KR100885609B1 - Catalyst composition comprising phosphine ligands and Hydroformylation reaction using the same - Google Patents

Abstract

Hydroformylation of an olefinic compound that produces an aldehyde by reacting a catalyst composition combining a potential metal catalyst with a coordination phosphorus compound containing oxygen, and reacting the catalyst composition with a mixture of an olefinic compound, carbon monoxide and hydrogen A method, a novel coordination phosphorus compound, and a hydroformylation method using the catalyst composition according to the present invention, in which the coordination phosphorus compound containing oxygen is applied not only to very high catalytic activity but also to isoaldehyde High selectivity.

Hydroformylation, catalysts, rhodium, ligands, phosphines, olefins, aldehydes, N / I selectivity, catalytic activity, synthesis gas

Description

Catalyst composition comprising phosphorus compound and hydroformylation reaction using the same {Catalyst composition comprising phosphine ligands and Hydroformylation reaction using the same}

The present invention relates to a catalyst composition comprising a coordinating phosphorus compound including oxygen, a hydroformylation reaction using the same, a novel coordinating phosphorus compound, and a preparation method thereof, and more particularly, to a hydroformylation reaction of an olefin compound. It relates to a bisphosphite compound used, a method for preparing the same, and a method for hydroformylation using the same.

Various olefins are reacted with carbon monoxide and hydrogen (CO + H ₂ ), commonly called synthetic gases, in the presence of homogeneous organometallic catalysts and ligands to increase carbon number by linear, normal and branched (iso). The hydroformylation reaction to produce aldehydes was first discovered in 1938 by Otto Roelen of Germany. Hydroformylation, commonly known as OXO, is an industrially important reaction for homogeneous catalysis. As of 2001, around 8.4 million tonnes of various aldehydes (including alcohol derivatives) are used in the oxo process. Are produced and consumed by the government ( SRI Report , November 2002, 682. 7000A). Various aldehydes synthesized by the oxo reaction are transformed into aldehyde derivatives acid and alcohol through oxidation or hydrogenation. In addition, after condensation reaction of Aldol, such as oxidation or hydrogenation may be transformed into various acids and alcohols containing long chain alkyl groups. In particular, the hydrogenated alcohol of the aldehyde by the oxo reaction is called oxo alcohol, which is widely used industrially such as solvents, additives, raw materials for various plasticizers, and synthetic lubricants.

It is known that a metal-carbonyl compound catalyst is active as a catalyst for hydroformylation reaction, and an industrially used catalyst is mainly produced according to the type and operating conditions of ligands applied in the cobalt (Co) and rhodium (Rh) series. The aldehyde's N / I selectivity (ratio of linear (normal) to branched (iso) isomers) varies. At present, more than 70% of the world's oxo plants are used for rhodium-based catalysts due to their high catalytic activity, high N / I selectivity, and relatively easy reaction conditions despite the disadvantages of expensive catalyst price and deterioration of catalyst activity due to poisoning. It adopts Low Pressure OXO Process with excessive amount of pin ligand.

In addition to cobalt (Co) and rhodium (Rh), the central metal of the oxo catalyst is iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), or nickel. (Ni) and the like can be applied. However, since each metal is known to exhibit catalytic activity in the order of Rh >>Co> Ir, Ru>Os>Pt>Pd>Fe> Ni, most of the processes and researches are focused on rhodium and cobalt. Ligands include phosphine (Phosphine, PR ₃ , R = C ₆ H ₅ , nC ₄ H ₉ ), phosphine oxide (Phosphine Oxide, O = P (C ₆ H ₅ ) ₃ ), phosphite, amine Amine, amide, or isonitrile are applicable, but few ligands surpass triphenylphosphine (TPP) in terms of catalytic activity and stability.

Eastman Kodak Company and Union Carbide Company (now integrated as Dow) have developed this coordination phosphine ligand with high catalytic activity and high N / I selectivity. (US 4,694,109 and US 4,668,651), bisphosphite ligands developed by Dow are known to be applied in some plants. However, the phosphite ligand represented by ligand B shown in Examples 6-9 of US Pat. No. 4,668,651 showed significantly lower N / I selectivity despite the very high catalytic activity. This shows that ligands of the same bisphosphite family have significantly different catalytic properties depending on their structure.

