CN106565485A - Vinylacetate hydroformylation method - Google Patents
Vinylacetate hydroformylation method Download PDFInfo
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- CN106565485A CN106565485A CN201510652453.7A CN201510652453A CN106565485A CN 106565485 A CN106565485 A CN 106565485A CN 201510652453 A CN201510652453 A CN 201510652453A CN 106565485 A CN106565485 A CN 106565485A
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- XEYWVOCQBWZJGE-UHFFFAOYSA-N Nc(cc1)ccc1P(c(cc1)ccc1N)c(cc1)ccc1N Chemical compound Nc(cc1)ccc1P(c(cc1)ccc1N)c(cc1)ccc1N XEYWVOCQBWZJGE-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a vinylacetate hydroformylation method. The vinylacetate hydroformylation method comprises the step that in the presence of a catalyst system, vinylacetate makes contact with carbonic oxide and hydrogen, and the catalyst system contains a rhodium complex which is at least one selected from rhodium(triphenylphosphine)carbonyl acetylacetonate, rhodium acetylacetonate and chlorocarbonylbis(triphenylphosphine)rhodium. With the adoption of the vinylacetate hydroformylation method provided by the invention, the high conversion rate of the vinylacetate can be ensured under the mild reaction condition, and the selectivity of 3-acetoxypropanal can be improved.
Description
Technical field
The present invention relates to a kind of method of vinylacetate hydroformylation.
Background technology
Vinylacetate under olefin hydroformylation catalyst action with synthesis gas (CO and H2Gaseous mixture
Body) hydroformylation reaction is carried out, generate 3- acetoxyl groups propionic aldehyde and 2- acetoxyl group propionic aldehyde, 3- acetyl oxygen
Base propionic aldehyde and 2- acetoxyl groups propionic aldehyde generate 3- second in the presence of aldehyde radical hydrogenation catalyst with hydrogen reaction
Acyloxy propanol and 2- acetoxyl group propanol, 3- acetoxyl groups propanol and 2- acetoxyl groups propanol can either be
Hydrolysis in the presence of ester hydrolysis catalyst generates 1,3-PD and 1,2-PD, again can be in oxidant
Effect is lower to generate lactic acid and 3- hydracrylic acids.1,3- Propylene Glycol, 1,2- Propylene Glycol, lactic acid and 3- hydroxyls third
Acid is important industrial chemicals, and especially, 1,3-PD is a kind of important polyester fiber monomer, tool
There is very high market value.Scientists are devoted to ensureing higher conversion always in the past few decades
Rate, on the premise of less by-product is generated, improves the yield of 3- acetoxyl group propionic aldehyde.
Numerous results of study show that rhodium-containing catalyst atom is during vinylacetate hydroformylation reaction
It is higher to the selectivity ratios of branched product, and there is a chiral centre in branched product.Due to market for
The demand of Pfansteihl so that major part scientific research at present all concentrates on using chiral ligand to improve rhodium-containing
The chiral selectivity of catalyst atom.And be directed to and 3- acetyl oxygen how is improved using rhodium-containing catalyst atom
The research of base propionic aldehyde selectivity of product compares less.
Early in 1977, (J.Mol.Catal.1977,2,301) just reported and use Rh document2O3Urge
Change the reaction of vinylacetate, reaction conversion ratio can reach 100%, and for 2- acetoxyl group propionic aldehyde
Selectivity reach 99%, but it is very low for the selectivity of 3- acetoxyl group propionic aldehyde, best result is
3- acetoxyl group propionic aldehyde：2- acetoxyl groups propionic aldehyde=5:95.
The researcher Chaudhari and Borol of India in 2005 is in document (Ind.Eng.Chem.Res.
