JP2014189525A - Method for producing linear dialdehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a linear dialdehyde capable of achieving improvement in catalytic activity and improvement in selectivity of a linear dialdehyde in the hydroformylation reaction of a linear olefin compound having each of an ethylenical double bond and an aldehyde group at each of the molecular terminals.SOLUTION: There is provided a method for producing a linear dialdehyde by reacting a linear olefin compound having each of an ethylenical double bond and an aldehyde group at each of the molecular terminals with carbon monoxide and hydrogen in the presence of a rhodium catalyst composed of a bisphosphite represented by the general formula (I) (wherein, Rand Reach independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; Rand Reach independently represents a hydrogen atom or a methyl group.) and a rhodium compound.

Description

  The present invention relates to a method for producing a linear dialdehyde. Specifically, the present invention relates to a method for industrially advantageously producing a linear dialdehyde by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end. The method of the present invention is useful, for example, as a method for producing 1,9-nonanediol which is a synthetic intermediate of 1,9-nonanediol from 7-octen-1-al. 1,9-nonanediol is useful as a raw material for producing polycarbonate, polyester, polyurethane and the like, a raw material for paints (polyester paints and epoxy resin paints), a resin modifier for polyester resins and epoxy resins, and the like.

  A reaction in which an olefinic compound having a carbon-carbon double bond is converted to an aldehyde by reacting with carbon monoxide and hydrogen in the presence of a rhodium catalyst composed of a rhodium compound and a phosphorus compound is called a hydroformylation reaction. The method for producing aldehydes using aldehyde has high industrial value.

  A hydroformylation reaction of a compound having an ethylenic double bond at the molecular end (hereinafter referred to as a terminal olefin compound) produces a linear aldehyde and a branched aldehyde. In some cases, an isomer in which the double bond is isomerized and an aldehyde in which the isomer is hydroformylated are by-produced.

  The catalytic activity and linear aldehyde selectivity in the hydroformylation reaction are, for example, the reaction temperature, the composition ratio of the mixed gas composed of carbon monoxide and hydrogen, the pressure of the mixed gas, the type and amount of the solvent used, the structure of the terminal olefin compound, It varies depending on various reaction conditions for hydroformylation, such as the type of phosphorus compound constituting the rhodium catalyst. In particular, the type of phosphorus compound constituting the rhodium catalyst greatly changes the electronic state of the rhodium atom as the central metal of the rhodium catalyst and the three-dimensional structure around the rhodium central metal in the rhodium complex intermediate that is the true active species of the rhodium catalyst. Therefore, it is known that the influence on the catalytic activity and the linear aldehyde selectivity is large (see Non-Patent Documents 1 and 2).

  In order to reduce the manufacturing cost of linear aldehydes, it is important to reduce the amount of expensive rhodium used by improving the catalytic activity, and also to improve the linear aldehyde selectivity. is important.

  On the other hand, a linear dialdehyde is obtained by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular terminal (hereinafter sometimes referred to as a linear unsaturated aldehyde). Manufacturing methods are known. For example, in the hydroformylation reaction of 7-octen-1-al using bisphosphine having a specific structure (2,2′-bis (diphenylphosphinomethyl) biphenyl), a linear dialdehyde (1,9-nonanedial) It is known that the selectivity is 93% and the branched dialdehyde (2-methyl-1,8-octane dial) selectivity is 3% (see Patent Document 1).

  In addition, it is known to use phosphite as a phosphorus compound for the purpose of enhancing the catalytic activity of hydroformylation, and among them, it is known that high linear aldehyde selectivity can be achieved with a bisphosphite having a specific structure ( (See Patent Documents 2 to 6 and Non-Patent Documents 2 to 5).

As the bisphosphite having the specific structure, the general formula (Z ₁ O) (Z ₂ O) PO—W—OP (OZ ₃ ) (OZ ₄ )
In the bisphosphite represented by the following formula, W is a bulky 1,1′-biaryl-2,2′-diyl group, such as 3,3 ′, 5,5′-tetra-t-butyl-1,1′- Biphenyl-2,2′-diyl group, 3,3′-di-t-butyl-5,5′-dimethoxy-1,1′-biphenyl-2,2′-diyl group, 3,3 ′, 5 Bisphosphites which are 5′-tetra-t-butyl-6,6′-dimethyl-1,1′-biphenyl-2,2′-diyl groups are known.
Further, bisphosphites which are 1,1′-biaryl-2,2′-diyl groups in which Z ₁ and Z ₂ and Z ₃ and Z ₄ are bonded to each other are known (hereinafter referred to as bisphosphite ( i); see Patent Documents 2-3 and Non-Patent Documents 2-4, respectively).
Furthermore, it is _{Z 1} and _{Z 2} include bulky 1,1'-biaryl-2,2'-diyl group, may not be attached even _{Z 3} and _{Z 4} are not each coupled, _{Z 3} Z ₄ an aryl group, the bisphosphite 1,1'-biaryl-2,2'-diyl group or alkylene group as Z ₃ and Z ₄ are attached is known to is not associated with (Hereinafter referred to as bisphosphite (ii); see Patent Documents 2-3, 5-6 and Non-Patent Documents 3, 5 respectively).
And bisphosphite in which Z ₁ and Z ₂ and Z ₃ and Z ₄ are each an aryl group is known (hereinafter referred to as bisphosphite (iii); see Patent Document 4).