Recently, the demand for isoaldehyde has increased due to the development of products made from isoaldehyde as well as linear (normal) aldehyde. For example, isobutylaldehyde may be used as a precursor of neopentylglycol, which is used as a raw material of polyester resin for surface coating, or may be transformed into isobutyl alcohol and used as a raw material for coating solvent or grain herbicide. . Eastman, meanwhile, produces a variety of products from the Tishichenko reaction of isobutylaldehyde, such as Texanol (adhesive for latex surface coating) and isobutyl isobutyrate (surface coating solvent). The demand for products made of such isobutylaldehyde is increasing day by day. As the commercial value of isobutyl aldehyde is increased, there is an urgent need for a catalyst composition showing high isoaldehyde selectivity while maintaining excellent catalytic activity in order to obtain isobutyl aldehyde.

The first technical problem to be achieved by the present invention is to provide a catalyst composition comprising this coordination ligand and a transition metal catalyst that exhibit high selectivity for high catalytically active isoaldehyde.

The second technical problem to be achieved by the present invention is to provide a method for hydroformylation of an olefin-based compound for preparing an aldehyde by reacting the catalyst composition with a mixed gas of an olefin-based compound, carbon monoxide and hydrogen.

The third technical problem to be achieved by the present invention is to provide a compound of the coordination ligand and its preparation.

The present invention to achieve the first technical problem,

(a) this coordination ligand represented by the following formula (1); And

(b) provides a catalyst composition comprising a transition metal catalyst represented by formula (2):

In Chemical Formula 1,

R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and are each independently hydrogen, -R ₇ , -OR ₇ , -Si (R ₇ ) ₃ , -Si (OR ₇ ) ₃ , -C ( O) R ₇ , -C (O) OR ₇ , -OC (O) R ₇ , -C (O) N (R ₇ ) ₂ , -S (O) ₂ R ₇ , -S (O) R ₇ , -SR ₇ , -N (R ₈ ) ₂ , -N (R ₈ ) C (O) R ₈ , -P (O) (R ₈ ) ₂ , halogen, nitro, cyano, or hydroxy,

Wherein R ₇ is the same or different and is each independently C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents an alkyl,

Each R ₈ is independently the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents alkyl,

n represents an integer of 3 to 20,

In Chemical Formula 2,

M represents a transition metal,

L ¹ , L ² and L ³ are the same or different and are each independently hydrogen, CO, cyclooctadiene, norbonene, chlorine, triphenylphosphine, or acetylacetonane Toe,

x, y, and z each have a value of 0 to 5, except that x, y, and z are zero at the same time.

The present invention also to achieve the second technical problem,

Provided is a method of hydroformylation of an olefinic compound in which the catalyst composition according to the present invention is reacted with a mixed gas of an olefinic compound, carbon monoxide and hydrogen to produce an aldehyde.

The present invention also to achieve the third technical problem,

It provides a compound represented by the following formula (1).

[Formula 1]

Where

R ₁ , R ₂ , R ₃ , R ₄ and n are as defined above.

In another aspect, the present invention is the first step of reacting a compound represented by the formula (4) with a base; And

Step of reacting the obtained product of the first step with a compound represented by the formula

It provides a method of preparing the following formula (1) comprising:

[Formula 1]

Where

R ₁ , R ₂ , R ₃ , R ₄ , and n are the same as above,

X represents a halogen.

Hereinafter, the present invention will be described in detail.

Catalyst composition according to the present invention

(a) this coordination ligand represented by the following formula (1); And

(b) a transition metal catalyst represented by the following formula (2).

[Formula 1]

[Formula 2]

In Chemical Formula 1,

R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and are each independently hydrogen, -R ₇ , -OR ₇ , -Si (R ₇ ) ₃ , -Si (OR ₇ ) ₃ , -C ( O) R ₇ , -C (O) OR ₇ , -OC (O) R ₇ , -C (O) N (R ₇ ) ₂ , -S (O) ₂ R ₇ , -S (O) R ₇ , -SR ₇ , -N (R ₈ ) ₂ , -N (R ₈ ) C (O) R ₈ , -P (O) (R ₈ ) ₂ , halogen, nitro, cyano, or hydroxy,

Wherein R ₇ is the same or different and is each independently C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents an alkyl,

Each R ₈ is independently the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents alkyl,

n represents an integer of 3 to 20,

In Chemical Formula 2,

M represents a transition metal,

L ¹ , L ² and L ³ are the same or different and are each independently hydrogen, CO, cyclooctadiene, norbonene, chlorine, triphenylphosphine, or acetylacetonane Toe,

x, y, and z each have a value of 0 to 5, except that x, y, and z are zero at the same time.

