JP2000136164A - Production of dicarboxylic acid diester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing under mild reaction conditions from an unsaturated hydrocarbon, carbon monoxide and an alcohol the subject dicarboxylic acid diester having two more carbon atoms than the unsaturated hydrocarbon, (i.e., such a diester that an ester group is added to the unsaturated bond of the unsaturated hydrocarbon) while suppressing the formation of byproduct oxalic diester and easily separating, recovering and circulating/reusing palladium catalyst, etc. SOLUTION: This method for producing the aimed dicarboxylic acid diester comprises reaction between an unsaturated hydrocarbon (e.g. an alkene), carbon monoxide and a nitrous ester in the presence of a catalyst with palladium immobilized on a strongly acidic cation exchanger >=0.01 meq/g in proton exchange capacity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an unsaturated hydrocarbon,
The present invention relates to a method for producing a diester of a dicarboxylic acid having two carbon atoms more than an unsaturated hydrocarbon from carbon monoxide and an alcohol source. For example, it relates to a method for producing a diester in which an ester group is added to an unsaturated bond (such as a carbon-carbon double bond) of an unsaturated hydrocarbon, such as succinic diester from ethylene and methyl succinic diester from propylene. Diesters of dicarboxylic acids are useful as raw materials for fragrances and resins.

[0002]

2. Description of the Related Art Diesters of dicarboxylic acids having two carbon atoms more than unsaturated hydrocarbons (diesters obtained by adding ester groups to unsaturated bonds of unsaturated hydrocarbons) from unsaturated hydrocarbons, carbon monoxide and alcohol sources. ) Is known as a method of reacting an unsaturated hydrocarbon, carbon monoxide, and an alcohol source (alcohol, nitrite, etc.) in the presence of a homogeneous palladium catalyst. 50-126608, JP-A-51-1412
JP, JP-A-53-40709, JP-A-61-40709
No. 289058). However, in these methods, since a homogeneous catalyst is used, separation, recovery, circulation and reuse of the palladium catalyst are complicated or difficult, and there is a problem as an industrial production method.

[0003] In addition, a method using a heterogeneous palladium catalyst is also known (JP-A-53-46913 and JP-A-54-81211). However, the former method using an activated carbon-supported palladium catalyst has a problem in that a large amount of oxalic acid diester, a product not involving unsaturated hydrocarbons, is by-produced. In the latter method using a palladium catalyst supported on activated carbon and a metal halide cocatalyst, the cocatalyst is uniformly dissolved in the reaction system, and the cocatalyst is separated, recovered, and circulated as in the case of the homogeneous catalyst. -There is a problem that reuse or the like is complicated or difficult.

[0004]

SUMMARY OF THE INVENTION The present invention relates to diesters of dicarboxylic acids having two carbon atoms more than unsaturated hydrocarbons (unsaturated bond of unsaturated hydrocarbons) from unsaturated hydrocarbons, carbon monoxide and alcohol sources. In the method of producing a diester having an ester group added thereto, a palladium catalyst or the like can be easily separated, recovered, circulated and reused,
An object of the present invention is to provide a method capable of producing a diester of a desired dicarboxylic acid by suppressing by-products of an oxalic acid diester under mild reaction conditions.

[0005]

An object of the present invention is to react an unsaturated hydrocarbon, carbon monoxide and a nitrite in the presence of a catalyst in which palladium is immobilized on a strongly acidic cation exchanger. It is solved by a method for producing a diester of a dicarboxylic acid characterized by the following.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a diester of a dicarboxylic acid (a diester in which an ester group is added to an unsaturated bond of an unsaturated hydrocarbon) includes an unsaturated hydrocarbon, carbon monoxide and a nitrite. It is produced by reacting a strongly acidic cation exchanger with palladium in the presence of an immobilized catalyst.

The unsaturated hydrocarbon used in the present invention includes, for example, ethylene, propylene, 1-butene, 2-
Examples thereof include linear or cyclic unsaturated hydrocarbons having 2 to 20 carbon atoms such as butene, isobutene, 1-hexene, and cyclohexene, and particularly linear or cyclic alkenes having 2 to 20 carbon atoms. These may have a substituent. Examples of the substituted or unsubstituted chain or cyclic alkene having 2 to 20 carbon atoms include styrene, vinylcyclohexene, vinyl methyl ether, and vinyl acetate.

[0008] Even carbon monoxide clean gas, but no problem be diluted with an inert gas such as nitrogen gas, 0.01 to 10 ⁴ moles of the unsaturated hydrocarbon 1 mole, more it is preferably used from 0.1 to 10 ³ moles. Further, the pressure is preferably 0.1 to 300 kg / cm ² , more preferably 0.5 to ²⁰⁰ kg / cm ² .

