KR20210004392A - Catalyst composition for hydroformylation and method for ptrparing aldehyde - Google Patents

Abstract

A catalyst composition for hydroformylation according to one embodiment of the present application includes: a phosphite-based ligand represented by chemical formula 1; a transition metal compound represented by following chemical formula 2: M(L1)_x(L2)_y(L3)_z; and a solvent, wherein a molar ratio of the phosphite-based ligand to a transition metal of the transition metal compound is 5 to 45. The catalyst composition for hydroformylation has excellent catalytic activity and stability.

Description

Catalyst composition for hydroformylation reaction and method for producing aldehyde using the same {CATALYST COMPOSITION FOR HYDROFORMYLATION AND METHOD FOR PTRPARING ALDEHYDE}

The present application relates to a catalyst composition for a hydroformylation reaction and a method of preparing an aldehyde using the same.

In the presence of a homogeneous organometallic catalyst and a ligand, various olefins react with carbon monoxide (CO) and hydrogen (H ₂ ), commonly referred to as synthetic gases, to increase the number of carbons by one (linear, normal) and branched, iso ) Hydroformylation reaction to produce aldehyde was first discovered in 1938 by Otto Roelen of Germany.

In general, a hydroformylation reaction known as an oxo (OXO) reaction is an industrially very important reaction in a homogeneous catalytic reaction, and various aldehydes including alcohol derivatives are produced and consumed through the oxo process worldwide.

Various aldehydes synthesized by oxo reaction may be converted into various acids and alcohols containing long alkyl groups by oxidation or hydrogenation after condensation reaction such as aldol. In particular, the hydrogenated alcohol of the aldehyde by the oxo reaction is referred to as oxo alcohol, and oxo alcohol is widely used industrially as a solvent, additives, raw materials for various plasticizers, synthetic lubricants, and the like.

In this regard, since the value of the linear aldehyde derivative (normal-aldehyde) among the aldehydes produced by the oxo reaction has been high in the past, most of the studies on the catalyst have been conducted in the direction of increasing the proportion of the linear aldehyde derivative. Branched aldehyde derivatives (iso-aldehyde) as raw materials, such as isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-1,3-pentanediol (2,2) ,4-trimethyl-1,3-pentanediol), isovaleric acid, etc., as the demand for isoaldehyde increases, research on increasing the selectivity of the branched aldehyde derivatives is ongoing. . Accordingly, there is a need to develop a catalyst having excellent catalytic stability and activity while lowering the n/i ratio of aldehyde normal/iso.

Korean Patent Publication No. 10-1150557

The present application provides a catalyst composition for a hydroformylation reaction and a method for producing an aldehyde using the same.

An exemplary embodiment of the present application,

A phosphite-based ligand represented by the following formula (1);

A transition metal compound represented by the following formula (2); And

Containing a solvent,

The molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is 5 to 45 to provide a catalyst composition for hydroformylation reaction.

[Formula 1]

In Formula 1,

R1 is an aryl group substituted with one or more of an alkyl group and an alkoxy group,

R2 to R5 are the same as or different from each other, and each independently an alkyl group,

[Formula 2]

M(L1)x(L2)y(L3)z

In Chemical Formula 2,

M is rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) or osmium (Os),

L1, L2, and L3 are the same as or different from each other, and each independently hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) Or acetylacetonato (AcAc),

The x, y and z are each independently an integer of 0 to 5, and x, y and z are not 0 at the same time.

In addition, another exemplary embodiment of the present application,

In the presence of the catalyst composition for hydroformylation reaction, including a hydroformylation step of reacting an olefin-based compound with a synthetic gas to produce an aldehyde,

The synthetic gas provides a method for producing an aldehyde containing carbon monoxide and hydrogen.

According to an exemplary embodiment of the present application, it is possible to provide a catalyst composition for hydroformylation reaction having excellent catalytic activity and stability.

In addition, according to an exemplary embodiment of the present application, by using the catalyst composition for the hydroformylation reaction, the selectivity of the normal/iso of the aldehyde generated during the hydroformylation reaction of the olefin-based compound is lowered. There are features that can be.

Hereinafter, the present specification will be described in more detail.

