JPH10114698A - Carbonylation process and production of carbonylated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep the catalytic activity over a long period and suppress the formation of by-products by reacting an acetylenic or olefinic unsaturated compound with carbon monoxide having low hydrogen content ion the presence of a carbonylation catalyst. SOLUTION: An acetylenically or olefinically unsaturated compound (preferably a 2-10C α-acetylenically or α-olefinically unsaturated compound) is carbonylated by reacting with carbon monoxide in the presence of a carbonylation catalyst. The reaction is carried out by using carbon monoxide having a hydrogen content of <=5vol.%, preferably 0.01-1vol.%. The catalyst preferably contains a contains a complex or a complex salt of palladium or platinum. The catalyst may be incorporated with a ligand or an acid. The ligand is preferably a tertiary organic phosphine such as triphenylphosphine. Preferably, the amount of the catalyst is 1×10<-4> to 1×10<-2> mol in terms of metallic atom and that of carbon monoxide is 1-5mol based on 1mol of the unsaturated compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method useful for carbonylating an acetylenic or olefinically unsaturated compound using a carbonylation catalyst to obtain an α, β-ethylenically unsaturated compound such as methyl methacrylate. About.

[0002]

2. Description of the Related Art An .alpha.,. Beta.-ethylenically unsaturated compound such as methyl methacrylate is an industrially useful compound as a raw material (monomer) for a synthetic resin. The α, β-
As a method for producing an ethylenically unsaturated compound, the acetone cyanohydrin method using acetone as a raw material is widely used industrially. In this method, a large amount of waste sulfuric acid and waste ammonium bisulfate are by-produced.

In recent years, as a method for obtaining an α, β-ethylenically unsaturated compound such as an alkyl methacrylate without using sulfuric acid, a carbonylation catalyst composed of a metal source of a Group VIII metal of the periodic table and phosphine has been used. Below, a carbonylation method has been proposed in which an acetylene-based and olefin-based unsaturated compound is reacted with carbon monoxide, an alcohol or the like. For example, EP-A1-10637
9, EP-A1-235864, EP-A1-2747
95, EP-A1-279777 discloses a method for carbonylating acetylene-based and olefin-based compounds using a carbonylation catalyst composed of a palladium compound, a triarylphosphine and a protonic acid.

Japanese Patent Publication No. 5-29212, Japanese Patent Application Laid-Open No. Sho 61
JP-176549, JP-A-62-72649 and JP-A-63-154646 disclose acetylene-based compounds in the presence of a carbonylation catalyst composed of a divalent palladium compound, an organic phosphine, and a protonic acid. Methods for carbonylating unsaturated compounds are disclosed. Further, JP-A-4-215851 discloses an acetylene catalyst using a carbonylation catalyst comprising a Group VIII metal source, a phosphine having an aromatic substituent containing an imino nitrogen atom, a proton source and an alkylsulfonic acid anion source. Methods for carbonylating olefin-based and olefinic compounds are disclosed. Japanese Patent Application Laid-Open No. Hei 4-215852 discloses a
A method for carbonylating acetylenic and olefinic compounds using a catalyst comprising a Group VIII metal source, a phosphine having an aromatic substituent containing an imino nitrogen atom, a proton source and a tertiary amine is disclosed.

JP-A-8-84933 discloses a catalyst comprising a Group VIII metal source excluding palladium, a non-heterocyclic ligand not containing a nitrogen atom as a hetero atom, a proton source and a catalyst containing an electron-donating compound. A method for carbonylating an acetylene-based compound and an olefin-based compound by carbonylation is disclosed.

When an alkyl methacrylate such as methyl methacrylate is industrially produced by using these carbonylation catalysts, not only does the catalytic activity significantly decrease with the progress of the carbonylation reaction, but also the secondary activity of alkyl isobutyrate and the like increases. A large amount of the product is produced, and the production efficiency of the alkyl methacrylate is reduced. Further, the effective amount of the metal source constituting the catalyst decreases as the reaction proceeds. Further, the by-product of the isobutyric acid alkyl ester is
In the production of methacrylic acid alkyl esters, there is a great industrial disadvantage. That is, the alkyl isobutyrate has very similar chemical properties (eg, boiling point) to the alkyl methacrylate of the target compound. Therefore, even if a separation method such as distillation is used for the alkyl methacrylate, isobutyric acid is used. The alkyl ester cannot be separated and removed, and the quality of the alkyl methacrylate deteriorates due to the mixed alkyl isobutyrate.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a carbonylation method capable of maintaining the catalytic activity of a carbonylation catalyst for a long period of time and suppressing the generation of by-products. Another object of the present invention is to provide carbonylation of acetylenic or olefinically unsaturated compounds,
An object of the present invention is to provide a carbonylation method capable of industrially and advantageously producing carbonylation reaction products such as carboxylic acids and carboxylic acid esters with high conversion and selectivity over a long period of time. Still another object of the present invention is to be useful for stably producing an α, β-ethylenically unsaturated carboxylic acid such as methyl methacrylate or a derivative thereof for a long period of time while suppressing generation of by-products. It is to provide a carbonylation method.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, in a carbonylation method for reacting an unsaturated hydrocarbon with carbon monoxide in the presence of a carbonylation catalyst, the present invention has been made. The present inventors have found that a specific amount of hydrogen contained in carbon oxide has an effect on the catalytic activity and the formation of by-products, and completed the present invention.