In the present invention, it is preferable to use a nitrite as the alcohol source, but the alcohol may be present in an amount of about 0 to 10 times the mole of the nitrite. Examples of the nitrite include those having 1 to 2 carbon atoms such as methyl nitrite, ethyl nitrite, propyl nitrite, and butyl nitrite.
And 0 alkyl nitrite. Among them, alkyl nitrite having 1 to 4 carbon atoms such as methyl nitrite, ethyl nitrite, propyl nitrite, and butyl nitrite is preferable. These nitrites may be prepared in advance, but nitrogen oxides such as nitrogen dioxide, dinitrogen trioxide, dinitrogen tetroxide, dinitrogen pentoxide and the corresponding alcohol are allowed to exist in the reaction system. Thus, the corresponding nitrite may be produced and used in the reaction system. Further, nitrite regenerated by reacting nitrogen dioxide generated in the reaction with corresponding alcohol and molecular oxygen may be used. The nitrite is preferably used in an amount of 0.01 to 20 times, more preferably 0.1 to 10 times, the mole of the unsaturated hydrocarbon.

The strongly acidic cation exchanger used in the present invention is preferably 0.01 meq / g or more, more preferably 0.01 to 0.01 meq / g.
Strongly acidic cation exchangers having a proton exchange capacity of 20 meq / g are preferred. As the strongly acidic cation exchanger, for example, a styrene-divinylbenzene copolymer,
Examples thereof include a phenol-formaldehyde copolymer or a perfluoroethylene polymer in which a sulfonic acid functional group is introduced, a sulfonated polyphenyl, a sulfonated cellulose, and the like. Specific examples of the sulfonated styrene-divinylbenzene copolymer include Dowex 50W (manufactured by Dow Chemical Company), and examples of the sulfonated perfluoroethylene polymer include Nafion NR-50 (manufactured by DuPont).

The catalyst in which palladium is immobilized on the strongly acidic cation exchanger can be prepared by a conventional ion exchange method using a palladium salt such as palladium acetate. For example, Inorganica Chemical
a A catalyst in which palladium is immobilized on Nafion NR-50 can be prepared by the method described in Acta, 150, 245-247 (1988). After washing and drying, the catalyst is preferably used as it is without reducing the immobilized palladium. The amount of immobilized palladium is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, based on the strongly acidic cation exchanger. The catalyst is preferably used such that the amount of immobilized palladium is 10 ^-5 to 1 mol, more preferably 10 ^-4 to 1 mol, per 1 mol of unsaturated hydrocarbon.

In the present invention, it is preferable to use one or more reaction solvents as necessary. The amount of the reaction solvent is not particularly limited as long as the reaction can be performed in a liquid phase. As the reaction solvent, for example, aromatic non-halogenated hydrocarbons such as benzene and toluene, aromatic halogenated hydrocarbons such as chlorobenzene, aliphatic non-halogenated hydrocarbons such as tetralin and cyclohexane, and methylene chloride and the like Aliphatic halogenated hydrocarbons, diethyl ether,
Ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, and ethyl acetate;
Esters such as ε-caprolactone; amides such as N, N-dimethylformamide and N-methylpyrrolidone; sulfones such as dimethyl sulfone and sulfolane; sulfoxides such as dimethyl sulfoxide; nitriles such as acetonitrile, benzonitrile and adiponitrile; And alcohols such as methanol, ethanol and butanol. Among these reaction solvents, aliphatic halogenated hydrocarbons, esters, and nitriles are preferred.

The reaction of the present invention is carried out, for example, in a pressure-resistant reactor.
After adding the catalyst and the nitrite, adding the unsaturated hydrocarbon, pressurized with carbon monoxide, under predetermined reaction conditions,
It can be carried out continuously or batchwise. In the case of a continuous reaction, the catalyst is used in a fixed or suspended bed. In addition,
In the present invention, the reaction temperature is 0 to 300 ° C., and furthermore 10 to 20 ° C.
Preferably it is 0 ° C.

After the reaction, the resulting diester of dicarboxylic acid is separated and purified by ordinary distillation. The catalyst is easily separated from the reaction solution by filtration or the like, washed with a solvent or the like, and then reused in the reaction.

[0015]

Next, the present invention will be described specifically with reference to examples. Example 1 [Preparation of catalyst] Under an argon gas atmosphere, 554 mg of palladium acetate was dissolved in 50 g of acetonitrile, and 10.02 g of Nafion NR-50 (manufactured by DuPont) was added thereto, followed by stirring at 68 ° C for 1 hour. After leaving overnight at room temperature, solvent removal by decantation, washing with acetonitrile, and drying were performed to obtain a yellow catalyst in which palladium was immobilized on Nafion NR-50. When the amount of immobilized palladium was measured by ICP analysis, it was 1.2% by weight based on the ion exchanger.

