CN111320649A - Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method - Google Patents

Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method Download PDF

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CN111320649A
CN111320649A CN201811544455.4A CN201811544455A CN111320649A CN 111320649 A CN111320649 A CN 111320649A CN 201811544455 A CN201811544455 A CN 201811544455A CN 111320649 A CN111320649 A CN 111320649A
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phosphine ligand
substituted
vinyl acetate
ligand compound
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CN111320649B (en
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徐向亚
冯华升
赵思源
张明森
冯静
刘红梅
姜健准
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • 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
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, 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
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    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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Abstract

The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application thereof, and a vinyl acetate hydroformylation method. The phosphine ligand compound has a structure shown in a formula (1); wherein A is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstituted C1‑C20Alkyl, substituted or unsubstituted phenyl of (a); A. r1、R2、R3And R4Wherein the substituents optionally present are each independently selected from C1‑C20Alkyl, halogen, C1‑C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups; the phosphorus ligand compound provided by the invention can effectively improve the conversion rate of vinyl acetate and the selectivity of 2-acetoxy propionaldehyde.

Description

Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
Technical Field
The invention relates to the field of vinyl acetate hydroformylation, in particular to a phosphine ligand compound and a preparation method thereof, a catalyst composition and application thereof, and a vinyl acetate hydroformylation method.
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 AasifAD on Catalysis commu in 2010, etc. know that the main product of the rhodium complex catalyst in catalyzing the hydroformylation of vinyl acetate 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 phosphine ligand compound, a preparation method thereof, a catalytic system and a method for hydroformylation of vinyl acetate.
In order to achieve the above object, a first aspect of the present invention provides a phosphine ligand compound having a structure represented by formula (1):
Figure BDA0001909010880000021
wherein A is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted phenyl of (a); A. r1、R2、R3And R4Wherein the substituents optionally present are each independently selected from C1-C20Alkyl, halogen, C1-C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
The second aspect of the present invention provides a process for producing the above phosphine ligand compound, which comprises: sequentially reacting ROH with PCl3Carrying out a first contact reaction and a second contact reaction with a compound represented by formula (6) to obtain a compound represented by formula (1);
Figure BDA0001909010880000022
wherein R is selected from R1、R2、R3And R4At least one of, and R1、R2、R3、R4And A in the compound represented by the formula (6) is as defined as in the above-mentioned phosphine ligand compound.
In a third aspect, the present invention provides a catalyst composition comprising a rhodium complex and a phosphine ligand compound according to the present invention.
In a fourth aspect, the present invention provides a use of the above catalyst composition in catalyzing hydroformylation of vinyl acetate.
In a fifth aspect, the present invention provides a method for hydroformylation of vinyl acetate, the method comprising: and carrying out a third contact reaction on the vinyl acetate and the synthesis gas in the presence of the catalyst composition.
Through the technical scheme, the invention provides the phosphine ligand compound with a novel structure, the phosphine ligand compound and the rhodium complex are matched to form the catalyst composition, and the catalyst composition is applied to the hydroformylation of vinyl acetate, so that the conversion rate of the vinyl acetate can be improved to more than 85 percent and the selectivity of 2-acetoxy propionaldehyde can be improved to more than 98 percent 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.
In a first aspect, the present invention provides a phosphine ligand compound, characterized in that the phosphine ligand compound has a structure represented by formula (1):
Figure BDA0001909010880000031
wherein A is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted phenyl of (a); A. r1、R2、R3And R4Wherein 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 of (a)" may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group or an isooctyl group.
In the present invention, the term "C" is used1-C10The "alkoxy group" of (A) may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, n-pentoxy, isopentoxy.
Preferably, the substituted or unsubstituted phenyl group represented by a is linked to the structure represented by formula (1) in an ortho, meta or para position.
Preferably, a is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstitutedSubstituted C1-C6Alkyl, substituted or unsubstituted phenyl of (a); and A, R1、R2、R3And R4Wherein the optional substituents are selected from C1-C6Alkyl, halogen, C1-C6At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
In the present invention, the term "C" is used1-C6The "alkyl group" of (a) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, or an isohexyl group.
In the present invention, the term "C" is used1-C6The "alkoxy group" of (A) may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, n-pentoxy, isopentoxy.
More preferably, a is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstituted C1-C3Alkyl, substituted or unsubstituted phenyl of (a); and R is1、R2、R3And R4Wherein the optional substituents are 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" of (a) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group.
In the present invention, the term "C" is used1-C3The "alkoxy group" of (a) may be, for example, methoxy, ethoxy, n-propoxy or isopropoxy.
According to a preferred embodiment of the invention, R is1、R2、R3And R4The same is true.
In the present invention, it is particularly preferable that the phosphine ligand compound is one selected from the group consisting of a compound represented by formula (2), a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5):
Figure BDA0001909010880000051
in a second aspect, the present invention provides a process for the preparation of a phosphine ligand compound according to the invention, which process comprises: sequentially reacting ROH with PCl3Carrying out a first contact reaction and a second contact reaction with a compound represented by formula (6) to obtain a compound represented by formula (1);
Figure BDA0001909010880000052
