JPS62187424A - Carbonylation of olefins - Google Patents

Abstract

PURPOSE:A sulfonate cation exchanger is used as an acidic substance to improve the corrosion troubles of the reactor and effect the efficient carboxylation of olefins in the presence of a palladium catalyst, an organic phosphine and the acidic substance. CONSTITUTION:In the production of carboxylic acid, ester or carboxylic anhydride by carbonylation of olefin with a hydroxyl compound selected from water, alcohol, and carboxylic acid, and carbon monoxide in the presence of a palladium catalyst, an organic phosphine and an acidic substance, a sulfonate cation exchanger with a proton-exchange capacity of at least 0.05meq/g is used as the acidic substance to largely decrease corrosion trouble in the reactor and facilitate the separation of the catalyst from the objective compound whereby the objective compound is obtained advantageously from an industrial point of view.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for carbonylating olefins. Specifically, the present invention carbonylates olefins,
The present invention relates to a method for producing a carboxylic acid, a carboxylic acid ester, or a carboxylic acid anhydride.

[Conventional technology]

BACKGROUND ART A method of producing a carboxylic acid, a carboxylic acid ester, or a carboxylic acid anhydride by reacting an olefin, carbon monoxide, water, alcohol, and/or carboxylic acid under high temperature and high pressure conditions is well known. It is also known that when this reaction is carried out in the presence of a palladium catalyst, the coexistence of hydrogen chloride or metal halides generally promotes this reaction (US Pat. No. 2, 8 Jtg).

and the specifications of the same No. 3.9/9272; J,
Org, Ch@m, .

I11j2gg! (/9ri&); Tetrahs
Dron Letters.

I'lJri (/94.7), same lzatt (tqts, y
), and PJbos (tqbda). ). However, the use of halogenated cocatalysts as described above is not preferred because it causes corrosion problems in the reactor.

On the other hand, even in the absence of a halogen compound, this reaction proceeds smoothly in the presence of palladium metal or palladium chalcogenide, an organic phosphine, and a strong acid with a pKa 'I or higher, as disclosed in the US patent. 101! It is described in the specifications of No. r/g, No. a, and No. 7'J & 7A. Examples of the strong acids include sulfuric acid, phosphoric acid, perchloric acid, and boric acid. Also European Patent No. 113312
The number describes the use of phosphoric acid, trifluoroacetic acid, etc. Further, US Pat. No. 1'l@tloq describes a method of using a palladium-catalyzed doper-fluorosulfonic acid in combination with an organic phosphine ligand. Further, JP-A No. 59-FF2336 describes the use of strong acids with a pKa or higher, and representative examples of the strong acids include perchloric acid, sulfuric acid, co-hydroxypropane-cosulfonic acid, p-)luene. Examples include sulfonic acid and trifluoromethanesulfonic acid.

[Problem that the invention seeks to solve]

However, the use of strong acids as described above, like the case of non-rogenic cocatalysts, has the problem of corrosion of the reaction equipment, and furthermore, it is difficult to separate the target product from the palladium catalyst and cocatalyst. It has some drawbacks.

[Means for solving problems]

In consideration of the above facts, the present inventors have conducted extensive studies on an industrially advantageous carbonylation method for olefins, and have found that when a specific cation exchanger is used as the acidic substance of the cocatalyst, the reaction equipment Not only is corrosion significantly reduced.

It was discovered that the separation operation from the target product can be carried out smoothly, and the present invention was achieved.

That is, the gist of the present invention is to react olefins and carbon monoxide with a hydroxyl compound selected from the group consisting of water, alcohol, and carboxylic acid in the presence of a palladium catalyst, an organic phosphine, and an acidic compound to prepare the olefins. In the method of carbonylating the acidic compound, at least 0.0! The present invention relates to a method for carbonylating olefins, characterized by using a sulfonic acid-based cation exchanger having a proton exchange capacity of r m@q / f.

Hereinafter, the present invention will be explained in detail.