That is, the carbonylation method of the present invention comprises:
A carbonylation method for reacting an acetylenic or olefinically unsaturated compound with carbon monoxide in the presence of a carbonylation catalyst, characterized by using carbon monoxide having a hydrogen content of 5% by volume or less. It is a carbonylation method. The carbonylation catalyst includes, for example, a catalyst composed of (1) a metal source of Group VIII metal of the periodic table, (2) a ligand, and (3) an acid. The Group VIII metal element includes, for example, at least one selected from cobalt, nickel, rhodium, palladium, and platinum. The ligand includes, for example, a phosphorus compound.

In the carbonylation method of the present invention, the acetylenic or olefinically unsaturated compound is α-
An acetylene-based or α-olefin-based unsaturated compound is included. In this method, when water, an alcohol, an organic carboxylic acid, or the like is further reacted, a saturated or unsaturated carboxylic acid or a derivative thereof (e.g., an α, β-unsaturated Esters such as acid esters or acid anhydrides).

In the present specification, the term "olefin-based unsaturated compound" means a compound having an ethylenically unsaturated double bond, regardless of the number of double bonds. Further, “hydrogen content” means the amount (ratio) of hydrogen to the total amount of carbon monoxide and hydrogen.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [Carbonylation catalyst] (1) Group VIII metal source in the periodic table The carbonylation catalyst contains at least a group VIII metal source in the periodic table. Group VIII metal elements include, for example, iron F
e, ruthenium Ru, osmium Os, cobalt Co,
Rhodium Rh, iridium Ir, nickel Ni, palladium Pd and platinum Pt are included. In addition, since 1990, the above-mentioned elements have been referred to as Group 8 elements of the periodic table (Fe,
Ru, Os), Group 9 elements (Co, Rh, Ir),
It is classified into Group 0 elements (Ni, Pd, Pt).

Preferred Group VIII metal elements include at least one selected from cobalt, rhodium, nickel, palladium and platinum. More preferably, they include cobalt, palladium and platinum, especially palladium and platinum. The oxidation number of the element is not particularly limited, and for example, 0, +2, +3, +
4 or the like. The group VIII metal source of the periodic table comprises:
It may be a simple metal, but is preferably a compound of a Group VIII metal element of the periodic table.

Compounds of Group VIII metal elements include, for example, inorganic acid salts (for example, hydrohalides such as nitrates, sulfates, perhalates, hydrochloric acid and hydrobromic acid); Organic acid salts (e.g., sulfonic acid salts such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, phosphonates, formic acid, acetic acid,
Carboxylates having 12 or less carbon atoms such as propionic acid, etc.), halides (eg, chloride, bromide, iodide, etc.), complexes (or complex salts) and the like are included.

The ligand constituting the complex is, for example, OH
(Hydroxo), a C _1-4 alkoxy group, a C _1-4 acyl group,
C _1-4 alkoxy-carbonyl group, acetylacetonato, cyclopentadienyl group, cyclooctadienyl group, benzylidene group, benzylideneacetone, benzylidene acetylacetone, benzylidene acetophenone, cycloalkadiene such as cyclooctadiene, halogen atom, CO , CN, oxygen atom, H ₂ O (Ako),
Phosphines (eg, triarylphosphines such as triphenylphosphine), NH ₃ (ammine), NO,
Examples include nitrogen-containing compounds such as NO ₂ (nitro), NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline. In the complex or complex salt, the same or different ligands may be coordinated by one kind or two or more kinds.