The results of the hydroformylation reaction of 1-octene using bisphosphite i-1 belonging to bisphosphite (i) and bisphosphite ii-1 belonging to bisphosphite (ii) are compared. . When bisphosphite ii-1 is used, the linear aldehyde (1-nonanal) selectivity is 95%, the branched aldehyde (2-methyl-1-octanal) selectivity is 5%, and isomers (2-octene, etc.) ) Selectivity is below the detection limit. On the other hand, when bisphosphite i-1 is used, linear aldehyde selectivity is 72.1%, branched aldehyde selectivity is 1.4%, and isomer selectivity is 26. .5% (see Non-Patent Document 3).
By hydroformylation of propylene using bisphosphite iii-1 belonging to bisphosphite (iii), an aldehyde product having a linear / branched ratio of 43.5 (linear aldehyde ratio: 97.76%) is collected. It is known that it can be acquired at a rate of 95.8% (see Patent Document 4).

Japanese Patent Laid-Open No. 2004-2287 JP 62-116535 A US Pat. No. 5,756,855 JP 10-45776 A JP-A-62-116587 JP-A-4-290551

Journal of American Chemical Society, Vol. 114, 1992, pages 5535-5543 Organometallics, Vol. 14, 1995, 3832-3838 Organometallics, Vol. 15, 1996, pages 835-847. Journal of American Chemical Society, Vol. 115, 1993, pp. 2066-2068 (Journal of American Chemical Society) Journal of Molecular Catalysis A Chemical (Vol.143, 1999, 85-97)

In Patent Document 1, when a bisphosphine having a specific structure (2,2′-bis (diphenylphosphinomethyl) biphenyl) is used, a high linear dialdehyde selectivity is obtained in a hydroformylation reaction of 7-octen-1-al. Although it can be achieved, it has a problem that the catalytic activity of the hydroformylation reaction itself is low.
In carrying out the hydroformylation reaction of 7-octen-1-al, bisphosphite ii disclosed in Non-Patent Document 3 and showing good linear aldehyde (1-nonanal) selectivity (95%) with 1-octene Using -1, it was found that both catalytic activity and linear dialdehyde selectivity were low. Moreover, when using bisphosphite iii-1 disclosed in Patent Document 4 and showing good linear aldehyde selectivity (97.76%) with propylene, there is a problem in using bisphosphite ii-1. Although the catalytic activity and the linear dialdehyde selectivity were improved, it was found that there was room for improvement because it was difficult to say that the results were satisfactory in view of industrial practice.

  The present inventor, in particular, in the hydroformylation reaction of 7-octen-1-al, is not good in linear aldehyde (1-nonanal) selectivity in hydroformylation with 1-octene disclosed in Non-Patent Document 3. Using bisphosphite i-1 (72.1%; isomer by-product with 26.5% selectivity), surprisingly significant improvement in catalytic activity and linear dialdehyde selectivity The inventors have found that a significant improvement can be achieved together, and have further studied to complete the present invention.

That is, the present invention
[1] General formula (I)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom or Represents a methyl group.)
In the presence of a rhodium catalyst comprising a bisphosphite (hereinafter referred to as bisphosphite (I)) and a rhodium compound, a linear olefin having an ethylenic double bond and an aldehyde group at each molecular end, respectively. A linear dialdehyde comprising reacting a functional compound (linear unsaturated aldehyde) with carbon monoxide and hydrogen;
[2] The linear unsaturated aldehyde is 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, 8-nonen-1-al, 9-decene-1-al, 10 -The manufacturing method of the linear dialdehyde of [1] which is either undecen-1-al and 11-dodecene-1-al;
[3] The method for producing a linear dialdehyde according to [1], wherein the linear unsaturated aldehyde is 7-octen-1-al;
[4] Bisphosphite (I) in which R ¹ and R ² are each independently a t-butyl group or a methoxy group, and R ³ and R ⁴ are both hydrogen atoms in general formula (I). A process for producing a linear dialdehyde according to any one of [1] to [3];
[5] The linear chain of [4], wherein bisphosphite (I) in which R ¹ and R ² are both t-butyl groups and R ³ and R ⁴ are both hydrogen atoms is used. A method for producing gaseous dialdehyde;
[6] The rhodium concentration in the reaction solution is 1.0 × 10 ^{−4 to} 6.0 × 10 ⁻¹ mmol / kg as rhodium atoms, and the amount of bisphosphite (I) used is 1 with respect to rhodium atoms. ˜100 mol times, reaction temperature is 50 to 120 ° C., the composition ratio of carbon monoxide and hydrogen is carbon monoxide / hydrogen = 0.1 / 1 to 10/1 as a molar ratio, and the reaction [7] The method for producing a linear dialdehyde according to any one of [1] to [5], wherein the pressure is 0.5 to 10.0 MPa (gauge pressure); and [7] The rhodium concentration in the reaction solution is rhodium. The number of atoms is 5.0 × 10 ^{−3 to} 2.5 × 10 ⁻¹ mmol / kg, the amount of bisphosphite (I) used is 2 to 20 moles per rhodium atom, and the reaction temperature is 70. ~ 100 ° C, and the composition ratio of carbon monoxide and hydrogen is The linear ratio of [6], wherein the carbon ratio is carbon monoxide / hydrogen = 0.5 / 1 to 5/1, and the pressure during the reaction is 1.0 to 5.0 MPa (gauge pressure). A method for producing an aldehyde;