The olefins used as raw materials in the process of the invention are compounds having at least one olefinic double bond, preferably substituted or unsubstituted olefins having 2 to 30 carbon atoms. Specific examples include ethylene, propylene, l-butene, coptene, isobutylene, l-pentene, copentene, 3-methyl-t-7
'ten, l-hexene, cohexene.

Alkenes such as 3-hexene, coethyl-l-hexene, l-octene, and l-dodecene; cycloalkenes such as cyclohexene, cyclooctene, and cyclododecene;
Arylalkenes such as styrene and vinyltoluene; vinyl chloride.

Allyl chloride, methyl allyl ether, acrolein, acrylonitrile, acrylamide.

Examples include ti-substituted alkenes such as methyl acrylate, methyl methacrylate, ethyl methacrylate, undecylenic acid, and oleic acid.

The other raw material used in the process of the invention is a hydroxyl compound selected from the group consisting of water, alcohols and carboxylic acids. The alcohol is not particularly limited, but those having 1 to -0 carbon atoms are preferably used.

Specific examples include methanol, ethanol, n-propanol, l-glopanol, n-butanol, s@a-
Examples include butanol, l-butanol, t-butanol, n-pentanol, n-hexanol, n-octatool, stearyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, phthanediol, and the like. The above carboxylic acid is also not particularly limited, but preferably those having 1-10 carbon atoms are used,
Specific examples include formic acid, 61, propionic acid, butyric acid, caproic acid, trimethylacetic acid, benzoic acid, succinic acid, adipic acid, and the like. The use of water, alcohol and/or carboxylic acid 9 is usually o, i to /, 000 mol, preferably /% 1 per 7 mol of double bonds of olefins.
The range is approximately 0.00 mol.

The main catalysts used in the process of the invention are palladium and palladium compounds. Examples of the palladium compound include mineral acid salts such as palladium chloride, radium nitrate, and palladium sulfate; organic acid salts or organic chelate compounds such as palladium acetate, palladium bis(acetylacetonato), and palladium trifluoromethanesulfonate; Coordination compounds such as triphenylphosphine)palladium, bis(triphenylphosphine)palladium cyclolide, and the like can be mentioned. The amount of radium used is usually as palladium atom per mole of double bond of olefins.
io"" to 1 mol, preferably /0-" to 0.1 mol.

Organic phosphines, which are one of the promoters, include trialkylphosphines, dialkylmonoarylphosphines,
Examples include monoalkyldiarylphosphines and triarylphosphines, with monoalkyldiarylphosphines and triarylphosphines being particularly preferred.

Specific examples include ethyldiphenylphosphine, furobildiphenylphosphine, l,6-heΦsamethylenebis(diphenylphosphine), triphenylphosphine, tri-tolylphosphine, tri-m-tolylphosphine, tri-p-)lylphosphine. , Tris (p
-methoxyphenyl)phosphine and the like. The organic phosphine is used in an amount of usually 1 to 10 mol, preferably 3 to 101 mol, per mol of palladium.

As another co-catalyst, a cation exchanger, it is at least 0.0! A sulfonic acid-based one-field ion exchanger with a proton exchange capacity of rm@q/9- is used. Specific examples of the cation exchanger include styrene-divinylbenzene co-ffi, phenol-formaldehyde copolymer or U-bar fluoroethylene polymer with a sulfonic acid functional group introduced, or sulfonated coal, sulfonated polyester, etc. Examples include phenyl, sulfonated polyphenylene oxide, and sulfonated cellulose.

Table 1 shows examples of commercially available sulfonic acid cation exchangers.

As a typical sulfonic acid-based cation exchanger, a styrene-divinylbenzene copolymer with a sulfonic acid functional group is known, and it is generally
It is available cross-linked with divinylbenzene.

The amount of the sulfonic acid barrier ion exchanger used is usually 1-to'' equivalent per mole of palladium atom, preferably S
~100 equivalents.