2005,44,9601) investigated in and pass through again after the hydroformylation reaction of vinylacetate a series of going back
The method of raw water solution prepares the technology path of 1,2- Propylene Glycol and 1,3- Propylene Glycol.The hydrogen first of vinylacetate
In acylation reaction, the catalyst of literature review includes HRh (CO) (PPh3)3、Rh(CO)2(acac)、
[Rh(COD)Cl]2、[Rh(CO)2Cl]2、RuCl2(CO)2Py2And Co2(CO)8, wherein catalyst
Co2(CO)8Best selectivity is shown for 3- acetoxyl group propionic aldehyde is generated, its result is 3- acetyl
Epoxide propionic aldehyde：2- acetoxyl groups propionic aldehyde=48：52, but, its reaction condition is more harsh, and temperature is
120 DEG C, synthesize atmospheric pressure (CO：H2=1:1) it is 12.4MPa, when using catalyst RuCl2(CO)2Py2
When not only severe reaction conditions, and for 3- acetoxyl group propionic aldehyde does not have selectivity, containing rhodium atom
In catalyst, HRh (CO) (PPh3)3It is best for the selectivity of 3- acetoxyl group propionic aldehyde, reach 3- acetyl
Epoxide propionic aldehyde：2- acetoxyl groups propionic aldehyde=9：91.
US20070213558A1 discloses a kind of method of vinylacetate hydroformylation, the catalysis for using
Agent is Co2(CO)8, the best embodiment reaction temperature of technique effect is 120 DEG C, synthesizes atmospheric pressure (CO：
H2=1:1) it is 7.6MPa.
CN102372603A discloses a kind of while the method for generating 1,3-PD and 1,2-PD,
Using Co2(CO)8For the hydroformylation reaction of main catalyst alkyl carboxylic acid vinyl acetate.
WO2011075905A1 discloses a kind of while generating the side of 1,3- Propylene Glycol and 1,2- Propylene Glycol
Method, with the complex HRhCo of metal Co and Rh3(CO)13(PPh3)3For catalyst vinyl acetate
The hydroformylation reaction of ester, reaction condition is very gentle, but this catalyst needs comparatively laborious preparation
Process.
To sum up, existing method carries out vinylacetate hydroformylation reaction process and there is 3- acetoxyl group propionic aldehyde
Product selectivity is poor, the shortcomings of reaction condition is harsher, therefore how under mild reaction conditions,
While ensureing vinylacetate higher conversion, the selectivity for improving 3- acetoxyl group propionic aldehyde is acetic acid second
The important problem that alkene ester hydroformylation reaction is faced.
The content of the invention
The invention aims to overcome in prior art product in vinylacetate hydroformylation process
3- acetoxyl group propionic aldehyde selectivity ratios are poor, a kind of harsher defect of reaction condition, there is provided acetic acid
The method of vinyl acetate hydroformylation.The method provided using the present invention can not only be in relatively mild reaction bar
Under part, it is ensured that the high conversion of vinylacetate, and the selectivity of 3- acetoxyl group propionic aldehyde can be improved.
To achieve these goals, the present invention provides a kind of method of vinylacetate hydroformylation, the party
Method includes：In the presence of a catalyst system, vinylacetate is contacted with carbon monoxide and hydrogen, it is described
Catalyst system contains rhodium complex, and the rhodium complex is selected from acetylacetonatodicarrhodium rhodium, second
At least one in acyl acetone rhodium and triphenylphosphine carbonyl radium chloride.
A kind of method of vinylacetate hydroformylation of the invention, can compared with low reaction temperatures and
Under reaction pressure, it is ensured that while higher conversion, during improving vinylacetate hydroformylation reaction
The selectivity of 3- acetoxyl group propionic aldehyde.In addition, the method provided using the present invention, even if depositing solvent-free
Reacted under, it is also possible under compared with low reaction temperatures and reaction pressure, it is ensured that higher conversion it is same
When, the selectivity of 3- acetoxyl group propionic aldehyde during vinylacetate hydroformylation reaction is improved, ensureing
On the premise of technique effect, it is to avoid energy waste, productivity effect is improve.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method of vinylacetate hydroformylation, the method includes：In catalyst
In the presence of system, vinylacetate is contacted with carbon monoxide and hydrogen, the catalyst system contains rhodium
Complex, the rhodium complex is selected from acetylacetonatodicarrhodium rhodium, acetylacetone,2,4-pentanedione rhodium and triphenyl
At least one in phosphine carbonyl radium chloride.
A preferred embodiment of the invention, the rhodium complex is acetylacetone,2,4-pentanedione triphenylphosphine carbonyl
Base rhodium.In the preferred implementation, can further carry under compared with low reaction temperatures and reaction pressure
The selectivity of high 3- acetoxyl groups propionic aldehyde.