  According to the present invention, a linear dialdehyde can be industrially advantageously produced by hydroformylating a linear unsaturated aldehyde. In particular, 1,9-nonanedial can be produced industrially advantageously from 7-octen-1-al.

Hereinafter, the production method of the present invention will be described in detail.
In the production method of the present invention, the rhodium catalyst is formed in a reaction system by supplying a solution in which a rhodium compound is dissolved in a solvent and a solution in which bisphosphite (I) is dissolved in a solvent, respectively, to the hydroformylation reaction system. Alternatively, the rhodium compound and bisphosphite (I) are dissolved in a solvent under an inert gas atmosphere, and then stirred preferably in a mixed gas atmosphere consisting of carbon monoxide and hydrogen to separately prepare a rhodium catalyst solution. The rhodium catalyst solution may be prepared and fed to the hydroformylation reaction system. From the viewpoint of sufficiently expressing the catalytic activity, a method of separately preparing a rhodium catalyst solution and then supplying it to the hydroformylation reaction system is preferable.

Examples of rhodium compounds that can be used in the production method of the present invention include Rh (NO ₃ ) ₂ , Rh (OAc) ₂ , Rh (acac) (CO) ₂ , Rh (acac) (CO) (PPh ₃ ). ), HRh (CO) (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , RhBr (CO) (PPh ₃ ) ₂ , RhCl (PPh ₃ ) ₃ , [Rh (μ-OAc) (CO) ₂ ] ₂ , [Rh (μ-OAc) (COD)] ₂ , [Rh (μ-Cl) (COD)] ₂ , [Rh (μ-Cl) (CO) ₂ ] ₂ , Rh ₄ (CO) ₁₂ , Rh ₄ (CO) ₈ (PPh ₃ ) ₄ , Rh ₆ (CO) ₁₆ , wherein OAc is an acetyl group, acac is an acetylacetonato group, Ph is a phenyl group, COD is 1,5-cyclooctadiene, Respectively) Etc., and the like. Among these, Rh (acac) (CO) ₂ is preferably used from the viewpoint that a rhodium catalyst can be easily prepared in a mixed gas atmosphere composed of carbon monoxide and hydrogen.

  In the production method of the present invention, the general formula (I)

(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
It is characterized by using the bisphosphite (I) shown by these as a component which comprises the rhodium catalyst used with the manufacturing method of this invention. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include those having an alkyl moiety as the alkyl group. Among them, any one of ^{R 1} and ^{R 2} t- butyl group or a methoxy group, preferably ^{R 3} and ^{R 4} are both hydrogen atoms, both ^{R 1} and ^{R 2} in t- butyl group And R ³ and R ⁴ are preferably both hydrogen atoms.

The bisphosphite (I) used in the production method of the present invention is preferably 2,2′-bisphenoxy to one molecule of 2,2′-bisphenol in an aprotic solvent under an inert gas atmosphere. It can be produced by reacting two phosphorous chloride molecules in a state where two or more amine molecules coexist.
Examples of 2,2′-bisphenols include 4,4 ′, 6,6′-tetra-t-butyl-2,2′-bisphenol, 4,4′-dimethoxy-6,6′-di-t-butyl. -2,2'-bisphenol, 3,3'-dimethyl-4,4'-dimethoxy-6,6'-di-t-butyl-2,2'-bisphenol and the like. For example, 4,4 ′, 6,6′-tetra-t-butyl-2,2′-bisphenol is obtained by using cupric chloride with respect to a solution obtained by dissolving 500 g of 2,4-di-t-butylphenol in 1 L of methanol. 2 g of dihydrate and 2 mL of N, N, N ′, N′-tetramethylethane-1,2-diamine were added, and the precipitate obtained by sufficiently stirring at room temperature with bubbling oxygen gas was recovered. The recovered product can be produced by recrystallization from methanol.
2,2′-bisphenoxyphosphorus chloride is mixed with, for example, 10 mL of phosphorus trichloride, 30 mL of triethylamine and 100 mL of tetrahydrofuran in an argon gas atmosphere and cooled to 0 ° C. Then, 20 g of 2,2′-bisphenol is added to this solution. A solution dissolved in 50 mL of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the mixture was naturally heated to room temperature and further heated to reflux temperature, reacted for 6 hours, allowed to cool to room temperature, and the precipitated triethylamine hydrochloride was filtered off. The obtained filtrate can be concentrated and then distilled under reduced pressure at 120 ° C./0.2 mmHg to obtain a white solid.
For example, bisphosphite i-1 is obtained by adding 0.92 g of 2,2′-bisphenoxyphosphorous chloride to 4,4 ′, 6,6′-tetra-t-butyl-2 at 50 ° C. in an argon gas atmosphere. , 2′-bisphenol 0.75 g and pyridine 1 mL in tetrahydrofuran 25 mL were added dropwise, and after completion of the addition, the reaction was carried out at room temperature for 2 days. The precipitated pyridine hydrochloride was filtered off, and the obtained filtrate was concentrated. Thereafter, it can be obtained by recrystallization with a mixed solvent of acetonitrile / toluene.

