CN111320652B - 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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CN111320652B
CN111320652B CN201811545406.2A CN201811545406A CN111320652B CN 111320652 B CN111320652 B CN 111320652B CN 201811545406 A CN201811545406 A CN 201811545406A CN 111320652 B CN111320652 B CN 111320652B
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vinyl acetate
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group
phosphine ligand
ligand compound
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CN111320652A (en
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徐向亚
赵思源
冯华升
张明森
刘红梅
冯静
刘东兵
姜健准
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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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • 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
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2423—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • 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
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • 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 biphenyl; b is1And B2Each independently selected from substituted or unsubstituted C1‑C20An alkylene group of (a); and A, B1And B2Wherein 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 are subjected to reaction 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 solve the problems of low vinyl acetate conversion rate and low 2-acetoxy propionaldehyde selectivity in the prior art, and provides a phosphine ligand compound, a preparation method thereof, a catalyst composition, application of the catalyst composition in catalyzing vinyl acetate hydroformylation and a vinyl acetate hydroformylation method.
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 BDA0001909215170000021
wherein the content of the first and second substances,
a is selected from substituted or unsubstituted biphenyl;
B1and B2Each independently selected from substituted or unsubstituted C1-C20An alkylene group of (a);
and A, B1And B2Wherein 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 preparing the above phosphine ligand compound, which comprises: HO-B-OH is sequentially reacted with PCl3Carrying out a first contact reaction and a second contact reaction with a compound represented by formula (4) to obtain a compound represented by formula (1);
Figure BDA0001909215170000022
wherein B is B1And/or B2And B is1、B2And A in the compound represented by the formula (4) is as defined as referred to in the phosphine ligand compound provided in the first aspect.
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 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 95 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 having a structure represented by formula (1):
Figure BDA0001909215170000031
wherein the content of the first and second substances,
a is selected from substituted or unsubstituted biphenyl;
B1and B2Each independently selected from substituted or unsubstituted C1-C20An alkylene group of (a);
and A, B1And B2Wherein 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 alkylene group "of (a) represents an alkylene group having 1 to 20 carbon atoms in total, and may be, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a heptylene group, an octylene group or the like.
In the present invention, said "C" is1-C20The "alkyl group" of (1) represents an alkyl group having 1 to 20 carbon atoms in total, and 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, an isooctyl group, etc.
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.
In the present invention, it is preferable that the substituted or unsubstituted biphenyl group represented by A is linked to the structure represented by formula (1) in a manner represented by formula (5),
Figure BDA0001909215170000041
wherein, the connecting positions on the two benzene rings can be any substituted position on the benzene rings respectively and independently.
Preferably, B1And B2Each independently selected from substituted or unsubstituted C1-C10An alkylene group of (a); and A, B1And B2Wherein the substituents optionally present are each independently selected from C1-C10Alkyl, halogen, C1-C10At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
In the present invention, the term "C" is used1-C10The alkylene group "of (a) represents an alkylene group having 1 to 10 carbon atoms in total, and may be, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group or the like.
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, a is selected from substituted or unsubstituted biphenyl; b is1And B2Each independently selected from substituted or unsubstituted C1-C6An alkylene group of (a); and A, B1And B2Wherein the substituents optionally present are each independently 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 alkylene group "of (a) represents an alkylene group having 1 to 6 carbon atoms in total, and may be, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, or the like.
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, methoxy, ethoxy, n-propoxyAlkyl, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, n-pentoxy, isopentoxy, and the like.
Preferably, a is selected from substituted or unsubstituted biphenyl; b is1And B2Each independently selected from substituted or unsubstituted C1-C3An alkylene group of (a); and A, B1And B2Wherein the substituents optionally present are each independently selected from C1-C4Alkyl, halogen, C1-C4At least one of alkoxy groups of (a).
In the present invention, the term "C" is used1-C3The alkylene group "of (a) represents an alkylene group having 1 to 3 carbon atoms in total, and may be, for example, a methylene group, an ethylene group, a propylene group or the like.
In the present invention, the term "C" is used1-C4The "alkyl group" in (1) represents an alkyl group having 1 to 4 carbon atoms in total, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group or the like.
In the present invention, the term "C" is used1-C4The "alkoxy group" of (1) 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, an n-butoxy group, an isobutoxy group or the like.
According to a preferred embodiment of the present invention, in formula (1), B1And B2The 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 BDA0001909215170000061
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: HO-B-OH is sequentially reacted with PCl3Carrying out a first contact reaction and a second contact reaction with a compound represented by formula (4) to obtain a compound represented by formula (1);
Figure BDA0001909215170000062
wherein B is B1And/or B2And B is1、B2And A in the compound represented by the formula (4) is as defined as referred to in the phosphine ligand compound provided in the first aspect of the present invention.