wherein R is selected from R1、R2、R3And R4At least one of, and R1、R2、R3、R4And A in the compound represented by the formula (6) is as defined as that referred to for the phosphine ligand compound.
In the present invention, the first contact reaction and the second contact reaction may employ reaction conditions commonly used in the art as long as the compound represented by formula (1) can be obtained.
To increase the yield of the compound represented by the formula (1), ROH and PCl are preferable3And the compound represented by the formula (6) is used in a molar ratio of 1: (2-4): (0.5-2).
Preferably, the conditions under which the first contact reaction is carried out include: the temperature is 60-100 ℃; the time is 1-3 h. Preferably, the conditions under which the second contact reaction is carried out include: the temperature is 40-60 ℃; the time is 1-3 h. Preferably, the second contacting reaction is carried out in the presence of 4-Dimethylaminopyridine (DMAP).
According to a preferred embodiment of the present invention, the method for preparing the phosphine ligand comprises:
1) ROH was added to the reactor under nitrogen atmosphere, and then PCl was added dropwise with stirring3After the dropwise adding is finished, heating to 60-100 ℃, and reacting for 1-3 h;
2) mixing the compound shown in the formula (6), DMAP and a solvent, and then dropwise adding the mixture into a reactor, after dropwise adding, heating to 40-60 ℃, and reacting for 1-3 h; preferably, the solvent is tetrahydrofuran;
wherein ROH and PCl3And the compound represented by the formula (6) is used in a molar ratio of 1: (2-4): (0.5-2).
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 a third aspect, the present invention provides a catalyst composition comprising a rhodium complex and a phosphine ligand compound according to the present invention.
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 fourth aspect, the invention provides a use of the catalyst composition of the invention in the catalysis of 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 98% when being applied to the catalysis of vinyl acetate hydroformylation.
In a fifth aspect, the present invention provides a method for hydroformylation of vinyl acetate, the method comprising: and carrying out a third contact reaction on the vinyl acetate and the synthesis gas in the presence of the catalyst composition.
Preferably, the conditions under which the third 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 the vinyl acetate is (0.01-10):1, 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 BDA0001909010880000071
the selectivity to aldehyde is calculated as follows:
Figure BDA0001909010880000081
the selectivity to 3-acetoxypropionaldehyde was calculated as follows:
Figure BDA0001909010880000082
the selectivity to 2-acetoxypropionaldehyde was calculated as follows:
Figure BDA0001909010880000083
preparation example 1
A process for producing a compound represented by the formula (2):
Figure BDA0001909010880000084
1) vacuumizing a 50L reaction kettle, introducing nitrogen for three times, adding 48.4mol of phenol, 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 ℃, the phosphorus trichloride is decompressed and steamed to a phosphorus trichloride elevated tank for recycling, and the distillation loss is estimated to be 0.5 liter.
2) 5L of anhydrous tetrahydrofuran was charged into the above reaction vessel, the premixing vessel was purged with nitrogen, 26.3mol of diphenol and 12.3mol of acid-binding agent DMAP (AR) were charged into the premixing vessel, 20L of anhydrous tetrahydrofuran was added to form a solution, and the solution was drained dropwise into the head tank. And heating the reaction kettle to 60 ℃, dropwise adding the solution into the reaction kettle, continuously stirring for 1h at 60 ℃ after three hours of addition, and monitoring the reaction process by chromatography. After the reaction is finished, evaporating tetrahydrofuran to a tetrahydrofuran head tank under reduced pressure, washing residues with 15L of acetonitrile, carrying out centrifugal filtration, returning filter cakes to the kettle for slurry washing, repeating for three times, and drying the target compound by using a vacuum double-cone dryer to obtain the compound shown in the formula (2).
The total yield is as follows: 79 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 6.73-6.91(m, 12H, aromatic CH), 7.02-7.29(m, 12H, aromatic CH).
Mass spectrum: [ MH+]542.1489。
Preparation example 2
A process for producing a compound represented by the formula (3):
Figure BDA0001909010880000091
the procedure is as in preparation example 1, except that diphenol is replaced by an equimolar amount
Figure BDA0001909010880000092
To obtain the compound shown in the formula (3).
The total yield is as follows: 86 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 2.37(s, 3H, CH3), 6.75-6.92(m, 12H, aromatic CH), 6.96-7.36(m, 11H, aromatic CH).
Mass spectrum: [ MH + ] 556.1579.
Preparation example 3
A process for producing a compound represented by the formula (4):
Figure BDA0001909010880000101
the procedure of preparation example 1 was followed, except that phenol was replaced with an equimolar amount of ethanol, to obtain a compound represented by formula (4).
The total yield is as follows: 91 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 1.67(t, J ═ 6.2Hz, 12H, CH3), 3.81(q, J ═ 6.2Hz, 8H, CH2), 7.11-7.30(m, 4H, aromatic CH).
Mass spectrum: [ MH + ] 351.0763.
Preparation example 4
A process for producing a compound represented by the formula (5):
Figure BDA0001909010880000102
the procedure of preparation example 2 was followed, except that phenol was replaced with an equimolar amount of ethanol, to obtain a compound represented by formula (5).
The total yield is as follows: 83 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 1.69(t, J ═ 6.2Hz, 12H, CH3), 2.37(s, 3H, CH3), 3.77(q, J ═ 6.2Hz, 8H, CH2), 6.02 (s, 1H, aromatic CH), 6.17(s, 2H, aromatic CH).
Mass spectrum: [ M + ] 364.0956.
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, 64.88mmol of vinyl acetate as a raw material for hydroformylation, 44mL of toluene as a solvent, 0.025mmol of triphenylphosphine carbonyl rhodium acetylacetonate and 0.054mmol of the compound represented by the formula (2) as a catalyst were charged, and the autoclave was sealed. Replaced three times with nitrogen, and the reaction mixture was purified with synthesis gas (CO:H2the 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 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 (4). The results are shown in Table 1.
Example 6
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 (5). The results are shown in Table 1.
Example 7
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 8
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 BDA0001909010880000131
The results in table 1 show that when the phosphine ligand compound provided by the invention is used for hydroformylation of vinyl acetate, the conversion rate of the vinyl acetate can be improved to more than 85%, and the selectivity of the 2-acetoxy propionaldehyde can be improved to more than 98%, even to 100%.
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 (18)