The present invention can be carried out in the absence of a solvent, that is, the reaction raw materials themselves can be used as a medium, but a solvent can also be used. Examples of such solvents include ethers such as diethyl ether, aninol, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane; ketones such as acetone, methyl ethyl ketone, and acetophenone; methanol, ethanol,
-7'l/- alcohols such as benzyl alcohol, phenol, ethylene glycol, diethylene glycol; carboxylic acids such as formic acid, acetic acid, propionic acid, toluic acid; esters such as methyl acetate, n-butyl acetate, benzyl benzoate, etc. Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and tetrazine; Aliphatic hydrocarbons such as n-hexane, n-octane, and cyclohexane; Halogenated hydrocarbons such as dichloromethane, trichloroethane, and chlorobenzene; and nitrohydrocarbons such as nitromethane and nitrobenzene. Compounds nitriethylamine, tri-n-butylamine, benzyldimethylamine, pyridine, α-
Tertiary amines such as picoline, cohydroxyviridine;
N, N-dimethylformamide, N.

Carboxylic acid amides such as N-dimethylacetamide and N-methylpyrrolidone; hexamethylphosphoric acid triamide, N
, N, N', N' Inorganic acid amides such as tetraethylsulfamide; N, r-dimethylimidazolitone, N
, N,N',N'-tetramethylurea and other ureas; dimethylsulfone and tetramethylenesulfone and other sulfones; dimethylsulfoxide;

Sulfoxides such as diphenyl sulfoxide; Lactones such as r-butyrolactone and C-caprolactone; Polyethers such as tetraglyme and /1-crown-6;
Nitriles such as acetonitrile and benzonitrile; carbonic acid esters such as dimethyl carbonate and ethylene carbonate; and water.

In order to carbonylate a diolefin by the method of the present invention, a reaction vessel is charged with the reaction raw material olefin, water, alcohol and/or carboxylic acid, a catalyst component, and optionally a solvent, and carbon monoxide is added to the reaction vessel. Just introduce it. Carbon monoxide may be diluted with a gas inert to the reaction, such as nitrogen or carbon dioxide. There is no problem if a small amount of water purple is mixed in as well. However, the presence of multiple water deposits will result in the production of by-products, so it is preferable to suppress the degree of water buildup in the reaction system to 10% or less of carbon monoxide.

The reaction temperature is usually 20~2Sθ℃, preferably go-is
It is oc. The partial pressure of carbon monoxide in the reaction system is usually l~JO
Oky/a/l, preferably j to i0okg/ad. Although it is not impossible to carry out the process under even lower or higher pressures, it is not industrially advantageous.

The reaction can be carried out either batchwise or continuously. Required reaction time in case of batch method is usually 1-2
It is 0 hours.

The target carbonylated compound can be recovered from the reaction product liquid by conventional separation and purification means such as distillation and extraction. Further, the distillation residue can be added to the reaction system as a catalyst component.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

The meanings of the abbreviations in the examples are as follows.

MEn: Methyl enanthate MCp: Methyl α-methylcaproate Mgvi: α
-Methyl ethylvalerate T, O,? , value: number of moles of product per mole of palladium atoms and hour of reaction time (mol/mol-Pdshr) Example/Palladium acetate Q, Q! ; mmo1% triphenylphosphine 0. ! ; mmol, l-hexene j'd
, methanol 15-1 water/- and the cation exchange resin listed in Table A (063 m@q as H+) were placed in a microautoclave made by No-Steroy C, filled with carbon monoxide at a pressure of 1 okp7 ad at room temperature, and sealed. did.

After raising the temperature to ioo℃, the total pressure becomes tokt due to the progress of one reaction.
When the pressure was less than lcr1, the reaction was carried out for one hour while supplementing carbon monoxide to maintain a constant pressure tOkp/d. After the reaction, the product was analyzed by gas chromatography using an internal standard method. Methyl enanthate, methyl α-methylcaproate and methyl α-ethelvalerate shown in Table A are obtained, respectively, and indicate the type and crosslinkage of the ion exchange resin.

Example Under the same catalyst, substrate and reaction conditions as in the Hugue example,
The reaction was carried out without adding 1- of water.

