CN111320652A - 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

Info

Publication number
CN111320652A
CN111320652A CN201811545406.2A CN201811545406A CN111320652A CN 111320652 A CN111320652 A CN 111320652A CN 201811545406 A CN201811545406 A CN 201811545406A CN 111320652 A CN111320652 A CN 111320652A
Authority
CN
China
Prior art keywords
phosphine ligand
vinyl acetate
ligand compound
formula
group
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.)
Granted
Application number
CN201811545406.2A
Other languages
Chinese (zh)
Other versions
CN111320652B (en
Inventor
徐向亚
赵思源
冯华升
张明森
刘红梅
冯静
刘东兵
姜健准
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 CN201811545406.2A priority Critical patent/CN111320652B/en
Publication of CN111320652A publication Critical patent/CN111320652A/en
Application granted granted Critical
Publication of CN111320652B publication Critical patent/CN111320652B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

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‑C10Alkoxy, hydroxy, carboxy and aldehyde ofAt least one of the 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 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 fromC1-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: 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, 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.
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, 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, 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 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) adding HO-B-OH into a reactor under a nitrogen environment, and then dropwise adding PCl 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 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 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 bookIn the 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 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 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 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 as follows:
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: 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. Heating the reaction kettle to 60 ℃, dropwise adding the solution into the reaction kettle, continuously stirring at 60 ℃ after three hours of addingStirring for 1h, 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. Replacement with nitrogen three times, with syngas (CO: H)2The volume ratio is 1: 1) replacing for three times, pressurizing to 4MPa with synthesis gas, heating to reaction temperature of 100 deg.C, and starting hydrogenAnd (3) formylation reaction. 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 0.05mmol of the compound represented by the formula (2) as a catalyst were charged, 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 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 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 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 (17)

1. A phosphine ligand compound, characterized in that the phosphine ligand compound has a structure represented by formula (1):
Figure FDA0001909215160000011
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.
2. The phosphine ligand compound of claim 1, wherein 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;
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).
3. The phosphine ligand compound according to claim 1 or 2, wherein B is1And B2The same is true.
4. The phosphine ligand compound according to any one of claims 1 to 3, wherein the phosphine ligand compound is a compound represented by formula (2) and/or a compound represented by formula (3):
Figure FDA0001909215160000012
5. a process for preparing a phosphine ligand compound as defined in any one of claims 1 to 4, 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 FDA0001909215160000021
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 4.
6. The method of claim 5, 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).
7. The method of claim 5, 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.
8. The process of any one of claims 5-7, wherein the second contacting is carried out in the presence of 4-dimethylaminopyridine.
9. A catalyst composition comprising a rhodium complex and a phosphine ligand compound as claimed in any one of claims 1 to 4.
10. The composition of claim 9, 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).
11. Use of the catalyst composition of claim 9 or 10 for catalyzing the hydroformylation of vinyl acetate.
12. 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 9 or 10.
13. The method of claim 12, wherein the conditions under which the third contact reaction is carried out comprise: the temperature is 80-120 ℃; the pressure is 3-6 MPa.
14. The process of claim 12 or 13, 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.
15. The process of any one of claims 12-14, wherein the third 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-C10Alcohol of (2)At least one of;
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.
16. The method of claim 15, wherein the volume ratio of solvent to vinyl acetate is (0.01-10):1, preferably (0.01-8): 1.
17. The method of any one of claims 12-14, wherein the third contacting reaction is conducted under solvent-free conditions.
CN201811545406.2A 2018-12-17 2018-12-17 Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method Active CN111320652B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811545406.2A CN111320652B (en) 2018-12-17 2018-12-17 Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811545406.2A CN111320652B (en) 2018-12-17 2018-12-17 Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method

Publications (2)

Publication Number Publication Date
CN111320652A true CN111320652A (en) 2020-06-23
CN111320652B CN111320652B (en) 2022-07-12

Family

ID=71166652

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811545406.2A Active CN111320652B (en) 2018-12-17 2018-12-17 Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method

Country Status (1)

Country Link
CN (1) CN111320652B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130190A (en) * 1996-10-29 1998-05-19 Mitsubishi Chem Corp Production of aldehyde compounds
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130190A (en) * 1996-10-29 1998-05-19 Mitsubishi Chem Corp Production of aldehyde compounds
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BATALOVA, T. A 等: "Cyclic biphenyl-2,2"-diyl diphosphites. Synthesis, oxidation, and complex formation", 《 ZHURNAL OBSHCHEI KHIMII》 *
化学工业出版社: "《化工百科全书 第10卷 空气调节-氯代醇》", 30 April 1996 *

Also Published As

Publication number Publication date
CN111320652B (en) 2022-07-12

Similar Documents

Publication Publication Date Title
US9795952B2 (en) Bidentate ligands for hydroformylation of ethylene
JP2015515461A (en) Deactivation of homogeneous hydrogenation catalysts for the production of ethylene glycol
CN111333680B (en) Phosphine ligand and preparation method and application thereof
GB2028677A (en) Carbonylation of olefinic compounds
CN110981709A (en) Method for preparing aldehyde by hydroformylation of internal olefin
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
Dabbawala et al. Regioselective hydroformylation of vinyl acetate catalyzed by rhodium complex of naphthyl-based monodentate bulky phosphine and phosphite ligands
CN111320652B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN111320653B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN111320654B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN107986943B (en) Synthesis method of cyclohexanedimethanol, catalyst and application thereof
CN114426469A (en) Method for preparing alcohol and aldehyde by olefin hydroformylation
Xu et al. Reductive Cleavage of C—O Bond in Model Compounds of Lignin
CN111320656A (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN110372513B (en) Vinyl acetate hydroformylation method
Arzoumanian et al. Palladium and phase transfer catalyzed carbonylation of propargyl derivatives
CN111318308A (en) Catalyst composition, application thereof and method for hydroformylation of vinyl acetate
CN114057558A (en) Synthetic method, catalytic system and application of 3,5, 5-trimethylhexanal
CN111318307A (en) Catalyst composition, application thereof and method for hydroformylation of vinyl acetate
CN113999096A (en) Method for synthesizing 6-methyl-5-octen-2-one by condensation hydrogenation
US9051229B2 (en) Transition metal catalysts for C—O hydrogenolysis and hydrodeoxygenation
Wegman et al. The role of phosphines and solvents in CoI2-catalyzed reductive carbonylation of methanol
CN108503595B (en) Method for preparing quinazolinone compound

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
GR01 Patent grant
GR01 Patent grant