Examples of the complex or complex salt include acetylacetone palladium, tetrakis (triphenylphosphine) palladium, bis (tri-o-tolylphosphine) palladium acetate, bis (diphenyl-2-pyridylphosphine) palladium acetate and bis (diphenyl-palladium). Palladium complexes or complex salts such as 2-pyridylphosphine) palladium, tetrakis (diphenyl-2-pyridylphosphine) palladium, bis (di-o-tolylpyridylphosphine) palladium acetate, bis (diphenylpyridylphosphine) palladium sulfate; dibenzylideneacetone platinum Dibenzylidene acetylacetone platinum, dibenzylidene acetophenone platinum, dibenzylidene ketone platinum, dicyclooctadiene platinum, dichlorobi (Triphenylphosphine) platinum, acetate bis (triphenylphosphine) platinum, sulfate bis (triphenylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (diphenyl -
2-pyridylphosphine) platinum, hexachloroplatinum (I
V) Platinum complexes or complex salts such as acids, and the corresponding complexes or complex salts of the Group VIII elements of the Periodic Table. Of these Group VIII metal sources, compounds of Group VIII metal elements, particularly complexes or complex salts, are often used.

(2) Ligand The catalyst may contain a ligand, if necessary. This ligand is often different from the ligand constituting the metal compound (complex or complex salt) of Group VIII of the periodic table. An organic phosphorus compound containing at least one phosphorus atom,
It includes an organic arsenic compound containing an arsenic atom, an organic antimony compound containing an antimony atom, and the like, and among them, an organic phosphorus compound (particularly, organic phosphine) is preferable. In many cases, these ligands can coordinate with a Group VIII element of the periodic table. The ligands can be used alone or in combination of two or more. The organic phosphine as the ligand may be any of a first phosphine (eg, isobutylphosphine, phenylphosphine, cyclohexylphosphine, etc.), a second phosphine (eg, diisobutylphosphine, diphenylphosphine, dicyclohexylphosphine, etc.) and a third phosphine. You may. Preferred organic phosphines include a third organic phosphine (particularly, a third organic phosphine having an aromatic homo- or heterocyclic group which may have a substituent).
Organic phosphine and a third organic phosphine having an aryl group which may have a substituent).

Examples of the third organic phosphine include triarylphosphine which may have a substituent such as triphenylphosphine, tri (4-methylphenyl) phosphine, tri (4-methoxyphenyl) phosphine; methyldiphenyl Mono C _1-10 alkyl diaryl phosphines such as phosphine and ethyl diphenyl phosphine; di C _1-10 alkyl mono aryl phosphine such as dimethyl phenyl phosphine and diethyl phenyl phosphine; tri C _1-10 alkyl phosphine such as trimethyl phosphine and triethyl phosphine ; di C _4-10 cycloalkyl monoaryl phosphines such as dicyclohexyl phenylphosphine; mono C _4-10 cycloalkyl diaryl phosphines such as cyclohexyl diphenylphosphine tricyclohexylphosphine Tri _C4-10 cycloalkyl phosphines such as phosphine; ethane-1,2-diylbisdiphenylphosphine, ethene-1,2-diylbisdiphenylphosphine, ethyne-1,2-diylbisdiphenylphosphine, 1,2-phenylene Bisdiphenylphosphine, hexafluorocyclopentene-1,2-
Diylbisdiphenylphosphine; 2-pyridylbisphenylphosphine, bis (2-pyridyl) phenylphosphine, tris (2-pyridyl) phosphine, tris (6-methyl-2-pyridyl) phosphine, 2-pyridylbismethylphosphine, bis ( 2-pyridyl) methylphosphine, 6-methoxy-2-pyridylbisphenylphosphine, bis (6-methoxy-2-pyridyl) phenylphosphine, bisphenyl (4,6-dimethyl-2)
-Pyridyl) phosphine, bis (6-chloro-2-pyridyl) phenylphosphine, bis (6-bromo-2-pyridyl) phenylphosphine, 2,6-bis (diphenylphosphino) pyridine, 2,6-bis (di Examples thereof include phosphines having a nitrogen-containing heterocyclic group such as a pyridyl group such as (p-tolylphosphino) pyridine.

As the organic phosphine, an inexpensive and highly versatile triarylphosphine such as triphenylphosphine which may have a substituent is often used. As the ligand, an organic arsenic compound (particularly, third organic arsine) or an organic antimony compound (particularly, third organic stibine) corresponding to the above-described organic phosphorus compound can also be used.

(3) Acid Further, the catalyst may contain an acid. The acids include, for example, various protic acids (inorganic and organic) and Lewis acids. Protic acids include, for example, inorganic acids (eg, sulfuric acid, nitric acid, hydrohalic acid, phosphoric acid, perhalic acid, heteropoly acid, etc.) and organic acids (eg, sulfonic acid, phosphonic acid, carboxylic acid, amino acid, etc.) And so on. These acids can be used alone or in combination of two or more. Because the acid functions as a proton source, or when a Lewis acid is used, it is often used in combination with another proton source.