In the present specification, when a member is said to be located "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

As described above, in the case of a hydroformylation reaction using propylene and syngas, n-butylaldehyde (n-BAL) and i-butylaldehyde (i-BAL) are produced together. In the present application, it was attempted to increase the selectivity of i-butylaldehyde among them, and to increase the activity of the reaction to increase the production with a low content of catalyst.

As in the prior art, when the reaction is performed using a phosphine ligand as a catalyst composition, the n-BAL/i-BAL molar ratio is high, making it difficult to obtain a composition having a desired molar ratio, and the activity is generally low. In addition, even when using a very high molecular weight Di-phosphite ligand, a low n-BAL/i-BAL molar ratio cannot be obtained.

Accordingly, in the present application, the n-BAL/i-BAL molar ratio is very low as 3 or less, and in order to exhibit very high activity compared to the conventional phosphine ligand, a catalyst composition including a ligand of a cyclic phosphite compound is prepared. I wanted to use it.

The catalyst composition for hydroformylation reaction according to an exemplary embodiment of the present application includes a phosphite-based ligand represented by Formula 1; A transition metal compound represented by the following formula (2); And a solvent.

The alkyl group of Formula 1 may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group And the like, but are not limited thereto.

It is preferable that the aryl group of Formula 1 has 6 to 20 carbon atoms. Specific examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group.

It is preferable that the alkoxy group of Formula 1 has 1 to 5 carbon atoms. Specific examples of the alkoxy group include, but are not limited to, a methoxy group and an ethoxy group.

In the exemplary embodiment of the present application, R1 in Formula 1 may be a phenyl group substituted with at least one of a methyl group, a tert-butyl group, and a methoxy group.

In the exemplary embodiment of the present application, R2 to R4 in Formula 1 are each independently a methyl group or a tert-butyl group. In addition, in the exemplary embodiment of the present application, R2 and R5 in Formula 1 are tert-butyl groups, and R3 and R4 are methyl groups.

According to an exemplary embodiment of the present application, a phenyl group substituted with at least one of a methyl group, a tert-butyl group, and a methoxy group is bonded to R1 of Formula 1, thereby providing a catalyst composition for a hydroformylation reaction having excellent catalytic activity and stability. Can provide.

In the exemplary embodiment of the present application, the phosphite-based ligand may be represented by any one of the following structural formulas.

In the exemplary embodiment of the present application, the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound may be 5 to 45, and may be 8 to 30. When the molar ratio is satisfied, the catalytic activity and stability are excellent, and the selectivity of i-butylaldehyde and the synthesis gas yield are high. When the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is less than 5, the reaction activity may be very reduced, and when it exceeds 45, the selectivity of i-butylaldehyde may decrease.

In the exemplary embodiment of the present application, based on the total weight of the catalyst composition for the hydroformylation reaction, the content of the phosphite-based ligand may be 1% by weight to 4% by weight, and may be 1% by weight to 3% by weight. have. By satisfying the content range of the phosphite-based ligand, it is possible to obtain an effect of having excellent stability and activity of the catalyst and having a low normal/iso selectivity ratio of the prepared aldehyde.

In the exemplary embodiment of the present application, the transition metal compound is cobaltcarbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonylrhodium [Rh(AcAc)(CO) ₂ ], acetylacetonatocarbonyl Triphenylphosphine rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine) rhodium[HRh(CO)(TPP) ₃ ], acetylacetonatodicarbonyl iridium [Ir (AcAc)(CO) ₂ ] and hydridocarbonyl tri(triphenylphosphine) iridium [HIr(CO)(TPP) ₃ ].

In the exemplary embodiment of the present application, the solvent is propane aldehyde, butyl aldehyde, pentyl aldehyde, valer aldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, It may contain at least one of tensanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and heptane. In addition, it is more preferable that the solvent includes at least one of butyl aldehyde and valer aldehyde, and in this case, purification of the hydroformylation reaction product may be facilitated and side reactions may be minimized.

In the exemplary embodiment of the present application, the catalyst composition may have a catalytic activity of 300% or more, 500% or more, or 500% to 1,000% based on the activity of the catalyst composition including the triphenylphosphine compound, for example, , There is an effect of excellent catalytic activity within this range.