As shown in Table A IK, the results showed that the high activity was excellent.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 using P-1 luenesulfonic acid instead of the ion exchange resin.

The results are shown in Table A, and it can be seen that the ion exchange resin has high activity.

Table A Example! After thoroughly washing the ion exchange resin used in the reaction in Example 3 with methanol, palladium acetate,
Equal amounts of triphenylphosphine, l-sehexane and methanol were added to the first reaction, and the reaction was carried out under the same reaction conditions and for the same time. Methyl dinandoate,
The yields of methyl α-methylcaproate and methyl α-ethelvalerate are sb, ochi, lza, hyoshi and co, respectively.
It was 3%. That is, it was confirmed that the ion exchange resin can be used repeatedly by such a method.

Example 6 A reaction was carried out in the same manner as in Example 6 except that methanol jm was used instead of methanol lj and toluene 10 was used as the solvent. The yields of methyl acetate, methyl α-methylcaproate, and methyl α-ethylvalerate were J/, 1%, g·5%, and 0.5%, respectively. q % and T of the total produced Nisder.

0, F, value is /? /Met.

Example In the system of Example 3, a reaction was carried out for 3 hours under the reaction conditions of 0° C. and a total pressure of 5 q/d. The yields of methyl dinandoate, methyl α-methylcaproate, and methyl α-ethylvalerate were 5z%, t%, and 1%, respectively, and T, O, F, The value was 2 Judas.

EXAMPLE A reaction was carried out using the same system as in Example 2, using diphenylisopropylphosphine instead of triphenylphosphine. The yields of methyl α-methylcaproate and methyl α-ethelvalerate were 29.
Article 7, 6. The T, O, F values of all produced esters were TRS.

Example 9 In the system of Example 3, palladium acetate o, ormmo
Bis(acetylacetonato)halazyme 0. The reaction was carried out using Oj mmol.

Methyl enanthate, methyl α-methylcaproate and α
- The yields of ethyl valerin methyl are 6 and 7%, respectively.
is, 17% and 0.95 bh, the T, O, F value of all produced esters was 321.

Example IO In the system of Example 3, methanol l! The reaction was carried out using ethanol is- instead of -. The yields of ethyl dinandoate, ethyl α-methylcaproate and ethyl α-ethylvalerate were 3/, jth, /:1. The values of T, O, and F of all produced esters were determined by λg.

Example // Haladium acetate 0. j mmol, triphenylphosphinha! r anol, Diaion ■PK-2 (7
45m@q, water l-1l-hexene jd, and toluene is- as the solvent.
The reaction was carried out at ℃ for 3 hours. Enanthic acid and α-methylcaproic acid were present in amounts of Q, CoII mmol and 0.0, respectively.
0ri-o1 was obtained.

Example 1 - In the undercurrent side 3 system, a reaction was carried out using cyclohexene j- instead of l-hexene Swt. Methyl cyclohexanecarboxylate was obtained in a modest yield and its T
, O,F, value was 3gg.

Example 13 In the system of Example J, l-hechitin! - Instead of -, straight chain l-olefin with 0 to t carbon atoms 4! ? When the reaction was carried out using n-butanol instead of methanol, an ester mixture corresponding to each olefin was obtained with a yield of 32%, and the T, O, ? , the value is 7
It was 9.41.

〔Effect of the invention〕

By the method of the present invention, diolefins can be efficiently carbonylated to obtain carboxylic acids, carboxylic esters, or carboxylic acid anhydrides.

The method of the present invention is industrially advantageous because there is less corrosion of the reactor and the separation between the product and the catalyst is easy.

Claims (1)

[Claims] (1) A method of carbonylating olefins by reacting olefins and carbon monoxide with a hydroxyl compound selected from the group consisting of water, alcohol, and carboxylic acid in the presence of a palladium catalyst, an organic phosphine, and an acidic compound. , at least 0.0 as the acidic compound
A method for carbonylating olefins, characterized in that a sulfonic acid-based cation exchanger having a proton exchange capacity of 5 meq/g is used.