A preferred embodiment of the invention, the catalyst system also contains Phosphine ligands, preferably
The rhodium complex is (0.1-3) with the mol ratio of Phosphine ligands：1, more preferably (0.2-2)：1.
In the preferred implementation, 3- can be further improved under compared with low reaction temperatures and reaction pressure
The selectivity of acetoxyl group propionic aldehyde.
A preferred embodiment of the invention, the Phosphine ligands are selected from containing as shown in formula (1)
The Organic substance containing phosphine shown in Organic substance containing phosphine, formula (3) and formula (4) shown in phosphine Organic substance, formula (2)
One or more in shown Organic substance containing phosphine.
Wherein, Ar is substituted or unsubstituted aryl in formula (1), formula (3) and formula (4), and formula
(1), the multiple Ar in formula (3) and formula (4) can be with identical or different.
Wherein, in formula (2), M be hydrogen, halogen or substituted or unsubstituted alkyl, and its
In multiple M can be with identical or different.
Wherein, t is the integer of 2-10 in formula (3).
In accordance with the present invention it is preferred that, Ar is respectively and takes in the formula (1), formula (3) and formula (4)
One or more in generation or unsubstituted phenyl or substituted or unsubstituted naphthyl.
The substituted phenyl can be the alkyl-substituted phenyl of para-position, ortho alkyl replace phenyl,
The alkyl-substituted phenyl in position, the phenyl of para-position halogen substiuted, the phenyl of ortho position halogen substiuted, meta halogen
Substituted phenyl, para-position and the dibasic phenyl of ortho alkyl, para-position and the dibasic phenyl of meta alkyl,
Meta and the dibasic phenyl of ortho alkyl, the phenyl of ortho position dialkyl group replacement, meta dialkyl group replace
Phenyl, para-position and the dibasic phenyl of ortho position halogen, para-position and the dibasic phenyl of meta halogen, meta
With the phenyl of the dibasic phenyl of ortho position halogen, the phenyl of the halogen substiuted of ortho position two and the halogen substiuted of meta two
In one or more.
The substituted naphthyl is preferably one or more in the naphthyl of 1 or 2 replacement.
It is further preferred that Ar is phenyl or naphthyl in the formula (1), formula (3) and formula (4),
And the multiple Ar in formula (1), formula (3) and formula (4) can be with identical or different, most preferably phenyl.
Under the preferable case, 3- acetyl oxygen can be further improved under compared with low reaction temperatures and reaction pressure
The selectivity of base propionic aldehyde.
A preferred embodiment of the invention, in the formula (2) M be hydrogen, halogen or
The alkyl of the substituted or unsubstituted C1-C8 of person, in further preferred formula (2) M be hydrogen, fluorine, chlorine,
Bromine, iodine, CCl3Or CH3, and multiple M therein can be with identical or different.In the side of being preferable to carry out
In formula, the choosing of 3- acetoxyl group propionic aldehyde under compared with low reaction temperatures and reaction pressure, can be further improved
Selecting property.
A preferred embodiment of the invention, t is the integer of 2-5 in the formula (3).At this
In preferred implementation, under compared with low reaction temperatures and reaction pressure, 3- acetoxyl groups third are further improved
The selectivity of aldehyde.
According to the present invention, the Phosphine ligands are preferably (+)-isopropyl alkene -2,3- sodium catchol disulfonates, the double diphenylphosphine fourths of 4-
Alkane, (+)-isopropyl alkene -2,3- sodium catchol disulfonates, 4 pairs two (2- naphthyls) phosphine butane, triphenylphosphine and three (4- chlorobenzenes
Base) one or more in phosphine, particularly preferably (+)-isopropyl alkene -2,3- sodium catchol disulfonates, the double diphenylphosphine fourths of 4-
Alkane.
The mol ratio of a preferred embodiment of the invention, the vinylacetate and rhodium complex
For (1000-5000)：1, more preferably (2000-3500)：1.In the preferred implementation,
Under compared with low reaction temperatures and reaction pressure, the selectivity of 3- acetoxyl group propionic aldehyde can be further improved.
According to the present invention, the condition that the vinylacetate is contacted with carbon monoxide and hydrogen can be ability
The conventional implementation condition of field technique.
In the preferred case, the temperature that the vinylacetate is contacted with carbon monoxide and hydrogen is
20-200 DEG C, more preferably 80-120 DEG C.