To increase the yield of the compound of formula (1), HO-B-OH and PCl are preferred3And the molar ratio of the compound shown in the formula (4) is 1 (4-8) to (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 for carrying out the second contact reaction 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) adding HO-B-OH into a reactor under nitrogen atmosphere, and then adding PCl dropwise while stirring3After the dropwise adding is finished, heating to 60-100 ℃, and reacting for 1-3 h;
2) mixing the compound shown in the formula (4), 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; the solvent is tetrahydrofuran; wherein HO-B-OH and PCl3And the molar ratio of the compound shown in the formula (4) is 1 (4-8) to (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 used for exemplary enumeration and do not indicate that they are necessary operations, and those skilled in the art can substitute conventional other means.
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 95% 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 (1) to (1) is preferably (0.1-10); more preferably (0.2-5): 1.
According to a preferred embodiment of the present invention, the third 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 alcohols of (a). More preferably, the solvent is selected from C5-C10Aliphatic hydrocarbon of (C)6-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 third contact reaction is carried out under the solvent-free condition, so that the use and recovery of the 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 BDA0001909215170000081
the selectivity to aldehyde is calculated according to the formula:
Figure BDA0001909215170000082
the selectivity to 3-acetoxypropionaldehyde was calculated as follows:
Figure BDA0001909215170000083
the selectivity to 2-acetoxypropionaldehyde was calculated as follows:
Figure BDA0001909215170000091
preparation example 1
Figure BDA0001909215170000092
3.3kg of sodium hydroxide (AR) and 83g of sodium dodecylsulfate (AR) are dissolved in 15L of distilled water, heated to 60 ℃ and 91mol of sodium dodecylsulfate (AR) are added
Figure BDA0001909215170000093
Heating to 80 ℃, dropwise adding 2.8L of hydrogen peroxide (30 wt%, AR) by using a metering pump, keeping the temperature not higher than 90 ℃ in the dropwise adding process, dropwise adding for 3 hours, after the dropwise adding is finished, continuously stirring for 0.5 hour, cooling to room temperature under stirring, centrifugally filtering, washing the filter cake in a kettle by using 15L of distilled water, centrifugally filtering, returning the filter cake to the kettle for pulp washing, repeating for three times, washing by using 15L of acetonitrile, centrifugally filtering, returning the filter cake to the kettle for pulp washing, repeating for three times, pumping the filter cake to a solvent distillation kettle, and distilling and recycling. Oven drying at 105 deg.C to obtain
Figure BDA0001909215170000094
Yield: 85 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 2.0(s, 18H, 6CH3), 2.27(s, 18H, 6CH3), 5.25(s, 2H, OH), 7.13(s, 2H, aromatic CH), 7.21(s, 2H, aromatic CH).
Mass spectrum: [ M + ] 410.3695.
Preparation example 2
Figure BDA0001909215170000101
The procedure is as in preparation example 1, except that
Figure BDA0001909215170000102
By replacing with equimolar amounts
Figure BDA0001909215170000103
To obtain
Figure BDA0001909215170000104
Yield: and 90 percent.
Preparation example 3
A process for producing a compound represented by the formula (2):
Figure BDA0001909215170000105
1) vacuumizing a 50L reaction kettle, introducing nitrogen for three times, adding 24.2mol of ethylene glycol, 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 added to the above reaction vessel, the premix vessel was replaced with nitrogen, and 26.3mol of tetrahydrofuran was added
Figure BDA0001909215170000106
And 12.3mol of acid-binding agent DMAP (AR) are added into the premixing kettle, 20L of anhydrous tetrahydrofuran is added to form a solution, and the solution is dripped into the upper tank. And (3) 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: 91 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 3.51(t, J ═ 4.5Hz, 8H, 4CH2), 7.03-7.31(m, 8H, aromatic CH).
Mass spectrum: [ M + ] 366.7284.
Preparation example 4
A process for producing a compound represented by the formula (3):
Figure BDA0001909215170000111
the process is carried out as in preparation 1) except that in step 2)
Figure BDA0001909215170000112
By replacing with equimolar amounts
Figure BDA0001909215170000113
To obtain the compound shown in the formula (3).
The total yield is as follows: 83 percent.
Nuclear magnetism: 1H NMR (CDCl3/TMS, 300MHz) delta (ppm): 1.51(s, 18H, 6CH3), 2.15(s, 18H, 6CH3), 3.57(t, J ═ 4.5Hz, 8H, 4CH2), 7.13(s, 2H, aromatic CH), 7.21(s, 2H, aromatic CH).
Mass spectrum: [ M + ] 590.7575.