  The solvent that can be used for the preparation of the rhodium catalyst is preferably an aprotic solvent from the viewpoint of suppressing hydrolysis of bisphosphite (I), and is a reaction that coexists in the hydroformylation reaction as necessary from the viewpoint of recovering and utilizing the solvent. It is preferable that it is the same kind of solvent as an inert solvent. Examples of such solvents include saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane; benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene, p-xylene. , O-ethyltoluene, m-ethyltoluene, p-ethyltoluene and other aromatic hydrocarbons; isopropanol, isobutanol, neopentyl alcohol and other alcohols; diethyl ether, dipropyl ether, butyl methyl ether, t-butyl methyl ether , Ethers such as dibutyl ether, ethyl phenyl ether, diphenyl ether, tetrahydrofuran, 1,4-dioxane; acetone, ethyl methyl ketone, methyl propyl ketone, diethyl ketone, ethyl Piruketon, etc. ketones such as dipropyl ketone. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, it is preferable to use toluene or tetrahydrofuran from a viewpoint that a rhodium compound and bisphosphite (I) can be uniformly dissolved with a small amount of solvent used.

It is preferable to increase the concentration of rhodium atoms contained in the rhodium catalyst solution as much as possible in terms of reducing the amount of solvent used, and it is preferable to strictly control the amount of bisphosphite used per mole of rhodium atoms. Therefore, the rhodium catalyst solution is preferably prepared batch-wise or semi-batch-wise using a complete mixing tank reactor.
Specifically, either a method of introducing a separately prepared rhodium compound solution and a solution of bisphosphite (I) into the reactor, or a method of introducing one of the solutions into the reactor and introducing the other as a solid, A method of introducing one as a solid into the reactor and introducing the other as a solution, a method of introducing both into the reactor as a solid, a method of introducing a solvent, a method of introducing a solvent into the reactor and introducing both as a solid, etc. Can be mentioned.

  The rhodium catalyst solution is preferably prepared in an inert gas atmosphere such as nitrogen, argon, or helium, and nitrogen is preferably used in terms of industrial availability and cost. Although there is no restriction | limiting in particular in the pressure of an inert gas, Usually, normal pressure -0.5 Mpa (gauge pressure) are preferable.

  In the preparation of the rhodium catalyst solution, the amount of bisphosphite (I) used is preferably 1 to 100 mol times, more preferably 2 to 20 mol times the rhodium atom. Within this range, both catalytic activity and linear dialdehyde selectivity are improved, and the effects of the present invention are further exhibited.

  10-80 degreeC is preferable and the temperature at the time of preparing the rhodium catalyst used with the manufacturing method of this invention has more preferable 20-50 degreeC.

  The rhodium catalyst solution prepared in an inert gas atmosphere is preferably in a mixed gas atmosphere composed of carbon monoxide and hydrogen in advance before being supplied to the hydroformylation reaction system. Although there is no restriction | limiting in particular in the pressure of the mixed gas which consists of carbon monoxide and hydrogen, Usually, it is preferable that it is a normal pressure-0.5 Mpa (gauge pressure).

  The production method of the present invention can be carried out by introducing a rhodium catalyst, preferably as a solution, into a linear unsaturated aldehyde in the presence of a mixed gas composed of carbon monoxide and hydrogen.

  The production method of the present invention can be carried out batch-wise or semi-batch-type using a complete mixing tank reactor, and is a complete mixing tank reactor or a tubular reactor, and further comprises two or three of them. You may implement by a continuous flow type using what was connected in series. When a plurality of reactors are connected in a continuous flow mode, the residence time, temperature, composition ratio of mixed gas, and pressure can be set independently for each reactor.