As used herein, the term "alkyl" includes both straight, branched, or cyclic alkyl, and the term "aryl" includes both mono- and condensed rings, such as phenyl or naphthyl.

Substituents R ₁ , R ₂ , R ₃ , and R ₄ of the coordination ligand compound represented by Formula 1 are the same or different, and each independently represent hydrogen, -R ₇ , or -OR ₇ , and R ₇ is C It is preferable to represent _1- C ₈ -alkyl, and more preferably to hydrogen, tert-butyl, or methoxy, respectively. In addition, considering the activity and N / I selectivity of the catalyst, the n value of the formula (1) should be 3 to 20, the preferred n value is 3 to 6, more preferably n value is 3 or 4.

Especially preferred coordinating ligand compounds represented by formula (1)

4,4 "-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl [4,4" -Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP], or

4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4,4 "'-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44-QP].

On the other hand, the transition metal of Formula 2 is rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium ( Group VIII transition metal selected from the group consisting of Os), and mixtures thereof, more preferably cobalt (Co), rhodium (Rh), or iridium (Ir), most preferably rhodium (Rh) .

In addition, L ¹ , L ² and L ³ of the formula (2) is the same or different and each independently is preferably CO, acetylacetonato, or triphenylphosphine. More preferably L ¹ is CO, L ² is acetylacetonato and x and y are 2 and 1, respectively; L ¹ is CO, L ² is acetylacetonato, L ³ is triphenylphosphine and x, y and z are all 1; Or L ¹ is CO, L ² is hydrogen, L ³ is triphenylphosphine and x, y and z are 1, 1 and 3, respectively.

Particularly preferred transition metal catalyst of formula 2 is

Cobalt carbonyl (Co ₂ (CO) ₈ ),

Acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ),

Acetylacetonatocarbonyltriphenylphosphindium (Rh (AcAc) (CO) (TPP)),

Hydridocarbonyltri (triphenylphosphine) rhodium (HRh (CO) (TPP) ₃ ),

Acetylacetonatodicarbonyliridium (Ir (AcAc) (CO) ₂ ), or

Hydridocarbonyltri (triphenylphosphine) iridium (HIr (CO) (TPP) ₃ ).

In the catalysis of the present invention, the content of the transition metal (M) is preferably 50 to 500 ppm based on the total solution of the catalysis. If the content of the transition metal is less than 50 ppm, the hydroformylation reaction rate is slowed down, which is not commercially desirable. If the content of the transition metal is higher than 500 ppm, the transition metal is expensive, so the cost is increased and the reaction rate does not show a more favorable effect. .

The content of the coordinating ligand is preferably 0.5 to 100 mol, more preferably 1 to 20 mol, based on 1 mol of the transition metal (M). At this time, when the content of the coordinating ligand is less than 0.5 mole, there is a problem in the stability of the catalyst system, when the content of more than 100 mole is not preferable because there is a problem of cost increase because of the excessive use of the expensive ligand without a particular gain.

In particular, the catalyst composition according to the present invention has a transition metal catalyst of acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ), and the coordination ligand is 4,4 ″ -bis (((4,4 '-Dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl [4,4 "-Bis (((4,4'-dimethoxy- 6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP], or

4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4,4 "'-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44-QP].

The present invention also relates to a method for hydroformylation of an olefinic compound wherein the catalyst composition is reacted with a mixed gas of an olefinic compound, carbon monoxide and hydrogen to produce an aldehyde.

It is preferable that the said olefin type compound is an olefin type compound represented by following formula (3).

In Chemical Formula 3,

R ₅ and R ₆ are the same or different and each independently hydrogen; C ₁ -C ₂₀ -alkyl unsubstituted or substituted with halogen; halogen; Or a C ₆ -C ₂₀ -aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro groups, halogens and C ₁ -C ₈ -alkyl.

Particularly preferred olefin compounds represented by the formula (3) are ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, or styrene.

The hydroformylation reaction according to the invention can be carried out in the presence of a solvent. Solvents that can be used include aldehydes such as propane aldehyde, butyl aldehyde and baler aldehyde; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and cyclohexanone; Aromatics such as benzene, toluene and xylene; Halogenated aromatics including orthodichlorobenzene; Ethers such as tetrahydrofuran, dimethoxyethane and dioxane; Halogenated paraffins including methylene chloride; Or paraffin hydrocarbons such as heptane, and the like, but is not limited thereto. Preferably, aromatics such as various aldehydes or toluene are used.