In addition, the catalyst composition is, for example, the catalyst stability after deactivation at a deactivation temperature of 90° C. or higher, 90° C. to 150° C., or 100° C. to 120° C. for 15 hours, the gas consumption of the catalyst composition containing the triphenylphosphine compound It may be 100% or more, 100% to 500%, or 100% to 250%, and the catalyst stability is excellent within this range.

In addition, another exemplary embodiment of the present application includes a hydroformylation step of reacting an olefin-based compound with a synthetic gas to produce an aldehyde in the presence of the catalyst composition for the hydroformylation reaction, wherein the synthetic gas contains carbon monoxide and hydrogen. It provides a method for producing an aldehyde containing.

The method for producing an aldehyde according to an exemplary embodiment of the present application may use a method known in the art, except for using the catalyst composition for hydroformylation reaction described above.

In the exemplary embodiment of the present application, the molar ratio of carbon monoxide: hydrogen may be 5:95 to 70:30, and 40:60 to 60:40.

In the exemplary embodiment of the present application, the hydroformylation step may be performed under a reaction temperature of 50°C to 130°C and a pressure of 5bar to 25bar, and a reaction temperature of 70°C to 110°C, and a reaction temperature of 5bar to 15bar. It can be carried out under pressure. When the reaction temperature in the hydroformylation step is less than 50°C, the activity of the reaction may decrease or the reaction may not be performed, and if it exceeds 130°C, the catalyst and ligand may be decomposed, and the reactivity may be reduced. have.

In the exemplary embodiment of the present application, the olefin-based compound may be at least one selected from ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and styrene, but is not limited thereto. . More preferably, the olefin-based compound may be propylene, and the aldehyde may be butylaldehyde.

In the exemplary embodiment of the present application, the molar ratio of n-butylaldehyde to i-butylaldehyde in the aldehyde may be 3 or less, and may be 2.5 or less.

Hereinafter, examples will be described in detail to describe the present application in detail. However, the embodiments according to the present application may be modified in various forms, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely describe the present application to those of ordinary skill in the art.

< Example >

< Contrast 1>

Acetylacetonatocarbonyltriphenylphosphine (rhodium acetylacetonato carbonyl triphenylphosphine, Rh(AcAc)(CO)(TPP), ROPAC) 0.12g (0.3mmol) and triphenylphosphine compound (triphenylphosphine, TPP) were added to valeraldehyde. (valeraldehyde) was dissolved in a solvent so that the total solution was 100g (Rh 250ppm, TTP 2% by weight), and then added to a 600ml autoclave reactor. Propylene and synthetic gas (CO/H ₂ ) were injected into the reaction solution to maintain the pressure in the reactor to be 8 bar, and reacted for 1 hour while stirring at 90°C.

< Example 1 to 9 and Comparative example 1 ~ 5>

The same method as in Comparative Example 1, except that the cyclic phosphite compound or the phosphine compound described in Table 1 below was added in the weight% described in Table 1 instead of the triphenylphosphine compound (triphenylphosphine, TPP) as a ligand in Comparative Example 1. It was carried out.

Thereafter, through gas chromatography (GC) analysis, the n-BAL content was divided by the i-BAL content to show the n/i-BAL molar ratio.

< GC Analysis conditions>

① Column: HP-1(L:30m, ID:0.32mm, film:1.05m)

② Injection volume: 1µl

③ Inlet Temp.: 260 ℃, Pressure: 6.92psi, Total flow: 64.2ml/min, Split flow: 60ml/min, spilt ratio: 50:1

④ Column flow: 1.2ml/min

⑤ Oven temp.: 70℃/3min-10℃/min-280℃/41min (Total 65min)

⑥ Detector temp.:280℃, H2: 35ml/min, Air: 300ml/min, He: 20ml/min

⑦ GC Model: Agilent 6890

<Normal activity, % )>

Based on 100% of the total amount of normal and isobutyl aldehyde produced by reaction according to Control Example 1, the total amount of normal and isobutyl aldehyde produced by the reaction according to each Example and Comparative Example was compared and calculated by the following equation And expressed as a percentage.