The inorganic acids include, for example, sulfuric acid; nitric acid; hydrohalic acids such as hydrochloric acid and hydrobromic acid; phosphoric acids such as orthophosphoric acid and pyrophosphoric acid; perhalic acids such as perchloric acid; Heteropoly acids containing V, W or Mo, such as molybdic acid, silicotungstic acid, and vanadomolybdic acid, and the like.

Examples of the organic acid include aryl sulfonic acids which may have a substituent such as benzene sulfonic acid, p-toluene sulfonic acid and naphthalene sulfonic acid; methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, Alkyl sulfonic acids which may have a substituent such as t-butyl sulfonic acid, 2-hydroxypropane sulfonic acid, trichloromethane sulfonic acid, trifluoromethane sulfonic acid; phosphonic acids such as benzene phosphonic acid; chloroacetic acid, dichloroacetic acid , Trichloroacetic acid, trifluoroacetic acid, acetylacetic acid, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearin It may have a substituent such as acid and oxalic acid. Unsaturated aliphatic carboxylic acids such as saturated aliphatic carboxylic acids, acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, and cycloaliphatic carboxylic acids such as cyclohexanecarboxylic acid Examples include carboxylic acids such as aromatic carboxylic acids such as acids, benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid; and amino acids such as aspartic acid and glutamic acid. The acid may be an acidic ion exchange resin, for example, an ion exchange resin having a sulfonic acid group, a phosphonic acid group, a phosphinic acid group and the like.

The Lewis acids include, for example, (C ₂ H ₅ ) OB
F ₃ , BF ₃ , AlCl ₃ , SnCl ₄ , SnCl ₂ , Ti
Cl ₄ , Ti [OCH (CH ₃ ) ₂ ] ₄ , NbF ₅ , Ta
_{F 5, PF 5, AsF 5} , the periodic table IIIB such as SbF ₅
Group, group IVA, group IVB, group VA and group VB halides or complex compounds thereof, or alkoxides (eg, C _1-5 alkoxides).

Preferred acids are protic acids, for example, inorganic acids such as sulfuric acid, hydrohalic acid, phosphoric acid and the like, sulfonic acids (arylsulfonic acids and alkylsulfonic acids),
Organic acids such as carboxylic acids (saturated and unsaturated aliphatic carboxylic acids) are included.

The proportion of each component constituting the catalyst can be selected in accordance with the type of each catalyst component and the like, as long as the catalyst activity is not impaired and the stability can be maintained. The proportion of the ligand is, for example, about 0.1 to 1000 mol, preferably about 0.5 to 500 mol, more preferably about 1 to 100 mol, per 1 mol of the Group VIII metal source in the periodic table. 1 to
It is often about 50 moles. The ratio of the acid (protic acid or the like as a proton source) is, for example, 0.1 to 1000 mol, preferably 1 to 1 mol per 1 mol of the group VIII metal source.
It is about 500 mol, more preferably about 5 to 250 mol, and often about 1 to 100 mol. The ratio of the ligand to 1 mol of an acid such as a protonic acid is not particularly limited, and is, for example, 0.01 to 50 mol, preferably 0.02 mol.
10 to 10 mol, more preferably about 0.05 to 5 mol, and often about 0.03 to 3 mol.

The catalyst may be either a homogeneous catalyst or a heterogeneous catalyst. When used for liquid phase reactions, the catalyst is usually homogeneous. If necessary, the catalyst may constitute a solid catalyst in which a catalyst component is supported on a carrier such as activated carbon, alumina, or silica.

The catalyst may contain an oligomer or polymer type organic phosphine in which an organic phosphine is bonded to a homopolymer or a copolymer as required, for example, to improve the catalytic activity or to suppress the decrease in the catalytic activity.

[Carbonylation reaction of acetylenic or olefinically unsaturated compound] In the carbonylation method of the present invention, an acetylenic or olefinic unsaturated compound is
A carboxylic acid or a derivative thereof is produced by reacting carbon monoxide with water, an alcohol, or a carboxylic acid as required.

Acetylene or olefinic unsaturated compound
Object acetylenic or olefinic unsaturated compound, preferably acetylene compounds of asymmetric or olefinic compounds, more preferably α- acetylenic compounds, alpha
-An olefin compound or an allene compound. The carbon number of the acetylene-based unsaturated compound is usually about 2 to 30, preferably 2 to 20, particularly about 2 to 10. The carbon number of the olefinically unsaturated compound and the allene-based compound is, for example, 2 to 30. , Preferably 2 to 20, especially 2 to
It is about 10. These unsaturated hydrocarbons include optionally substituted alkynes, alkenes (olefins), cycloalkenes, cycloalkadienes and bridged unsaturated hydrocarbons. The unsaturated hydrocarbon is 1
The molecule may have a triple bond and a double bond, or may have two or more double bonds.