The composition of the synthesis gas CO / H ₂ used in the hydroformylation reaction of the present invention can vary within a wide range. The molar ratio of CO / H ₂ is usually in the range of about 5:95 to 70:30, preferably about 40:60 to 60:40, particularly preferably about 1: 1.

The temperature and pressure of the hydroformylation reaction of the present invention are not particularly limited and may be carried out under conventional temperature and pressure conditions. Specifically, the reaction temperature is in the range of about 20 to 180 ° C., preferably about 50 to 150 ° C., and the reaction pressure is in the range of about 1 to 700 bar, preferably 1 to 300 bar.

For the hydroformylation reaction, first, the catalyst and ligands for the hydroformylation reaction are dissolved in a solvent such as benzene, toluene, ethanol, pentanol, octanol, texanol, butylaldehyde, or pentylaldehyde, and the catalyst and ligand are mixed. Prepare a solution. As the ligand in the above reaction, this coordination phosphorus compound containing nitrogen and this coordination phosphorus compound containing oxygen can be used independently or in combination.

In addition to the mixed solution of the catalyst and the ligand, a mixed gas of an olefin compound, carbon monoxide and hydrogen represented by the following Chemical Formula 3 may be injected into a reactor, and heated and pressurized while stirring to proceed the hydroformylation reaction.

The present invention also relates to a compound represented by the following general formula (1):

[Formula 1]

In Chemical Formula 1,

R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and are each independently hydrogen, -R ₇ , -OR ₇ , -Si (R ₇ ) ₃ , -Si (OR ₇ ) ₃ , -C ( O) R ₇ , -C (O) OR ₇ , -OC (O) R ₇ , -C (O) N (R ₇ ) ₂ , -S (O) ₂ R ₇ , -S (O) R ₇ , -SR ₇ , -N (R ₈ ) ₂ , -N (R ₈ ) C (O) R ₈ , -P (O) (R ₈ ) ₂ , halogen, nitro, cyano, or hydroxy,

Wherein R ₇ is the same or different and is each independently C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -ar-C ₁ -C ₂₀ -alkyl,

Each R ₈ is independently the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents alkyl,

n represents the integer of 3-20.

In another aspect, the present invention is the first step of reacting a compound represented by the formula (4) with a base; And

Step of reacting the obtained product of the first step with a compound represented by the formula

It relates to a method of preparing the following Chemical Formula 1, comprising:

[Formula 4]

[Formula 5]

[Formula 1]

Where

R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and are each independently hydrogen, -R ₇ , -OR ₇ , -Si (R ₇ ) ₃ , -Si (OR ₇ ) ₃ , -C ( O) R ₇ , -C (O) OR ₇ , -OC (O) R ₇ , -C (O) N (R ₇ ) ₂ , -S (O) ₂ R ₇ , -S (O) R ₇ , -SR ₇ , -N (R ₈ ) ₂ , -N (R ₈ ) C (O) R ₈ , -P (O) (R ₈ ) ₂ , halogen, nitro, cyano, trifluoromethyl or hydroxy Indicates,

Wherein R ₇ is the same or different and is each independently C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents an alkyl,

Each R ₈ is independently the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₁ -C ₂₀ -alk-C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ - are -C ₁ -C ₂₀ - represents alkyl,

n represents an integer of 3 to 20,

X represents a halogen.

Looking at the manufacturing method of the compound of Formula 1 specifically as follows. First, the compound of Formula 4 is dissolved in a solvent, and then a base is added to the reaction solution. Thereafter, the compound of Formula 5 may be added dropwise, and the precipitate obtained may be filtered, purified, and dried to obtain this coordination compound including oxygen of Formula 1.

Anhydrous hydrofuran, benzene, toluene, ether, dichloromethane, and the like may be used as a solvent used in the method for preparing the compound of Formula 1, in particular, anhydrous hydrofuran is preferable. The base may also be n-Butyl Lithium, tert-ButylLithium, sodium hydride (NaH), potassium hydride (KH), trialkyl amine, or pyridine It may be selected from the group consisting of.