[Equation 1]

Catalytic activity = total amount of normal and isobutyl aldehyde in Example or Comparative Example / total amount of normal and isobutyl aldehyde in Control Example 1 × 100

<Normal stability, % )>

After reacting according to Comparative Example 1, the consumption of propylene gas used in the reaction was measured, and the catalyst solutions prepared in Examples and Comparative Examples were deactivated at deactivation temperature for 15 hours, and then hydroformylation in the same manner. After reacting, the consumption of propylene gas used for the reaction was measured, and the consumption of propylene gas before deactivation of Comparative Example 1 and the propylene gas after 15 hours of deactivation of Comparative Example 1, Example or Comparative Example ( gas) consumption was compared and calculated by Equation 2 below and expressed as a percentage.

[Equation 2]

Catalyst stability = Propylene gas consumption of the reaction after deactivation of Control Example 1, Example or Comparative Example for 15 hours / Propylene gas consumption before deactivation of Control Example 1 × 100

[Table 1]

[TPP, triphenylphosphine]

[TDMPP, tris(2,4-dimethylphenyl)phosphite]

[TPTP, tri-p-tolylphosphine]

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

As described above, according to the exemplary embodiment of the present application, a catalyst composition for hydroformylation reaction having excellent catalytic activity and stability can be provided.

In addition, according to an exemplary embodiment of the present application, by using the catalyst composition for the hydroformylation reaction, the selectivity of the normal/iso of the aldehyde generated during the hydroformylation reaction of the olefin-based compound is lowered. There are features that can be.

Claims (10)

A phosphite-based ligand represented by the following formula (1);
A transition metal compound represented by the following formula (2); And
Containing a solvent,
The molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is 5 to 45, wherein the catalyst composition for hydroformylation reaction:
[Formula 1]

In Formula 1,
R1 is an aryl group substituted with at least one of an alkyl group and an alkoxy group,
R2 to R5 are the same as or different from each other, and each independently an alkyl group,
[Formula 2]
M(L1)x(L2)y(L3)z
In Chemical Formula 2,
M is rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) or osmium (Os),
L1, L2 and L3 are the same or different from each other, and each independently hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) Or acetylacetonato (AcAc),
The x, y and z are each independently an integer of 0 to 5, and x, y and z are not 0 at the same time. The catalyst composition for hydroformylation reaction according to claim 1, wherein the phosphite-based ligand is represented by any one of the following structural formulas:

The catalyst composition for hydroformylation reaction according to claim 1, wherein the content of the phosphite-based ligand is 1% to 4% by weight based on the total weight of the catalyst composition for the hydroformylation reaction. The method according to claim 1, wherein the transition metal compound is cobaltcarbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonylrhodium [Rh(AcAc)(CO) ₂ ], acetylacetonatocarbonyltriphenylphosphine Rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium[HRh(CO)(TPP) ₃ ], acetylacetonatodicarbonyliridium [Ir(AcAc)( CO) ₂ ] and hydridocarbonyl tri (triphenylphosphine) iridium [HIr (CO) (TPP) ₃ ] The catalyst composition for a hydroformylation reaction comprising at least one of. The method of claim 1, wherein the solvent is propane aldehyde, butyl aldehyde, pentyl aldehyde, valer aldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, tensanol, benzene , Toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and a catalyst composition for a hydroformylation reaction comprising at least one of heptane. In the presence of the catalyst composition for hydroformylation reaction of any one of claims 1 to 5, a hydroformylation step of reacting an olefin-based compound with a synthetic gas to produce an aldehyde,
The synthetic gas is a method for producing an aldehyde containing carbon monoxide and hydrogen. The method of claim 6, wherein the molar ratio of carbon monoxide: hydrogen is 5:95 to 70:30. The method of claim 6, wherein the hydroformylation step is performed under a reaction temperature of 50°C to 130°C and a pressure of 5 bar to 25 bar. The method of claim 6, wherein the olefinic compound is propylene, and the aldehyde is butylaldehyde. The method of claim 9, wherein the aldehyde has a molar ratio of n-butylaldehyde to i-butylaldehyde of 3 or less.