Examples of the alkyne include acetylene,
Propyne, 1-butyne, 2-butyne, 1-pentyne, 1
-Hexyne, 1-heptin, 1-octin, 2-octy
, 4-octyne, 1,7-octadiyne, 5-methyl
-3-heptin, 4-propyl-2-pentyne, 1-no
Nin, phenylacetylene, benzylethyne and cycle
Lohexyl ethyne and the like can be exemplified. Lower unsaturated carbo
When the acid ester is produced, the alkyne is α-
Acetylene hydrocarbons, for example, acetylene, propyne
C such as (methylacetylene)_2-6 Place where alkyne is used
Often. Alkenes include, for example, ethylene, propylene
Phenylethylene, 1-butene, 2-butene, 1-
Pentene, 3-methylpentene-1, 4-methylpente
-1,1-hexene, 1-heptene, 1-octene,
Allene type conversion of 2-octene, 4-octene, allene, etc.
Compounds, cyclohexene and norbornadiene, etc.
I will. For producing lower saturated or unsaturated carboxylic acids
In the case where the alkene is an α-olefin hydrocarbon, for example,
For example, C such as ethylene, propylene, and allene _2-6 Al
Ken is often used.

[0031] The unsaturated hydrocarbon may be substituted by various substituents, e.g., halogen atoms such as fluorine, chlorine, bromine; C _4-10
Aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; cyano groups; C _1-7 acyl groups such as formyl and acetyl groups; C _2-7 acyloxy groups such as acetyloxy groups; hydroxyl groups; _C1-6 alkoxy group such as ethoxy group; haloalkyl group such as trifluoromethyl and trichloromethyl group; haloalkoxy group such as trifluoromethoxy and trichloromethoxy group; carboxyl group; _C1-6 alkoxy such as methoxycarbonyl group -Carbonyl group; N-substituted amino group such as amino group, monoalkylamino group and dialkylamino group; and N-substituted amide group such as amide group and acetamido group.

[0032] Characteristics of the carbon monoxide present invention, the presence of the carbonylation catalyst, a carbon monoxide used in the carbonylation reaction of unsaturated hydrocarbons, hydrogen content 5% by volume or less [0-5 volume% ( For example, 0.0001 to 5% by volume), preferably 0.001%.
To 3% by volume, more preferably about 0.01 to 2% by volume, particularly about 0.01 to 1% by volume]. When the hydrogen content in carbon monoxide exceeds 5% by volume, the catalytic activity is remarkably reduced as the carbonylation reaction proceeds, and a large amount of by-products is produced. Further, the metal source constituting the catalyst is deposited, and the effective amount of the metal source is significantly reduced. Therefore, in the method of the present invention, a carbonylation product (a carboxylic acid or a derivative thereof) can be continuously and stably produced over a long period of time.

In the present invention, carbon monoxide which is inexpensive and easily available industrially can be used, and is extremely economically advantageous in industrially carbonylating an acetylenic or olefinically unsaturated compound.

As carbon monoxide, carbon monoxide obtained by various industrial production methods can be used. For example, carbon monoxide produced by the decomposition of methyl formate and containing no hydrogen can be used. However, since carbon monoxide produced by the decomposition of the methyl formate is expensive, industrially, usually, carbon monoxide produced by partial oxidation of coal coke, petroleum coke, asphalt, naphtha or natural gas, etc. Is used. Therefore, carbon monoxide used industrially usually contains hydrogen. For example, in the case of producing carbon monoxide by naphtha reforming, the generation ratio of hydrogen and carbon monoxide is, for example, hydrogen / carbon monoxide (volume ratio) = 1/1 to 1
It is about 2/1. In the present invention, even carbon monoxide containing such a relatively large amount of hydrogen can be used by removing hydrogen or adjusting the hydrogen concentration. Hydrogen in carbon monoxide can be removed by, for example, a cryogenic separation method or a pressure swing adsorption method (PSA method). In addition, in order to completely remove hydrogen in carbon monoxide, equipment costs, utility costs, and the like become large, which is economically disadvantageous. Therefore, industrially, usually, a small amount of hydrogen is contained. Carbon monoxide has been used. In the present invention, carbon monoxide containing such a small amount of hydrogen (for example, when the hydrogen content is 0.0001 to 5% by volume (preferably 0.001
-3% by volume) of carbon monoxide) can very advantageously be used industrially to produce carbonylation products.

The carbon monoxide may be diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide before use.

Other Reactants The unsaturated hydrocarbon may be carbonylated alone,
The carbonylation may be carried out in the presence of another reactant (eg, a nucleophilic compound having hydrogen or a removable hydrogen atom). The nucleophilic compound having a removable hydrogen atom includes, for example, water, a compound having a hydroxyl group (eg, alcohols), a carboxylic acid, and the like.