Hereinafter, the present invention will be described in more detail with reference to the following synthesis examples and examples, the following synthesis examples and examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Synthesis Example 1, 2 Synthesis of Bidentate Phosphorus Compound Containing Oxygen

Synthesis Example  1: 4,4 "-bis (((4,4'- Dimethoxy -6,6'-d- Tert -Butyl-2,2'- Bisphenoxy Phosphino) Oxy ) Terphenyl  [4,4 "-Bis (((4,4'- dimethoxy -6,6'- di - tert -butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP]

160 g of sulfuric acid was heated to 110 ° C., and then 50 g of terphenyl was added, followed by reaction at 140 ° C. for 4 hours. After lowering the temperature of the reaction solution to 100 ℃ 150ml of water was added. The resulting white solid was filtered to obtain 105 g of terphenyl-4,4-sulfonic acid. 30 g of the resulting terphenyl-4,4-disulfonic acid, 7.2 g of sodium carbonate, and 72 g of potassium hydroxide were heated to 330 ° C, and reacted for 3 hours to obtain 13 g of 4,4 "-dihydroxyterphenyl (4 , 4 "-dihydroxyterphenyl) was obtained. 3.2 g of 4,4 "-dihydroxyterphenyl was dissolved in anhydrous hydrofuran, and anhydrous hydrofuran in which 9 ml of triethylamine was dissolved was added. 4,4'-dimethoxy-6, 10 g of 6'-di-tert-butyl-2,2'-bisphenoxy phosphorus chloride (4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxyphosphorous chloride) The dissolved anhydrous hydrofuran was slowly added dropwise The reaction solution was stirred overnight at room temperature The resulting precipitate was filtered and the solvent was removed under reduced pressure, and then the resulting liquid was subjected to column chromatography (elute: 12.5% EtOAc / hexane). The solvent was removed under reduced pressure, and then dissolved in acetonitrile and recrystallized in a freezer.

¹ H NMR (CDCl ₃ ): 1.51 (s, 36H, -C ₄ H ₉ ), 3.85 (s, 12H, -OCH ₃ ), 6.78 (s, 4H, Ar-H), 7.04 (s, 4H, Ar -H), 7.19 (d, 4H, Ar-H), 7.58 (d, 4H, Ar-H), 7.63 (d, 4H, Ar-H).

Synthesis Example  2: 4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4 , 4 "'-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44- QP Synthesis

6.25 g of 4-hydroxy-4'-bromo biphenyl was added dropwise to 40 g of 10% sodium hydroxide solution, heated to 90-95 ° C., and reacted for 1 hour. After cooling the solution to 80 ° C., 0.06 g of 5% palladium / carbon catalyst was added, and then heated to 95 ° C., and 6.5 g of water in which 1.75 g of hydroxyl amine hydrochloride was dissolved was added dropwise for 1 hour. After further reacting at the same temperature for 2 hours and cooling to room temperature, 3.5 g of 4,4 "'-dihydroxy quarter phenyl was obtained through filtration and neutralization. The compound described above was synthesized in the same manner as in Synthesis Example 1, except that 2.45 g of the produced 4,4 ″ ′-dihydroxy quarter phenyl was applied.

¹ H NMR (CDCl ₃ ): 1.52 (s, 36H, -C ₄ H ₉ ), 3.86 (s, 12H, -OCH ₃ ), 6.78 (s, 4H, Ar-H), 7.05 (s, 4H, Ar -H), 7.20 (d, 4H, Ar-H), 7.60 (d, 4H, Ar-H), 7.65 (d, 4H, Ar-H), 7.72 (d, 4H, Ar-H).

Example  1 to 4: Acetylacetonatodicarbonyldium  (Rh ( AcAc ) (CO) ₂ ) And 4,4 "-bis (((4,4'- Dimethoxy -6,6'-d- Tert -Butyl-2,2'- Bisphenoxy ) Phosphino ) Oxy ) Terphenyl [4,4 "-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP] Propene Hydroformylation  reaction

0.100 mg (0.390 mmol) of Rh (AcAc) (CO) ₂ as a catalyst in the reactor of High Throughput Screen Unit (HTS) manufactured by Auto Clave, hexadecane (GC analysis) Hexadecane) was added after dissolving this coordination ligand 44-TP in toluene solvent to 100 mL according to the molar ratio to rhodium shown in Table 1 below. The reaction solution having a molar ratio of 1: 1 propene: CO: H ₂ was injected into the reaction solution, and the pressure in the reactor was maintained at 6 bar, followed by 2.5 hours of stirring at 85 ° C.