  In the production method of the present invention, the effect of the present invention is improved, that is, the catalytic activity is improved and the linear chain is improved by increasing the dissolution rate of the mixed gas composed of carbon monoxide and hydrogen in the linear unsaturated aldehyde in which the rhodium catalyst is dissolved. From the viewpoint of achieving both improvements in the selectivity to the gaseous dialdehyde. In the case of using a complete mixing tank reactor or a tubular reactor, from the viewpoint of increasing the dissolution rate of the mixed gas, the mixed gas may be continuously supplied from the bottom of the reactor, or an ejector having a mixing chamber. A loop venturi reactor may be used as a tubular reactor equipped with

  Examples of the linear unsaturated aldehyde include 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, 8-nonen-1-al, 9-decene-1-al, 10 -Undecen-1-al, 11-dodecene-1-al and the like. In particular, the effect of the invention is remarkable when 7-octen-1-al is used. In the production method of the present invention, 7-octen-1-al having a purity of 95% by mass or more can also be used. 7-octen-1-al can be produced, for example, by isomerizing 2,7-octadien-1-ol in the presence of a copper-based catalyst. The 7-octen-1-al produced in this way includes 1-octanal, 7-octen-1-ol, trans-6-octen-1-al, cis-6-octen-1-al and the like. Included as product. Since these by-products do not significantly poison the rhodium catalyst used in the production method of the present invention, it is possible to hydroformylate 7-octen-1-al while containing these impurities. That is, the scope of the invention is not limited by the purity of the linear unsaturated aldehyde.

  You may perform the manufacturing method of this invention in presence of a solvent. Preferred examples of the solvent include the same solvents as those described above that can be used in preparing the rhodium catalyst solution. When the solvent is present, the amount used is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, based on the entire reaction solution. In addition, the usage-amount of a solvent means the sum total of the solvent supplied as a rhodium catalyst solution, and the solvent supplied separately to a reaction system.

In the production method of the present invention, the amount of rhodium used in the reaction solution is preferably 1.0 × 10 ^{−4 to} 6.0 × 10 ⁻¹ mmol / kg as rhodium atoms, and 5.0 × 10 ⁻ More preferably, it is ^{3 to} 2.5 × 10 ⁻¹ mmol / kg. The amount of bisphosphite (I) used in the reaction solution is preferably 1 to 100 mol times, more preferably 2 to 20 mol times relative to the rhodium atom. In these ranges, high catalytic activity and high linear dialdehyde selectivity can be achieved.

  In the production method of the present invention, the reaction temperature is preferably 50 to 120 ° C, more preferably 70 to 100 ° C. When the reaction temperature is within the above range, high catalytic activity and high linear dialdehyde selectivity can be achieved without decomposition of the rhodium catalyst.

  In the production method of the present invention, the composition ratio of the mixed gas composed of carbon monoxide and hydrogen used for the reaction is usually in the range of carbon monoxide / hydrogen = 0.1 / 1 to 10/1 as a molar ratio. The range of 0.5 / 1 to 5/1 is preferable, and 1/1 to 3/1 is more preferable. The pressure during the reaction of such a mixed gas is preferably 0.5 to 10.0 MPa (gauge pressure), and more preferably 1.0 to 5.0 MPa (gauge pressure).

  In addition, in the manufacturing method of this invention, you may further coexist phosphorus compounds other than bisphosphite (I) as needed. Examples of such phosphorus compounds include triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tribenzylphosphine, triphenylphosphine, tris (p-methoxyphenyl) phosphine, tris (p-N, N--). Dimethylaminophenyl) phosphine, tris (p-fluorophenyl) phosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (pentafluorophenyl) phosphine, bis (pentafluorophenyl) Phenylphosphine, diphenyl (pentafluorophenyl) phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, cyclohexyldiphenylphosphine, dimethylphenylphosphine, diethylphenyl Sphin, 2-furyldiphenylphosphine, 2-pyridyldiphenylphosphine, 4-pyridyldiphenylphosphine, m-diphenylphosphinobenzenesulfonic acid or its metal salt, p-diphenylphosphinobenzoic acid or its metal salt, p-diphenylphosphino Phosphines such as phenylphosphonic acid or metal salts thereof; triethyl phosphite, triphenyl phosphite, tris (p-methoxyphenyl) phosphite, tris (o-methylphenyl) phosphite, tris (m-methylphenyl) phosphite, Tris (p-methylphenyl) phosphite, tris (o-ethylphenyl) phosphite, tris (m-ethylphenyl) phosphite, tris (p-ethylphenyl) phosphite, tris (o-propylphenyl) Nyl) phosphite, tris (m-propylphenyl) phosphite, tris (p-propylphenyl) phosphite, tris (o-isopropylphenyl) phosphite, tris (m-isopropylphenyl) phosphite, tris (p-isopropyl) Phenyl) phosphite, tris (ot-butylphenyl) phosphite, tris (pt-butylphenyl) phosphite, tris (p-trifluoromethylphenyl) phosphite, tris (2,4-dimethylphenyl) Examples thereof include phosphites such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, and tris (2-t-butyl-4-methylphenyl) phosphite. In the case where a phosphorus compound is further allowed to coexist, the amount used is preferably 1 to 100 mol times, more preferably 2 to 20 mol times relative to the rhodium atom.