The alcohol may be an aliphatic, alicyclic, aromatic alcohol or phenol, or a monohydric or polyhydric alcohol. The alcohols also include silanols. The alcohols may have one or more substituents other than the hydroxyl group among the substituents described in the section of the unsaturated hydrocarbon. Monohydric alcohols include, for example, methanol, ethanol, 1-
Propanol, 2-propanol, 1-butanol, 2
-Butanol, 1-methylpropan-1-ol, 2-
Methylpropan-2-ol, 1-pentanol, 1-
Saturated aliphatic alcohols such as hexanol, 1-octanol, 2-ethylhexanol and stearyl alcohol; unsaturated aliphatic alcohols such as allyl alcohol and propargyl alcohol; cyclopentanol, cyclohexanol, 4-methylcyclohexanol, cycloheptanol; Alicyclic alcohols such as cyclooctanol and borneol; aromatic alcohols such as benzyl alcohol; Phenols include phenol, alkylphenol, resorcinol, 2,2-
Bis (4-hydroxyphenyl) propane and the like.

The polyhydric alcohol includes compounds having 2 to 6 hydroxyl groups in the molecule, for example, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and the like.

Preferred alcohols include those having 1 to 2 carbon atoms.
About 0, especially about 1 to 10 carbon atoms, especially 1 to 1 carbon atoms
It contains about 5 monohydric alcohols. As the alcohol, a saturated aliphatic alcohol (particularly, methanol) is often used.

The carboxylic acids include, for example, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, pivalic acid,
Valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, aliphatic carboxylic acids such as stearic acid, alicyclic carboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, phthalic acid, isophthalic acid, Examples include aromatic carboxylic acids such as terephthalic acid, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and oleic acid.

As the nucleophilic compound having a removable hydrogen atom, water and / or alcohol are often used.

In the carbonylation reaction, for example, when water is used as a reactant, carboxylic acid and α, β-
An unsaturated carboxylic acid such as an unsaturated carboxylic acid is formed.
When alcohols are used, esters corresponding to the carboxylic acids and unsaturated carboxylic acids are formed. Furthermore, when a carboxylic acid is used, an acid anhydride corresponding to the carboxylic acid and the unsaturated carboxylic acid is generated. More specifically, for example, when allene is used as the olefinically unsaturated compound and methanol is used as the reactant, methyl methacrylate is generated by the reaction with carbon monoxide.
Also, when propyne or acetylene is used as the acetylene-based unsaturated compound and methanol is used as a reactant,
Methyl methacrylate or methyl acrylate is formed.

In a preferred method, the acetylenic or olefinically unsaturated compound includes acetylene, propyne,
Methods using allene, ethylene, propylene and the like are included. In particular, acetylene-based or olefin-based compounds such as acetylene, propyne and other C _2-4 alkynes, allenes and other conjugated C _2-4 alkadienes, and C _1-20 alcohols as reactants are used to form α, β- A method for producing an ethylenically unsaturated carboxylic acid ester (particularly an alkyl (meth) acrylate) is preferred.

The proportion of each component in the carbonylation reaction can be selected within a wide range. For example, the proportion of the catalyst is 1 mole as the metal atom of the Group VIII metal source per 1 mole of the acetylenic or olefinically unsaturated compound. × 10 ^{-6 to} 2 ×
It is about 10 ^-1 mol, preferably about 1 x 10 ^-5 to 1 x 10 ^-1 mol, and often about 1 x 10 ^-4 to 1 x 10 ^-2 mol.

The ratio of carbon monoxide is, for example, 0.1 to 100 mol (for example, 1 to 50 mol), preferably 0.8 to 10 mol, per mol of the acetylenic or olefinic unsaturated compound. Mol (for example, 1 to 10 mol), and more preferably about 1 to 5 mol. Carbon monoxide is
In many cases, an excess mole (for example, about 1 to 20 moles) is used per mole of the acetylenic or olefinically unsaturated compound, and the reaction system may be used as a large excess carbon monoxide atmosphere. The amount of the alcohol used as a reactant is, for example, 0.1 to 100 mol (for example, 1 to 5 mol) per 1 mol of the acetylenic or olefinically unsaturated compound.
0 mol), preferably 1 to 25 mol (for example, 1 to 10 mol), and more preferably about 1 to 5 mol. When an alcohol is used as a reactant, it is often an excess mole (for example, about 1 to 10 moles) relative to 1 mole of the unsaturated compound. The reactant can be used as a reaction solvent.