[Production of diester of dicarboxylic acid] 9 ml of acetonitrile, 1.07 g of the catalyst prepared above, and 9.5 mmol of n-butyl nitrite were placed in a 30 ml pressure-resistant reactor containing a Teflon rotor, and sealed. Then, a mixed gas of ethylene and carbon monoxide (ethylene: carbon monoxide (molar ratio) = 1: 1) so that the total pressure becomes 40 kg / cm ^2.
1) was introduced and the reaction was carried out at 50 ° C. for 1 hour. After the reaction was completed, the products were analyzed by gas chromatography to find that 1.04 mmol of dibutyl succinate and 0.02 mmol of dibutyl oxalate were formed.

Example 2 [Production of diester of dicarboxylic acid] The same operation as in Example 1 was carried out except that acetonitrile was changed to 9 ml of methylene chloride. As a result, dibutyl succinate 0.51 m
mol, 0.10 mmol of dibutyl oxalate.

Example 3 [Production of diester of dicarboxylic acid] The catalyst used in Example 2 was separated by filtration, washed sufficiently with acetonitrile and methylene chloride, and then used as a catalyst. The same operation was performed. As a result, dibutyl succinate 0.69 mmol and dibutyl oxalate 0.0
5 mmol had been formed.

Example 4 [Production of diester of dicarboxylic acid] Acetonitrile 10 was placed in a 50 ml pressure-resistant reactor containing a Teflon rotor.
8. ml, 1.00 g of a catalyst prepared as described above (amount of immobilized palladium: 1.0% by weight), and n-butyl nitrite
After 9 mmol was added and sealed, the vessel was cooled and 1.3 g (31.0 mmol) of propylene was introduced. Thereafter, carbon monoxide was introduced so that the total pressure became 70 kg / cm ^2, and the reaction was carried out at 75 ° C. for 1 hour. After the reaction was completed, the product was analyzed by gas chromatography to find that dibutyl methyl succinate (1.91 mmol) and dibutyl oxalate (0.02 mmol) were produced.

Example 5 [Production of diester of dicarboxylic acid]
The total pressure was 5 instead of 0.8 g (14.3 mmol) of butene.
The same operation as in Example 4 was performed except that carbon monoxide was introduced so as to be 0 kg / cm ² . As a result, 1.41 mmol of dibutyl ethyl succinate and 0.01 mmol of dibutyl oxalate were produced.

Example 6 [Production of diester of dicarboxylic acid] The procedure of Example 1 was repeated except that propylene was replaced with 1.00 g (9.10 mmol) of vinylcyclohexane and carbon monoxide was introduced so that the total pressure became 50 kg / cm ^2. The same operation as in Example 4 was performed. As a result, dibutyl cyclohexylsuccinate 1.59 mm
ol and 0.01 mmol of dibutyl oxalate.

Example 7 [Preparation of catalyst] Nafion NR-50 was converted to Dowex 5
The same operation as in Example 1 was performed except that 3.0 g of 0W-8X (manufactured by Dow Chemical) was used. The amount of immobilized palladium in the obtained catalyst was 7.2% by weight.

[Production of diester of dicarboxylic acid] Example 1 was repeated except that 0.50 g of the above catalyst was used as a catalyst.
The same operation as described above was performed. As a result, dibutyl succinate 0.80 mmol, dibutyl oxalate 0.12 mmol
Had been generated.

[0024]

According to the present invention, diesters of dicarboxylic acids having two carbon atoms more than unsaturated hydrocarbons (ester groups are formed on unsaturated bonds of unsaturated hydrocarbons) from unsaturated hydrocarbons, carbon monoxide and alcohol sources. In the process for producing the added diester), the palladium catalyst and the like can be easily separated, recovered, circulated, and reused. Can be produced.

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Claims (3)

[Claims] 1. A method for producing a diester of a dicarboxylic acid, comprising reacting an unsaturated hydrocarbon, carbon monoxide, and a nitrite in the presence of a catalyst having palladium immobilized on a strongly acidic cation exchanger. Method. 2. The method for producing a diester of a dicarboxylic acid according to claim 1, wherein the unsaturated hydrocarbon is an alkene. 3. The method according to claim 1, wherein the strongly acidic cation exchanger is 0.01 meq.
The method for producing a diester of a dicarboxylic acid according to claim 1, which has a proton exchange capacity of at least / g.