  In the production method of the present invention, a nitrogen-containing compound may further coexist as necessary. Examples of the nitrogen-containing compound include triethylamine, tributylamine, tri-n-octylamine, N, N, N ′, N′-tetramethyl-1,2-diaminoethane, N, N, N ′, N′— Tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,4-diaminobutane, N, N-diethylethanolamine, triethanolamine, N-methylpiperidine, N-methyl Examples include pyrrolidine, N-methylmorpholine, pyridine, picoline, lutidine, collidine, and quinoline. When the nitrogen-containing compound is further allowed to coexist, the amount used is preferably 100 to 3000 moles, more preferably 500 to 2000 moles, relative to the rhodium atom. When a nitrogen-containing compound is further allowed to coexist, it is possible to suppress the linear dialdehyde as the target product from further reacting under reaction conditions to become a high-boiling product.

  In the production method of the present invention, since the rhodium content in the reaction solution after completion of the hydroformylation reaction is industrially acceptable, the reaction solution is left as it is without performing the operation of recovering rhodium from the reaction solution. It can be used directly in the next reaction such as a hydrogenation reaction or a reductive amination reaction. Of course, if desired, a step of purifying the linear dialdehyde from the reaction solution by separating it from the rhodium catalyst component may be performed. There is no restriction | limiting in particular in the separation / purification method of linear dialdehyde from this reaction liquid, A well-known method is applicable. For example, low-boiling components can be distilled off from the hydroformylation reaction solution under reduced pressure, and the residue can be further purified by distillation to separate it into a distillation residue containing unreacted raw materials, linear dialdehyde and rhodium catalyst. You may reuse an unreacted raw material and distillation residue for the manufacturing method of this invention. Prior to distillation separation, the constituents of the rhodium catalyst may be separated by subjecting the residue to methods such as evaporation, extraction, and adsorption.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by this Example and comparative example.
7-Octene-1-al used as a raw material in each example and comparative example has a purity of 95.4% by mass, and main impurities are 1-octanal, trans-6-octen-1-al, cis-6- Octen-1-al. Unless otherwise specified, the rhodium catalyst was prepared at room temperature, normal pressure, and nitrogen atmosphere, and the raw materials and solvent were previously purified by distillation and purged with nitrogen.
Bisphosphite has the following chemical formula

The compound shown in was used. The phosphorus compound A is bisphosphite i-1 described in the background art, the phosphorus compound B is bisphosphite ii-1 described in the background art, and the phosphorus compound C is bisphosphite iii- described in the background art. Each of the compounds was synthesized according to a known method.
The consumption amount (conversion rate) of 7-octen-1-al in the reaction solution and the production amounts of 1,9-nonanedial and other products as target products were analyzed and quantified by gas chromatography.

The consumption of 7-octen-1-al is first order with respect to the concentration of 7-octen-1-al, the reaction rate constant is k ₁ (hr ⁻¹ ), and 7-octen-1- When the number of moles of R is [C] ₀ and the number of moles of 7-octen-1-al contained in the reaction solution after the reaction t (hr) is [C] _t , Formula 1 is established.

The rhodium concentration in the charged reaction solution is [C] _cat (mmol / kg), and the reaction rate constant k ₁ (hr ⁻¹ ) calculated from Equation 1 is used to determine the catalyst activity (kg · mmol ⁻¹ · hr ^{− 1} ) was calculated by the following mathematical formula 2.

  By hydroformylation of 7-octen-1-al, 1,9-nonane dial (target product) as a linear dialdehyde, 2-methyl-1,8-octane dial as a branched dialdehyde, isomerism 6-octen-1-al by hydrogenation and 1-octanal by hydrogenation are produced. The selectivity of these products was calculated by the following formula 3. Each amount in the formula is (mol).

Example 1
In a 100 mL three-necked flask equipped with a magnetic rotor, 18.6 mg (0.072 mmol) of Rh (acac) (CO) ₂ , 302.4 mg (0.360 mmol) of phosphorus compound A, 100 g of toluene under a nitrogen atmosphere The mixture was stirred at 50 ° C. for 30 minutes to dissolve, then cooled to room temperature, replaced with a mixed gas atmosphere of carbon monoxide / hydrogen = 1/1 (molar ratio), and then stirred for another 30 minutes. A solution was prepared.
On the other hand, after replacing the inside of an autoclave having an internal volume of 100 ml equipped with a gas inlet, a gas outlet and a sampling port with a mixed gas atmosphere of carbon monoxide / hydrogen = 1/1 (molar ratio), 7-octene- 1-R (purity 95.4% by mass) 41.38 g and 0.87 g of the catalyst solution prepared above were charged, the temperature was raised to 85 ° C. within 10 minutes with stirring, and carbon monoxide / hydrogen The total pressure inside the autoclave was set to 3.0 MPa (gauge pressure) using a mixed gas of = 1/1 (molar ratio), and the reaction was started. During the reaction, a mixed gas of carbon monoxide / hydrogen = 1/1 (molar ratio) was supplied to keep the total pressure inside the autoclave at 3.0 MPa (gauge pressure). When the point at which the internal temperature of the reaction solution reached 85 ° C. was 0 hr, the conversion rate of 7-octen-1-al after 8 hr after the reaction was 95.9%, and the catalyst activity was 26.98 (kg · mmol ⁻¹ · hr ⁻¹ ), the 1,9-nonane dial selectivity is 85.6%, the 2-methyl-1,8-octane dial selectivity is 1.6%, and 6-octen-1-al. The selectivity was 4.9% and the octanal selectivity was 7.9%.