The carbonylation reaction can be carried out efficiently in either a liquid phase system or a gas phase system. When the reaction is performed in a liquid phase system, the reaction can be performed in a solvent inert to the reaction.
As such a solvent, a wide range of organic solvents can be used, but in many cases, an electron-donating compound having coordination with the Group VIII metal element (for example, amines and ethers) is used.

Examples of the organic solvent include hydrocarbons (for example, aliphatic hydrocarbons such as hexane and octane;
Alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; chloroform;
Halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, and chlorobenzene; amines (eg, aliphatic amines such as ethylamine and triethylamine; alicyclic amines such as cyclohexylamine);
Aromatic amines such as aniline and N-methylaniline; alkanolamines such as triethanolamine; heterocyclic amines such as imidazole, pyridine, α-picoline, lutidine, bipyridine, o-toluidine and piperidine; and imines (eg. , Ethyleneimine, N-phenylethyleneimine, etc.), amides (eg, N, N
Dimethylformamide, etc.), sulfoxides (eg, dimethylsulfoxide, diisopropylsulfoxide, etc.), aldehydes (eg, aliphatic aldehydes such as acetaldehyde; aromatic aldehydes such as benzaldehyde), ethers (eg, diethyl ether, diethylene glycol dimethyl ether) Chain ethers such as anisole and diphenyl ether; cyclic ethers such as tetrahydrofuran, 1,3-dioxolan, tetrahydropyran, and 1,4-dioxane), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone) Aliphatic ketones; alicyclic ketones such as cyclohexanone; aromatic ketones such as acetophenone); lactones (eg, ε-capro Octone); esters (eg, organic carboxylic acid alkyl esters such as methyl acetate and ethyl propionate; unsaturated carboxylic acid alkyl esters such as methyl (meth) acrylate); and nitriles (eg, acetonitrile, acrylonitrile, benzol). A nitro compound (eg, an aliphatic nitro compound such as nitromethane; an aromatic nitro compound such as nitrobenzene), or a mixed solvent thereof.

When the above-mentioned (3) acid or reactant (such as alcohol) is used as the solvent, it is not necessary to use the above-mentioned organic solvent.

In the reaction system, a resin or an ion having a basic group such as an amino group, a substituted amino group (for example, a mono- or dialkylamino group) or a quaternary ammonium group may be used, if necessary, for example, to improve the catalytic activity. Exchange resin (for example,
For example, an amine resin such as a pyridine resin formed by a reaction between pyridine and formaldehyde may be added.

The carbonylation reaction is, for example, 10 to 25.
0 ° C., preferably 25-200 ° C., more preferably 3 ° C.
In many cases, the reaction is performed at a temperature of about 0 to 170 ° C. and a normal pressure to about 150 atm (preferably normal pressure to about 100 atm, usually about 10 to 70 atm). The reaction can be performed by a conventional method such as a batch system, a semi-batch system, or a continuous system. In the present invention, since the catalytic activity can be maintained for a long period of time, and by-products are hardly generated, carbon monoxide having a hydrogen content of 5% by volume or less (preferably 0.001 to 3% by volume) is supplied. However, it is advantageous to carry out the reaction continuously.

In the present invention, the generation of by-products, which are extremely difficult to separate from the target reaction product, can be suppressed. For example,
When producing alkyl methacrylate, alkyl isobutyrate, which is extremely difficult to separate from alkyl methacrylate, is hardly produced as a by-product. for that reason,
The reaction product can be easily separated and purified by a conventional method, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or the like, or a separation method combining these.

[0052]

According to the carbonylation method of the present invention, the catalytic activity can be maintained for a long period of time, and the generation of by-products can be suppressed. Further, it is possible to suppress a decrease in the effective amount of the metal source constituting the catalyst over a long period of time. Therefore, the acetylene-based or olefin-based unsaturated compound can be carbonylated at a high conversion and selectivity, and a carbonylation product such as a carboxylic acid or a carboxylic acid ester can be industrially advantageously produced. In addition, an α, β-ethylenically unsaturated carboxylic acid such as methyl methacrylate or a derivative thereof can be stably and continuously produced over a long period of time without generating by-products.

[0053]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Using a device in which a gas-liquid separator and a distillation column were connected to a pressure vessel with stirring and having a capacity of 1000 mL, in which methyl methacrylate was coated with a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, was used. Continuously manufactured.

The pressure vessel (reaction vessel) has supply ports for supplying propyne, carbon monoxide, methanol, methacrylic acid, and a circulating catalyst solution, respectively, and has a constant level of the reaction mixture in the reaction vessel. An outlet for the reaction mixture was provided to maintain The reaction mixture extracted from the outlet of the reaction vessel is separated into gas components (non-condensed components and dissolved gas components) and liquid components by a gas-liquid separator at normal pressure, and the separated liquid components are supplied to the distillation column. Then, the desired compound (methyl methacrylate) was obtained from the top of the distillation column, and the low liquid (circulating catalyst solution) of the distillation column containing the catalyst component was circulated to the reaction vessel at a rate of 468 g / h.

