 (1-5).
6. Use of a catalyst composition according to any one of claims 1 to 5 for the catalysis of the hydroformylation of vinyl acetate.
7. A method for hydroformylation of vinyl acetate, comprising: the vinyl acetate is subjected to a contact reaction with synthesis gas in the presence of the catalyst composition according to any one of claims 1 to 5.
8. The method of claim 7, wherein the conditions under which the contact reaction is carried out comprise: the temperature is 80-120 ℃; the pressure is 3-6 MPa.
9. The process of claim 7 or 8, wherein the molar ratio of vinyl acetate to the rhodium complex is 1 (0.0001-0.01);
preferably, the syngas is CO and H2The content molar ratio of (B)/(A) is (0.1-10):1, more preferably (0.2-5): 1.
10. The process according to any one of claims 7 to 9, wherein the contact reaction is carried out in the presence of a solvent;
preferably, the solvent is selected from C5-C20Aliphatic hydrocarbon of C6-C12Aromatic hydrocarbon of (2), C5-C20Ether of (C)5-C20At least one of the alcohols of (a);
preferably, the solvent is selected from C5-C10Aliphatic hydrocarbon of C6-C10Aromatic hydrocarbon of (2), C5-C10Ether of (C)5-C10At least one of the alcohols of (a);
preferably, the solvent is at least one selected from the group consisting of n-hexane, cyclohexane, n-heptane, benzene, toluene, 1, 3-xylene, 1, 4-xylene, 1,3, 5-trimethylbenzene, naphthalene, methyl t-butyl ether, isopropyl ether and isoprene glycol.
11. The method of claim 10, wherein the volume ratio of solvent to vinyl acetate is (0.01-10):1, preferably (0.01-8): 1.
12. The method of any one of claims 7-9, wherein the contacting reaction is performed in the absence of a solvent.
CN201811544467.7A 2018-12-17 2018-12-17 Catalyst composition, application thereof and method for hydroformylation of vinyl acetate Pending CN111318308A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811544467.7A CN111318308A (en) 2018-12-17 2018-12-17 Catalyst composition, application thereof and method for hydroformylation of vinyl acetate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811544467.7A CN111318308A (en) 2018-12-17 2018-12-17 Catalyst composition, application thereof and method for hydroformylation of vinyl acetate

Publications (1)

Publication Number Publication Date
CN111318308A true CN111318308A (en) 2020-06-23

Family

ID=71166199

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811544467.7A Pending CN111318308A (en) 2018-12-17 2018-12-17 Catalyst composition, application thereof and method for hydroformylation of vinyl acetate

Country Status (1)

Country Link
CN (1) CN111318308A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960949A (en) * 1988-12-22 1990-10-02 Eastman Kodak Company Low pressure rhodium catalyzed hydroformylation of olefins
US6020441A (en) * 1996-05-31 2000-02-01 Basf Aktiengesellschaft Hydroformylation of ethylenically unsaturated polymers in aqueous dispersion
CN106550597A (en) * 2015-07-13 2017-03-29 Lg化学株式会社 Carbon monoxide-olefin polymeric comprising the part based on phosphorus and the hydroformylation process using the carbon monoxide-olefin polymeric
CN106565476A (en) * 2015-10-10 2017-04-19 中国石油化工股份有限公司 Method for hydroformylation of vinyl acetate
CN106565485A (en) * 2015-10-10 2017-04-19 中国石油化工股份有限公司 Vinylacetate hydroformylation method
US20180290132A1 (en) * 2016-07-08 2018-10-11 Lg Chem, Ltd. HYDROFORMYLATION CATALYST, COMPOSITION INCLUDING HYDROFORMYLATION CATALYST, AND METHOD OF PREPARING ALDEHYDE USING HYDROFORMYLATION CATALYST (As Amended)

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960949A (en) * 1988-12-22 1990-10-02 Eastman Kodak Company Low pressure rhodium catalyzed hydroformylation of olefins
US6020441A (en) * 1996-05-31 2000-02-01 Basf Aktiengesellschaft Hydroformylation of ethylenically unsaturated polymers in aqueous dispersion
CN106550597A (en) * 2015-07-13 2017-03-29 Lg化学株式会社 Carbon monoxide-olefin polymeric comprising the part based on phosphorus and the hydroformylation process using the carbon monoxide-olefin polymeric
CN106565476A (en) * 2015-10-10 2017-04-19 中国石油化工股份有限公司 Method for hydroformylation of vinyl acetate
CN106565485A (en) * 2015-10-10 2017-04-19 中国石油化工股份有限公司 Vinylacetate hydroformylation method
US20180290132A1 (en) * 2016-07-08 2018-10-11 Lg Chem, Ltd. HYDROFORMYLATION CATALYST, COMPOSITION INCLUDING HYDROFORMYLATION CATALYST, AND METHOD OF PREPARING ALDEHYDE USING HYDROFORMYLATION CATALYST (As Amended)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
AASIF A. DABBAWALA ET AL.: "Regioselective hydroformylation of vinyl acetate catalyzed by rhodium complex of naphthyl-based monodentate bulky phosphine and phosphite ligands", 《APPLIED CATALYSIS A: GENERAL》 *

Similar Documents

Publication Publication Date Title
Prechtl et al. Direct coupling of alcohols to form esters and amides with evolution of H 2 using in situ formed ruthenium catalysts
Ahlsten et al. Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
Hamers et al. Hydroaminomethylation of n‐Alkenes in a Biphasic Ionic Liquid System
CN106565476B (en) A kind of method of vinylacetate hydroformylation
EP2678304B1 (en) Hydrogenation of dienals with rhodium complexes under carbon monoxide free atmosphere
Zhang et al. Copper‐Dipyridylphosphine‐Polymethylhydrosiloxane: A Practical and Effective System for the Asymmetric Catalytic Hydrosilylation of Ketones
EP1339491B1 (en) Phosphonite ligands, catalyst compositions and hydroformylation process utilizing same
CN114057558A (en) Synthetic method, catalytic system and application of 3,5, 5-trimethylhexanal
Zhang et al. Transfer hydrogenation of aldehydes catalyzed by silyl hydrido iron complexes bearing a [PSiP] pincer ligand
Boogaerts et al. High chemo and regioselective formation of alcohols from the hydrocarbonylation of alkenes using cooperative ligand effects
CN111320653B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
Bruneau et al. Ruthenium catalysts for selective nucleophilic allylic substitution
US9902673B2 (en) Methods for producing butanol
JP6869441B2 (en) Production of BDO by hydroformylation of glycerin allyl alcohol
CN111320649B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN111320655B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
EP0102341B1 (en) Improved hydroformylation process to prepare glycol aldehydes
Xu et al. Reductive Cleavage of C—O Bond in Model Compounds of Lignin
CN111318308A (en) Catalyst composition, application thereof and method for hydroformylation of vinyl acetate
CN111318307A (en) Catalyst composition, application thereof and method for hydroformylation of vinyl acetate
CN111320654B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN106607093B (en) Carbon monoxide-olefin polymeric and application thereof
CN111320652B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN110372513B (en) Vinyl acetate hydroformylation method
CA1157047A (en) Hydroformylation of olefinically unsaturated compounds

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200623