In the preferred case, the pressure that the vinylacetate is contacted with carbon monoxide and hydrogen is
0.5-10MPa, more preferably 3-4MPa.In the present invention, the pressure refers to gauge pressure.
The method that the present invention is provided can be carried out under solvent existence condition, it is also possible under condition of no solvent
Carry out.
According to the present invention, the solvent is referred to for hydroformylation reaction inertia but can effectively dissolve original
The solvent of material, product and catalyst.
In the case of solvent is present, the solvent is preferably selected from C5-C20Aliphatic hydrocarbon, C6-C12Aromatic hydrocarbon,
C5-C20Ether and C5-C20One or more in alcohol, further preferred C5-C10Alkane, C6Aromatic hydrocarbon,
C5-C10Ether and C5-C10One or more in alcohol, for example, hexane, hexamethylene, heptane, benzene, first
Benzene, 1,3- dimethylbenzene, 1,4- dimethylbenzene, 1,3,5- trimethylbenzenes, naphthalene, methyl tertiary butyl ether(MTBE), diisopropyl ether and
One kind in one or more in isoprene, more preferably toluene, hexamethylene and methyl tertiary butyl ether(MTBE)
Or it is various.
According to the present invention, the solvent is preferably (0.01-10) with the volume ratio of vinylacetate：1, enter
One step is preferably (0.01-8)：1.
The method that the present invention is provided can also be carried out under condition of no solvent, eliminate prior art acetic acid second
Solvent using and reclaiming during alkene ester hydroformylation reaction, and resource wave is avoided to a certain extent
Take.
Can be (0.1-10) according to the volume ratio of the present invention, carbon monoxide and hydrogen:1, preferably
(0.2-5):1.The present invention does not have particular/special requirement to the source of carbon monoxide and hydrogen, preferably an oxygen
Change carbon and hydrogen to be provided by synthesis gas.
Hereinafter will be described the present invention by embodiment, but the present invention is not limited to this.
In following examples, reactant liquor gas chromatographic analysiss, inner mark method ration calculates vinylacetate
Conversion ratio and 3- acetoxyl group propionic aldehyde, the selectivity of 2- acetoxyl group propionic aldehyde.
The conversion ratio of vinylacetate is calculated according to the following formula：
The selectivity of 3- acetoxyl group propionic aldehyde is calculated according to the following formula：
The selectivity of 2- acetoxyl group propionic aldehyde is calculated according to the following formula：
Raw material used in following examples and comparative example is commercially available.
Embodiment 1
In 100ml autoclaves, 6ml vinylacetates (64.88mmol) are added to be hydrogen formyl
Change reaction raw material, 44ml hexamethylene be solvent, 12.2mg acetylacetonatodicarrhodium rhodiums
(0.02mmol) with 26.8mg (+)-isopropyl alkene -2,3- sodium catchol disulfonates, double diphenylphosphines butane (0.05mmol) of 4-
For catalyst, sealed reactor.With nitrogen displacement three times, with synthesis gas (CO：H2Volume ratio is 1：
1) replace three times, and 4.0MPa is pressurized to synthesis gas, be warming up to 100 DEG C of reaction temperature, start hydrogen
Formylation reaction.The synthesis gas that reaction is consumed is indicated by gas reservoir pressure change, until no longer consuming gas
Body is reaction end.Reactor drops to room temperature, discharges unreacting gas, then by nitrogen displacement 3 times after,
Reactor is opened, is constituted with gas chromatographic analysiss product, inner mark method ration, calculated vinyl acetate and turn
The selectivity of rate, the selectivity of 2- acetoxyl group propionic aldehyde and 3- acetoxyl group propionic aldehyde.The results are shown in Table 1.
Comparative example 1
According to the method for embodiment 1, except for the difference that, the catalyst of addition is the (triphenyls of 22.4mg tri-
Phosphine) carbonyl hydrogenation Rh (0.02mmol).The results are shown in Table 1.
Comparative example 2
According to the method for embodiment 1, except for the difference that, the catalyst of addition is the (triphenyls of 22.4mg tri-
Phosphine) carbonyl hydrogenation Rh (0.02mmol) and 26.8mg (+)-isopropyl alkene -2,3- sodium catchol disulfonates, the double diphenylphosphines of 4-
Butane (0.05mmol).The results are shown in Table 1.