In this reaction vessel, 5.66 g of tetrakistriphenylphosphine platinum and triphenylphosphine 2
0.6 g, methacrylic acid 81.0 g, anisole 401
g and 91.5 g of methanol, and a mixed liquid having the same composition as the charged mixed liquid was supplied also to a gas-liquid separator and a distillation column. The reaction mixture is drawn out from the outlet using a liquid level meter so that the reaction mixture is always 600 g in the reaction vessel, and the hydrogen content is 0.1% by volume. 21.6 L / h of carbon oxide, 25.7 g / h of propyne, 80.2 g / h of methanol, and 5 g / h of methacrylic acid are supplied from each supply port in order to keep the methacrylic acid concentration in the reaction solution constant. Then, the reaction was continuously performed at a reaction temperature of 140 ° C. and a reaction pressure of 55 atm.

Twenty hours after the start of the reaction, the concentration of platinum in the circulating liquid was 1,749 ppm, the amount of methyl methacrylate obtained from the top of the distillation column was 66.6 g / h, and no methyl isobutyrate was detected. The reaction was further continued for 480 hours, and 500 hours after the start of the reaction, the platinum concentration in the circulating solution was 17
It was 12 ppm, and 66.0 g of methyl methacrylate was obtained per hour from the top of the distillation column.

Example 2 Methyl methacrylate was produced in the same manner as in Example 1 except that carbon monoxide having a hydrogen content of 1% by volume was used.

Twenty hours after the start of the reaction, the platinum concentration in the circulating solution was 1,738 ppm, the methyl methacrylate obtained from the top of the distillation column was 65.8 g / h, and the methyl methacrylate contained methyl isobutyrate. The content was 0.03% by weight. The reaction was further continued for 180 hours,
After 00 hours, the platinum concentration in the circulating liquid was 1605 ppm, and methyl methacrylate was added at 62.6 h / h from the top of the distillation column.
g was obtained.

Comparative Example Methyl methacrylate was produced in the same manner as in Example 1 except that carbon monoxide having a hydrogen content of 6% by volume was used.

Twenty hours after the start of the reaction, the platinum concentration in the circulating solution was 1,662 ppm, the methyl methacrylate obtained from the top of the distillation column was 65.9 g / h, and the methyl methacrylate contained methyl isobutyrate. The content was 0.32% by weight. The reaction was further continued for 180 hours,
After 00 hours, the platinum concentration in the circulating liquid was 861 ppm, and methyl methacrylate was added 32.6 per hour from the top of the distillation column.
g was obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 69/54 C07C 69/54 Z // C07B 61/00 300 C07B 61/00 300

Claims (9)

[Claims] 1. A carbonylation method for reacting an acetylenic or olefinically unsaturated compound with carbon monoxide in the presence of a carbonylation catalyst, wherein carbon monoxide having a hydrogen content of 5% by volume or less is used. A carbonylation method comprising: 2. The method according to claim 1, wherein the carbonylation catalyst is at least one of those in the periodic table.
2. A carbonylation process according to claim 1 comprising a Group VIII metal source. 3. The method according to claim 1, wherein the carbonylation catalyst comprises:
The carbonylation method according to claim 1, comprising a group metal source, (2) a ligand, and (3) an acid. 4. The carbonylation method according to claim 2, wherein the Group VIII metal of the periodic table is at least one selected from cobalt, nickel, rhodium, palladium and platinum. 5. The carbonylation method according to claim 3, wherein the ligand is a phosphorus compound. 6. The carbonylation method according to claim 1, further comprising reacting water, an alcohol or a carboxylic acid. 7. The carbonylation method according to claim 1, wherein the reaction is continuously performed while supplying carbon monoxide having a hydrogen content of 0.001 to 3% by volume. 8. In the presence of the carbonylation catalyst according to claim 3, an α-acetylene-based or α-olefin-based hydrocarbon is reacted with carbon monoxide and water, an alcohol or an organic carboxylic acid to form carbonylation. Carbonylation method using carbon monoxide having a hydrogen content of 0.001 to 3% by volume. 9. In the presence of the carbonylation catalyst according to claim 3, at least one selected from acetylene, propyne and arene, carbon monoxide having a hydrogen content of 5% by volume or less, water, alcohol and organic carboxylic acid. Subjecting at least one selected from acids to a carbonylation reaction to obtain α, β
-A method for producing an ethylenically unsaturated carboxylic acid or a derivative thereof.