Types of catalysts and ligands for the reaction and molar ratios of ligands to catalysts, N / I selectivity and catalytic activity are described in detail in Table 1.

In Table 1 below, N / I selectivity is a value obtained by dividing the amount of normal butylaldehyde (normal-butyraldehyde) generated in the reaction by the amount of isobutyl aldehyde (iso-butyraldehyde), and the amount of each aldehyde is added as an internal substance. Based on the amount of hexadecane, it was obtained by gas chromatography (GC) analysis.

Catalytic activity is a value obtained by dividing the total amount of normal aldehyde and isoaldehyde generated by the reaction by the molecular weight of butylaldehyde, the concentration of the catalyst used, and the reaction time. In this case, the unit of catalytic activity is mol _{( BAL )} / mol _(Rh) / h.

Example  5 to 8: Acetylacetonatodicarbonyldium  (Rh ( AcAc ) (CO) ₂ ) And 4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4 , 4 "'-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44- QP ] Propene Hydroformylation  reaction

4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl instead of 44-TP Catalytic activity experiments were performed in the same manner as in Examples 1 to 4 except for applying (44-QP), and the results are shown in Table 2.

Comparative example  One: Acetylacetonatodicarbonyldium  (Rh ( AcAc ) (CO) ₂ Catalyst and Triphenylphosphine ( triphenylphosphine , TPP With) Propene Hydroformylation  reaction

Catalytic activity experiments were performed in the same manner as in Example 1 except that TPP was used as the ligand and the molar ratio of ligand to rhodium was 100. The results are shown in Table 3.

Comparative example  2 to 4: Acetylacetonatodicarbonyldium  (Rh ( AcAc ) (CO) ₂ ) Catalyst and 1,4-bis (((4,4'- Dimethoxy -6,6’-d- Tert -Butyl-2,2'- Bisphenoxy ) Phosphino ) Oxy ) Phenyl (1,4-bis (((4,4'- dimethoxy -6,6’- di - tert -butyl-2,2’- bisphenoxy ) phosphino ) oxy) phenyl, Ligand  Using B) Propene Hydroformylation  reaction

Ligand B shown in Examples 6-9 of USP 4,668,651 instead of TPP was used as a ligand, and catalytic activity experiment was carried out in the same manner as in Comparative Example 1 except that the molar ratio of ligand to rhodium was 3, 5, or 10. Is shown in Table 3.

As shown in Comparative Example 1, the catalytic activity and N / I selectivity of the hydroformylation reaction of propene using TPP, which is a coordinating compound, as a ligand, were 95.8 mol _{( BAL )} / mol _(Rh) / h and N / I selectivity is 3.9.

When Ligand B of USP 4,668,651 was applied, it showed low N / I selectivity of 2 or less as shown in Comparative Examples 2 to 4, and also showed high catalytic activity of 150 mol _{( BAL )} / mol _(Rh) / h or more. However, in the hydroformylation of propene with Ligand B, the catalytic activity decreased and the selectivity for isobutylaldehyde also decreased as the molar ratio of ligand to rhodium increased.

On the other hand, the catalytic activity and N / I selectivity for the hydroformylation reaction of propene to which the coordination phosphorus compound containing oxygen used in Examples 1 to 8 were applied, when n was 3 or 4 ligand was applied. As shown in Tables 3 and 4, it showed low N / I selectivity of about 1.0 ~ 1.3, and it was very high above 290 mol _{( BAL )} / mol _(Rh) / h without changing the activity even if the ligand molar ratio to rhodium was increased. It showed stable catalytic activity. As such, in the case of 44-TP and 44-QP, the catalytic activity thereof has an average of twice the activity of Ligand B, and has the advantage that the activity as well as the selectivity are stably maintained.

The hydroformylation reaction of the catalyst composition in which the coordinating phosphorus compound containing oxygen according to the present invention is applied as a ligand shows not only very high catalytic activity but also high selectivity to isoaldehyde.