Example 2
In Example 1, a mixed gas of carbon monoxide / hydrogen = 1/1 (molar ratio) was supplied during the reaction to keep the total pressure inside the autoclave at 3.0 MPa (gauge pressure), and the mixed gas was 15 L / The reaction was carried out in the same manner as in Example 1 except that it was circulated in hr. The conversion of 7-octen-1-al after 8 hours of reaction was 94.9%, the catalytic activity was 25.15 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediol selectivity was 90.9%, 2-methyl-1,8-octane dial selectivity was 1.8%, 6-octen-1-al selectivity was 2.7%, and octanal selectivity was 4.5%. .

Example 3
The reaction was carried out in the same manner as in Example 1 except that a mixed gas of carbon monoxide / hydrogen = 2.5 / 1 (molar ratio) was used in Example 1 and this mixed gas was circulated at 15 L / hr. The conversion of 7-octen-1-al after the reaction 8 hr was 61.7%, the catalytic activity was 8.13 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediar selectivity was 88.9%, 2-methyl-1,8-octane dial selectivity was 2.9%, 6-octen-1-al selectivity was 3.4%, and octanal selectivity was 4.8%. .

Example 4
The reaction was carried out in the same manner as in Example 1 except that the temperature was changed to 75 ° C. in Example 1. The conversion of 7-octen-1-al after 8 hours of reaction was 80.6%, the catalytic activity was 13.83 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediar selectivity was 88.6%, 2-methyl-1,8-octane dial selectivity was 1.4%, 6-octen-1-al selectivity was 3.8%, and octanal selectivity was 6.2%. .

Example 5
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the total pressure inside the autoclave was maintained at 3.0 MPa (gauge pressure). The conversion of 7-octen-1-al after 8 hr after the reaction was 79.0%, the catalytic activity was 13.18 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediol selectivity was 87.5%, 2-methyl-1,8-octane dial selectivity was 3.4%, 6-octen-1-al selectivity was 5.7%, and octanal selectivity was 3.4%. .

Comparative Example 1
The reaction was carried out in the same manner as in Example 1 except that 408.9 mg (0.360 mmol) of phosphorus compound B was used instead of 302.4 mg (0.360 mmol) of phosphorus compound A in Example 1. The conversion of 7-octen-1-al after 8 hours of reaction was 20.8%, the catalytic activity was 1.96 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediar selectivity was 27%, 2-methyl-1,8-octanedial selectivity was 11%, 6-octen-1-al selectivity was 17%, and octanal selectivity was 45%.

Comparative Example 2
The reaction was carried out in the same manner as in Example 1 except that 384.1 mg (0.360 mmol) of phosphorus compound C was used instead of 302.4 mg (0.360 mmol) of phosphorus compound A. The conversion of 7-octen-1-al after 8 hours of reaction was 22.8%, the catalytic activity was 2.16 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediar selectivity was 32%, 2-methyl-1,8-octane dial selectivity was 10%, 6-octen-1-al selectivity was 16%, and octanal selectivity was 42%.

Comparative Example 3
The reaction was carried out in the same manner as in Example 1 except that 303.9 mg (0.360 mmol) of phosphorus compound D was used instead of 302.4 mg (0.360 mmol) of phosphorus compound A. The conversion of 7-octen-1-al after 8 hours of reaction was 79.8%, the catalytic activity was 13.52 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanediol selectivity was 85%, 2-methyl-1,8-octane dial selectivity was 1%, 6-octen-1-al selectivity was 6%, and octanal selectivity was 8%.

Comparative Example 4
The reaction was carried out in the same manner as in Example 1 except that 221.5 mg (0.360 mmol) of phosphorus compound E was used instead of 302.4 mg (0.360 mmol) of phosphorus compound A in Example 1. The conversion rate of 7-octen-1-al after 8 hours of reaction was 1% or less.

Comparative Example 5
In Example 1, instead of using 18.6 mg (0.072 mmol) of Rh (acac) (CO) ₂ , 44.6 mg (0.173 mmol) is used; instead of using phosphorus compound A of 302.4 mg (0.360 mmol) The reaction was carried out in the same manner as in Example 1 except that 953.1 mg (1.730 mmol) of phosphorus compound F was used and 4.33 g of the prepared rhodium-containing solution was used. The conversion of 7-octen-1-al after 8 hours of reaction was 91.1%, the catalytic activity was 1.69 (kg · mmol ⁻¹ · hr ⁻¹ ), and the 1,9-nonanedial selectivity was 93%, 2-methyl-1,8-octane dial selectivity was 3%, 6-octen-1-al selectivity was 4%, and octanal selectivity was 0%.