1. A phosphine ligand compound, characterized in that the phosphine ligand compound has a structure represented by formula (1):
Figure FDA0001909010870000011
wherein the content of the first and second substances,
a is selected from substituted or unsubstituted phenyl;
R1、R2、R3and R4Each independently selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted phenyl of (a);
A、R1、R2、R3and R4Wherein 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 phosphine ligand compound according to claim 1, wherein the substituted or unsubstituted phenyl group represented by a is bonded to the structure represented by formula (1) in an ortho-, meta-or para-position.
3. The phosphine ligand compound of claim 1 or 2, wherein a is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted phenyl of (a); and A, R1、R2、R3And R4Wherein the optional substituents are selected from C1-C6Alkyl, halogen, C1-C6At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups;
preferably, a is selected from substituted or unsubstituted phenyl; r1、R2、R3And R4Each independently selected from substituted or unsubstituted C1-C3Alkyl, substituted or unsubstituted phenyl of (a); and R is1、R2、R3And R4Wherein the optional substituents are selected from C1-C3Alkyl, halogen, C1-C3At least one of alkoxy groups of (a).
4. The phosphine ligand compound of any one of claims 1-3, wherein R is1、R2、R3And R4The same is true.
5. The phosphine ligand compound according to any one of claims 1 to 4, wherein the phosphine ligand compound is one selected from the group consisting of a compound represented by formula (2), a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5):
Figure FDA0001909010870000021
6. a process for preparing a phosphine ligand compound as defined in any one of claims 1 to 5, which process comprises: sequentially reacting ROH with PCl3Carrying out a first contact reaction and a second contact reaction with a compound represented by formula (6) to obtain a compound represented by formula (1);
Figure FDA0001909010870000022
wherein R is selected from R1、R2、R3And R4At least one of, and R1、R2、R3、R4And A in the compound represented by the formula (6) is as defined in any one of claims 1 to 5.
7. The method of claim 6, wherein ROH is in contact with PCl3And the compound represented by the formula (6) is used in a molar ratio of 1: (2-4): (0.5-2).
8. The method of claim 6, wherein the conditions under which the first contact reaction is carried out comprise: the temperature is 60-100 ℃; the time is 1-3 h;
preferably, the conditions under which the second contact reaction is carried out include: the temperature is 40-60 ℃; the time is 1-3 h.
9. The process of any one of claims 6-8, wherein the second contacting is carried out in the presence of 4-dimethylaminopyridine.
10. A catalyst composition comprising a rhodium complex and a phosphine ligand compound as claimed in any one of claims 1 to 5.
11. The composition of claim 10, 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).
12. Use of the catalyst composition of claim 10 or 11 in the catalysis of hydroformylation of vinyl acetate.
13. A method for hydroformylation of vinyl acetate, comprising: a third contact reaction of vinyl acetate with synthesis gas in the presence of the catalyst composition of claim 10 or 11.
14. The method of claim 13, wherein the conditions under which the third contact reaction is carried out comprise: the temperature is 80-120 ℃; the pressure is 3-6 MPa.
15. The process of claim 13 or 14, 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.
16. The process of claim 13 or 14, wherein the contacting 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.
17. The method of claim 16, wherein the volume ratio of solvent to vinyl acetate is (0.01-10):1, preferably (0.01-8): 1.
18. The method of any one of claims 13-15, wherein the contacting is performed in the absence of a solvent.
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