Claims (22)

(a) this coordination ligand represented by the following formula (1); And (b) a catalyst composition comprising a transition metal catalyst represented by formula (2): [Formula 1]

[Formula 2]

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each independently represent hydrogen, -R ₇ , or -OR ₇ , R ₇ represents C ₁ -C ₈ -alkyl, n represents an integer of 3 to 20, In Chemical Formula 2, M represents a transition metal, L ¹ , L ² and L ³ are the same or different and are each independently hydrogen, CO, cyclooctadiene, norbonene, chlorine, triphenylphosphine, or acetylacetonane Toe, x, y, and z each have a value of 0 to 5, except that x, y, and z are zero at the same time. delete The catalyst composition of claim 1, wherein R ₁ , R ₂ , R ₃ , and R ₄ in Formula 1 are the same or different and are each hydrogen, tert-butyl, or methoxy. The catalyst composition of claim 1, wherein n in Formula 1 is 3 or 4. The compound of claim 1 wherein 4,4 "-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl [4,4" -Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP], or 4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4,4 Catalyst composition characterized in that "'-Bis ((((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44-QP] . According to claim 1, wherein the transition metal of formula (2) is rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) ), Osmium (Os), and a group VIII transition metal selected from the group consisting of a mixture thereof. The catalyst composition of claim 6, wherein the transition metal of Formula 2 is cobalt (Co), rhodium (Rh), or iridium (Ir). The catalyst composition of claim ¹ , wherein L ¹ , L ² and L ³ of Formula 2 are the same or different and are each independently CO, acetylacetonato, or triphenylphosphine. The method of claim 1, wherein the transition metal catalyst Cobalt carbonyl (Co ₂ (CO) ₈ ), Acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ), Acetylacetonatocarbonyltriphenylphosphindium (Rh (AcAc) (CO) (TPP)), Hydridocarbonyltri (triphenylphosphine) rhodium (HRh (CO) (TPP) ₃ ), Acetylacetonatodicarbonyliridium (Ir (AcAc) (CO) ₂ ), or A catalyst composition, characterized in that it is hydridocarbonyltri (triphenylphosphine) iridium (HIr (CO) (TPP) ₃ ). The catalyst composition according to claim 1, wherein the content of the transition metal is 50 to 500 ppm based on the total solution of the catalysis. The catalyst composition of claim 1, wherein the content of the coordinating ligand is 0.5 to 100 moles based on 1 mole of the transition metal. The method of claim 1, wherein the transition metal catalyst is acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ), and the coordination ligand is 4,4 ″ -bis ((((4,4′-dimeth). Methoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl [4,4 "-Bis (((4,4'-dimethoxy-6,6 '-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP] or 4,4 "'-bis (((4,4'-dimethoxy-6,6'-di -Tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4,4 "'-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl -2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44-QP]. A method for hydroformylation of an olefinic compound, wherein the catalyst composition of any one of claims 1 and 3 to 7 is reacted with a mixed gas of an olefinic compound, carbon monoxide and hydrogen to produce an aldehyde. The hydroformylation method according to claim 13, wherein the olefin compound is an olefin compound represented by the following formula (3). [Formula 3]

In Chemical Formula 3, R ₅ and R ₆ are the same or different and each independently hydrogen; C ₁ -C ₂₀ -alkyl unsubstituted or substituted with halogen; halogen; Or a C ₆ -C ₂₀ -aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro groups, halogens and C ₁ -C ₈ -alkyl. The hydroformylation method according to claim 14, wherein the olefinic compound is ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, or styrene. Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each independently represent hydrogen, -R ₇ , or -OR ₇ , R ₇ represents C ₁ -C ₈ -alkyl, n represents the integer of 3-20. delete The compound of claim 16, wherein R ₁ , R ₂ , R ₃ , and R ₄ in Formula 1 are the same or different and each is hydrogen, tert-butyl, or methoxy. 17. The compound of claim 16, wherein n in Formula 1 is 3 or 4. 17. The compound of claim 16, wherein the compound of formula 1 is 4,4 "-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) force) Pino) oxy) terphenyl [4,4 "-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) terphenyl, 44-TP Or 4,4 "'-bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quaterphenyl [4 , 4 "'-Bis (((4,4'-dimethoxy-6,6'-di-tert-butyl-2,2'-bisphenoxy) phosphino) oxy) quarterphenyl, 44-QP] . A first step of reacting a compound represented by Formula 4 with a base; And Reacting the obtained product of the first step with a compound represented by the formula Method for preparing a formula 1 characterized in that it comprises a: [Formula 4]

[Formula 5]

[Formula 1]

Where R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each independently represent hydrogen, -R ₇ , or -OR ₇ , R ₇ represents C ₁ -C ₈ -alkyl, n represents an integer of 3 to 20, X represents a halogen. The method of claim 21, wherein the base is n-Butyl Lithium, tert-Butyl Lithium, sodium hydride (NaH), potassium hydride (KH), trialkyl amine, And pyridine.