Embodiment 2
In 100ml autoclaves, 46ml vinylacetates (497.41mmol) are added to be hydrogen first
The raw material of acylation reaction, 122mg acetylacetonatodicarrhodium rhodiums (0.2mmol) and 60mg (+)-
Isopropyl alkene -2,3- sodium catchol disulfonates, double diphenylphosphines butane (0.12mmol) of 4- are catalyst, sealed reactor.
With nitrogen displacement three times, with synthesis gas (CO：H2Volume ratio is 1：1) replace three times, and with synthesize
Gas is pressurized to 3.5MPa, is warming up to 80 DEG C of reaction temperature, starts hydroformylation reaction.What reaction was consumed
Synthesis gas is indicated by gas reservoir pressure change, until no longer consuming gas for reaction end.Reactor drops
To room temperature, discharge unreacting gas, then by nitrogen displacement 3 times after, open reactor, use gas chromatogram
Analytical reactions product is constituted, inner mark method ration, calculates vinyl acetate conversion ratio, 2- acetoxyl group propionic aldehyde
The selectivity of selectivity and 3- acetoxyl group propionic aldehyde.The results are shown in Table 1.
Comparative example 3
According to the method for embodiment 2, except for the difference that, the catalyst of addition is the (triphenyls of 122mg tri-
Phosphine) carbonyl hydrogenation Rh (0.13mmol) and 60mg (+)-isopropyl alkene -2,3- sodium catchol disulfonates, the double diphenylphosphine fourths of 4-
Alkane (0.12mmol).The results are shown in Table 1.
Embodiment 3
According to the method for embodiment 2, except for the difference that, with 61mg acetylacetonatodicarrhodium rhodiums
(0.1mmol) with 35.2mg (+)-isopropyl alkene -2,3- sodium catchol disulfonates, 4 pairs two (2- naphthyls) phosphine butane
(0.05mmol) it is catalyst, reaction pressure is 3.0MPa, and temperature is 120 DEG C.The results are shown in Table 1.
Embodiment 4
According to the method for embodiment 1, except for the difference that, (+)-isopropyl alkene -2,3- sodium catchol disulfonates, 4- are not contained in catalyst
Double diphenylphosphine butane.The results are shown in Table 1.
Embodiment 5
According to the method for embodiment 2, except for the difference that, the catalyst for using is 122mg acetylacetone,2,4-pentanediones three
Phenylphosphine rhodium carbonyl (0.2mmol) and 16.5mg triphenylphosphines (0.06mmol).The results are shown in Table 1.
Embodiment 6
According to the method for embodiment 3, except for the difference that, the catalyst for using is 85.0mg triphenylphosphine carbonyls
Base radium chloride (0.12mmol) and 35.2mg (+)-isopropyl alkene -2,3- sodium catchol disulfonates, 4 pairs two (2- naphthyls) phosphines
Butane (0.05mmol).The results are shown in Table 1.
Embodiment 7
According to the method for embodiment 2, except for the difference that, the catalyst for using is 80.0mg acetylacetone,2,4-pentanedione rhodiums
(0.2mmol) with 36.6mg tri- (4- chlorphenyls) phosphine (0.1mmol).The results are shown in Table 1.
Comparative example 4
In 100ml autoclaves, 6ml vinylacetates (64.88mmol) are added to be hydrogen formyl
The raw material of change, 44ml hexamethylene be solvent, 200mg Co2(CO)8(0.58mmol) it is catalyst, it is close
Envelope reactor.With nitrogen displacement three times, with synthesis gas (CO：H2Volume ratio is 1：1) replace three times,
And 4.0MPa is pressurized to synthesis gas, and 100 DEG C of reaction temperature is warming up to, start hydroformylation reaction.Instead
The synthesis gas that should be consumed is indicated by gas reservoir pressure change, until no longer consuming gas for reaction end.
Reactor drops to room temperature, discharges unreacting gas, then by nitrogen displacement 3 times after, open reactor, use
Gas chromatographic analysiss product constitute, inner mark method ration, calculate vinyl acetate conversion ratio, to 2- acetyl
The selectivity of epoxide propionic aldehyde and the selectivity to 3- acetoxyl group propionic aldehyde.The results are shown in Table 1.