  Table 1 summarizes the hydroformylation reaction results of Examples 1 to 5 and Comparative Examples 1 to 5. In Table 1, the molar ratio of carbon monoxide / hydrogen in the mixed gas is the gas ratio, the flow rate of the mixed gas is the gas amount (L / hr), the 1,9-nonane dial selectivity is NL (%), 2-methyl The -1,8-octane dial selectivity is abbreviated as MOL (%), the 6-octen-1-al selectivity is abbreviated as IS (%), and the octanal selectivity is abbreviated as HY (%).

In the hydroformylation reaction of 1-octene, bisphosphite (II) is known to give suitable reaction results, but according to a comparison of Examples 1-5 and Comparative Examples 1-2, linear unsaturation It is clear that when the aldehyde is hydroformylated, the phosphorus compound belonging to bisphosphite (I) can achieve both high catalytic activity and high linear dialdehyde selectivity.
Regarding the performance of bisphosphite (iii), it can be seen from the comparison between Examples 1 to 5 and Comparative Example 3 that the phosphorus compound belonging to bisphosphite (I) can achieve high catalytic activity.
According to a comparison between Examples 1 to 5 and Comparative Example 4, among bisphosphites (I), 1,1′-biaryl-2,2 ′ is bulky as a divalent organic group that bonds two phosphorus atoms. It can be seen that a high catalytic activity can be achieved with a phosphorus compound having a diyl group.
According to comparison between Examples 1-5 and Comparative Example 5, conventionally, compared to phosphorus compounds known to achieve high linear dialdehyde selectivity by hydroformylation reaction of linear unsaturated aldehyde, It can be seen that when a phosphorus compound belonging to bisphosphite (I) is used, high catalytic activity can be achieved and the linear aldehyde selectivity can be maintained high.

  The present invention provides a method for industrially advantageously producing a linear dialdehyde by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end. . In particular, an industrially advantageous method for producing 1,9-nonanediol from 7-octen-1-al is provided. From 1,9-nonanediol, 1,9-nonanediol, which is useful as a raw material for producing polycarbonate, polyester, polyurethane, etc., a raw material for paints (polyester paint, epoxy resin paint), a resin modifier for polyester resins and epoxy resins, etc. It can be produced industrially advantageously.

Claims (7)

Formula (I)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom or Represents a methyl group.)
In the presence of a rhodium catalyst comprising a bisphosphite and a rhodium compound represented by the formula, a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular terminal is reacted with carbon monoxide and hydrogen, respectively. A process for producing a linear dialdehyde characterized by Linear olefinic compounds each having an ethylenic double bond and an aldehyde group at the molecular terminals are 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, and 8-nonene-1. The method for producing a linear dialdehyde according to claim 1, which is any one of -R, 9-decene-1-R, 10-undecene-1-R, and 11-dodecene-1-R. The method for producing a linear dialdehyde according to claim 1, wherein the linear olefinic compound having an ethylenic double bond and an aldehyde group at the molecular terminals is 7-octen-1-al. In the general formula (I), R ¹ and R ² are each independently a t-butyl group or a methoxy group, and R ³ and R ⁴ are both bisphosphites in which a hydrogen atom is used, The manufacturing method of the linear dialdehyde in any one of Claims 1-3. The linear dialdehyde according to claim 4, wherein bisphosphite in which R ¹ and R ² are both t-butyl groups and R ³ and R ⁴ are both hydrogen atoms is used. Production method. The rhodium concentration in the reaction solution is 1.0 × 10 ^{−4 to} 6.0 × 10 ⁻¹ mmol / kg as rhodium atoms, and the amount of bisphosphite used is 1 to 100 mol times the rhodium atoms. The reaction temperature is 50 to 120 ° C., the composition ratio of carbon monoxide and hydrogen is carbon monoxide / hydrogen = 0.1 / 1 to 10/1 as a molar ratio, and the pressure during the reaction is 0.5 The manufacturing method of the linear dialdehyde in any one of Claims 1-5 which is-10.0MPa (gauge pressure). The rhodium concentration in the reaction solution is 5.0 × 10 ^{−3 to} 2.5 × 10 ⁻¹ mmol / kg as rhodium atoms, and the amount of bisphosphite used is 2 to 20 mol times the rhodium atoms. The reaction temperature is 70 to 100 ° C., the composition ratio of carbon monoxide and hydrogen is carbon monoxide / hydrogen = 0.5 / 1 to 5/1 as a molar ratio, and the pressure during the reaction is 1.0. The manufacturing method of the linear dialdehyde of Claim 6 which is -5.0 Mpa (gauge pressure).