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. Displacing with nitrogen three times, using synthesis gas (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. Cooling the reaction kettle to room temperature (25 deg.C), discharging unreacted gas, displacing with nitrogen for 3 times, opening the reaction kettle, and analyzing reaction product group by gas chromatographyThe results of the quantification by the internal standard method are shown in Table 1.
Example 2
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 0.05mmol of a compound represented by the formula (2) as a catalyst were placed 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 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 gas storage tank pressure 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 acetylacetonatodicarbonylrhodium, and 0.5mmol of the compound represented by the formula (2) as a catalyst were added to 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 BDA0001909215170000131
Figure BDA0001909215170000141
The results in table 1 show that the conversion of vinyl acetate can be increased to 85% or more and the selectivity of 2-acetoxypropionaldehyde can be increased to 95% or more when the phosphine ligand compound provided by the present invention is used for 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 various technical features being combined 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 (21)

1. A method for hydroformylating vinyl acetate, comprising: subjecting vinyl acetate and synthesis gas to a third contact reaction in the presence of a catalyst composition;
wherein the composition comprises a rhodium complex phosphine ligand compound;
wherein the rhodium complex is at least one of acetylacetonatocarbonyltriphenylphosphine rhodium, acetylacetonatodicarbonylrhodium and triphenylphosphine rhodium hydride;
wherein the phosphine ligand compound has a structure represented by formula (1):
Figure FDA0003542562700000011
wherein, the first and the second end of the pipe are connected with each other,
a is selected from substituted or unsubstituted biphenyl;
B1and B2Each independently selected from substituted or unsubstituted C1-C20An alkylene group of (a);
and A, B1And B2Wherein 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 method of claim 1, wherein a is selected from substituted or unsubstituted biphenyl; b1And B2Each independently selected from substituted or unsubstituted C1-C6An alkylene group of (a); and A, B1And B2Wherein the substituents optionally present are each independently selected from C1-C6Alkyl, halogen, C1-C6At least one of alkoxy, hydroxyl, carboxyl and aldehyde groups.
3. The method of claim 2, wherein a is selected from substituted or unsubstituted biphenyl; b is1And B2Each independently selected from substituted or unsubstituted C1-C3An alkylene group of (a); and A, B1And B2Wherein the substituents optionally present are each independently selected from C1-C4Alkyl, halogen, C1-C4At least one of alkoxy groups of (a).
4. The method of any one of claims 1-3, wherein B1And B2The same is true.
5. The method according to any one of claims 1 to 4, wherein the phosphine ligand compound is a compound represented by formula (2) and/or a compound represented by formula (3):
Figure FDA0003542562700000021
6. the method according to any one of claims 1 to 5, wherein the phosphine ligand compound is prepared by a method comprising: HO-B-OH is sequentially reacted with PCl3Carrying out a first contact reaction and a second contact reaction with a compound represented by formula (4) to obtain a compound represented by formula (1);
Figure FDA0003542562700000022
wherein B is B1And/or B2And B is1、B2And A in the compound represented by the formula (4) is as defined in any one of claims 1 to 5.
7. The method of claim 6, wherein HO-B-OH and PCl3And the compound represented by the formula (4) is used in a molar ratio of 1: (4-8): (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;
and/or, the conditions under which the second contact reaction is carried out comprise: 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. The process according to claim 1, wherein the rhodium complex and the phosphine ligand compound are contained in a molar ratio of 1: (1-10).
11. The process of claim 10, wherein the rhodium complex and the phosphine ligand compound are present in a molar ratio of 1: (1-5).
12. The method of claim 1, wherein the conditions under which the third contact reaction is carried out comprise: the temperature is 80-120 ℃; the pressure is 3-6 MPa.
13. The process of claim 1 or 12, wherein the molar ratio of vinyl acetate to rhodium complex used is 1: (0.0001-0.01);
and/or, CO and H in the syngas2The content mole ratio of (0.1-10): 1.
14. the method of claim 13, wherein the syngas is CO and H2The content mole ratio of (0.2-5): 1.
15. the process of any one of claims 1, 12-14, wherein the third contacting reaction is carried out in the presence of a solvent.
16. The method of claim 15, wherein 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).
17. The method of claim 16, wherein 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).
18. The method of claim 17, wherein the solvent is selected from at least one of n-hexane, cyclohexane, n-heptane, benzene, toluene, 1, 3-xylene, 1, 4-xylene, 1,3, 5-trimethylbenzene, naphthalene, methyl tert-butyl ether, isopropyl ether, and isoprene glycol.
19. The method of claims 15-18, wherein the solvent to vinyl acetate volume ratio is (0.01-10): 1.
20. the method of any one of claims 15-18, wherein the volume ratio of solvent to vinyl acetate is (0.01-8): 1.
21. the method of any one of claims 1, 12-14, wherein the third contacting reaction is conducted under solvent-free conditions.
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