Table 1
Embodiment 1 and comparative example 1, the comparing result of comparative example 2 and embodiment 2 and contrast from table
The comparing result of example 3 can be seen that under solvent or solvent-free state, using currently preferred catalysis
Agent system is lived under the conditions of same reaction temperature, reaction pressure and catalyst amount with higher reaction
The selectivity of property and 3- acetoxyl group propionic aldehyde, with the superiority that prior art is incomparable.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method of vinylacetate hydroformylation, the method includes：Exist in catalyst system
Under, vinylacetate is contacted with carbon monoxide and hydrogen, it is characterised in that the catalyst system contains
There is rhodium complex, the rhodium complex is selected from acetylacetonatodicarrhodium rhodium, acetylacetone,2,4-pentanedione rhodium and three
At least one in Phenylphosphine carbonyl radium chloride.
2. method according to claim 1, wherein, the rhodium complex is acetylacetone,2,4-pentanedione triphen
Base phosphine rhodium carbonyl.
3. method according to claim 1 and 2, wherein, the catalyst system also contains phosphine
Part, the rhodium complex is (0.1-3) with the mol ratio of the Phosphine ligands：1, preferably (0.2-2)：
1；The Phosphine ligands are selected from organic containing phosphine shown in the Organic substance containing phosphine as shown in formula (1), formula (2)
One or more in the Organic substance containing phosphine shown in Organic substance containing phosphine and formula (4) shown in thing, formula (3),
Wherein, in formula (1), formula (3) and formula (4) Ar be substituted or unsubstituted aryl, formula (2)
Middle M is hydrogen, halogen or substituted or unsubstituted alkyl, and t is the integer of 2-10 in formula (3).
4. method according to claim 3, wherein, the formula (1), formula (3) and formula (4)
Middle Ar is respectively phenyl or naphthyl, preferably phenyl.
5. method according to claim 3, wherein, M is hydrogen, halogen family in the formula (2)
Element or substituted or unsubstituted C1-C8Alkyl, preferably hydrogen, fluorine, chlorine, bromine, iodine, CCl3
Or CH3。
6. method according to claim 3, wherein, in the formula (3) t for 2-5 integer.
7. the method according to any one in claim 1-6, wherein, the vinylacetate
It is (1000-5000) with the mol ratio of the rhodium complex：1, preferably (2000-3500)：1.
8. the method according to any one in claim 1-6, wherein, the vinylacetate
The condition contacted with carbon monoxide and hydrogen includes：Temperature is 20-200 DEG C, preferably 80-120 DEG C, is pressed
Power is 0.5-10MPa, preferably 3-4MPa.
9. the method according to any one in claim 1-8, wherein, the method is solvent-free
Under the conditions of carry out.
10. the method according to any one in claim 1-9, wherein, carbon monoxide and hydrogen
Volume ratio be (0.1-10):1, preferably (0.2-5):1；Preferably, carbon monoxide and hydrogen are by closing
Supply into air stripping.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111318308A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Catalyst composition, application thereof and method for hydroformylation of vinyl acetate |
| CN111320649A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method |
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| JPS56122330A (en) * | 1980-03-03 | 1981-09-25 | Kuraray Co Ltd | Hydroformylation of vinyl carboxylate |
| EP0103891B1 (en) * | 1982-09-21 | 1986-03-26 | Kuraray Co., Ltd. | Process for producing alpha-acetoxypropionaldehyde |
| CN102826974A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing butyraldehyde through hydroformylation of propylene |
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2015
- 2015-10-10 CN CN201510652453.7A patent/CN106565485B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56122330A (en) * | 1980-03-03 | 1981-09-25 | Kuraray Co Ltd | Hydroformylation of vinyl carboxylate |
| EP0103891B1 (en) * | 1982-09-21 | 1986-03-26 | Kuraray Co., Ltd. | Process for producing alpha-acetoxypropionaldehyde |
| CN102826974A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing butyraldehyde through hydroformylation of propylene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111318308A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Catalyst composition, application thereof and method for hydroformylation of vinyl acetate |
| CN111320649A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method |
| CN111320649B (en) * | 2018-12-17 | 2022-07-12 | 中国石油化工股份有限公司 | Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method |
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| CN106565485B (en) | 2019-09-27 |
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