Patent Grant
10300472
This application Is a National Stage Application of International Application No. PCT/KR2016/011067 filed on Oct. 4, 2016, which claims the benefit of Korean Patent Application No. 10-2015-0139571, filed on Oct. 5, 2015 , all of which are hereby incorporated by reference in their entirety for all purposes as if fully set forth herein.
The present invention relates to a catalyst composition including a phosphorous-based ligand and a hydroformylation method using the catalyst composition. More particularly, the present invention relates to a catalyst composition that lowers a selection ratio of normal aldehyde to iso aldehyde (n/i ratio), which are generated during hydroformylation of an olefinic compound, and exhibits superior catalytic activity and stability and a method of hydroformylating an olefinic compound using the catalyst composition.
Hydroformylation, for production of linear (normal) and branched (iso) aldehydes, a carbon number of each of which is increased by one, by reacting various olefins with carbon monoxide (CO) and hydrogen (H2), which are generally referred to as synthesis gases, in the presence of a homogeneous organometallic catalyst and a ligand, was first discovered by Otto Roelen in Germany in 1938.
Hydroformylation, which is also known as oxo synthesis, is very important in industrial homogeneous catalytic reaction. Throughout the world, various aldehydes including alcohol derivatives are produced and consumed through the oxo process.
Various aldehydes, which are synthesized by oxo reaction, may be modified into various acids and alcohols with a long alkyl group by performing oxidization and hydrogenation after performing condensation reaction with aldol or the like. In particular, a hydrogenated alcohol, which is derived from an aldehyde synthesized by such oxo synthesis, is called an oxo alcohol. Such an oxo alcohol is widely utilized industrially as a raw material of solvents, additives, various plasticizers, synthetic lubricating oils, and the like.
Conventionally, the value of linear (normal) aldehyde derivatives among aldehydes generated by oxo synthesis was high, whereby most research on catalysts has focused on increasing the proportion of linear aldehyde derivatives. However, in recent years, isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-1,3-pentanediol, isovaleric acid and the like, which use a branched aldehyde derivative (iso-aldehyde) as a raw material, were developed, and thus, demand for iso-aldehydes has increased. Accordingly, research has been carried out to increase selectivity for the branched aldehyde derivative. Therefore, there is an urgent need for a catalyst exhibiting superior catalyst stability and activity while lowering a selection ratio of normal aldehyde to iso aldehyde (n/i ratio).
[Patent Document] (Patent Document 1) KR 2010-0092399 A
Therefore, the present invention has been made in view of the above problems, and it is one object of the present invention to provide a catalyst composition that lowers a selection ratio of normal aldehyde to iso aldehyde (n/i ratio), which are generated during hydroformylation of an olefinic compound, and exhibits superior catalytic activity and stability.
It is another object of the present invention to provide a method of hydroformylating an olefinic compound using the catalyst composition.
The above and other objects can be accomplished by the present disclosure described below.
In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a catalyst composition including a monocoordinated phosphine ligand represented by Formula 1 below; a monocoordinated phosphine ligand represented by Formula 2 below; and a transition metal catalyst represented by Formula 3 below:
wherein R1, R2 and R3 are each independently a C1 or C2 alkyl group or a C1 or C2 alkoxy group,
wherein Z is a C5 to C10 cycloalkyl group, and
M(L1)x(L2)y(L3)z [Formula 3]
wherein M is one selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os), L1, L2 and L3 are each independently one selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP), and acetylacetonato (AcAc), and x, y and z are each independently 0 to 5, but x, y and z are not simultaneously 0.
In accordance with another aspect of the present invention, there is provided a method of hydroformylating an olefinic compound, the method including a step of preparing an aldehyde by reacting an olefinic compound with a synthetic gas of carbon monoxide and hydrogen (CO/H2) in the presence of the catalyst composition.
As apparent from the above description, the present invention provides a catalyst composition that lowers a selection ratio of normal aldehyde to iso aldehyde (n/i ratio), which are generated during hydroformylation of an olefinic compound, and exhibits superior catalytic activity and stability.
In addition, the present invention provides a method of hydroformylating an olefinic compound using the catalyst composition.
Hereinafter, the present invention is described in detail.
The present inventors confirmed that, when two different kinds of monocoordinated phosphine ligands, which respectively have specific structures, are simultaneously applied to a catalyst composition used for hydroformylation of an olefin, superior catalytic activity and stability are exhibited while lowering a selection ratio of normal aldehyde to iso aldehyde (n/i ratio), compared to a catalyst composition to which a conventional phosphine ligand is applied, thus completing the present invention.
The catalyst composition according to the present invention is characterized by including two different kinds of monocoordinated phosphine ligands and a transition metal catalyst.
Constituents of the catalyst composition are now described in detail.
The two different monocoordinated phosphine ligands may be respectively represented by, for example, Formulas 1 and 2 below:
wherein R1, R2 and R3 may be each independently a C1 or C2 alkyl group or a C1 or C2 alkoxy group. In another embodiment, R1, R2 and R3 may be each independently a methyl group or a methoxy group.
In a specific embodiment, the monocoordinated phosphine ligand represented by Formula 1 may be tri-o-tolylphosphine or tris(o-methoxyphenyl)phosphine. In this case, a selection ratio of normal aldehyde to iso aldehyde (n/i ratio) may be lowered.
wherein Z may be a C5 to C10, C5 to C8, or C5 to C7 cycloalkyl group.
In a specific embodiment, the monocoordinated phosphine ligand represented by Formula 2 may be cyclopentyldiphenylphosphine or cyclohexyldiphenylphosphine. In this case, superior catalytic activity and stability are exhibited.
The content of each of the monocoordinated phosphine ligands represented by Formulas 1 and 2 may be, for example, 0.1 to 5% by weight, 0.1 to 3% by weight, or 0.5 to 3% by weight with respect to the catalyst composition. Within this range, superior catalytic activity and stability are exhibited and a selection ratio of normal aldehyde to iso aldehyde (n/i ratio) is lowered.
A total of the monocoordinated phosphine ligands represented by Formulas 1 and 2 may be included in an amount of, for example, 0.2 to 10% by weight, 1 to 8% by weight, or 2 to 5% by weight with respect to the catalyst composition. Within this range, superior catalytic activity and stability are exhibited and a selection ratio of normal aldehyde to iso aldehyde (n/i ratio) is lowered.
A mix ratio by weight of the monocoordinated phosphine ligand represented by Formula 1 the monocoordinated phosphine ligand represented by Formula 2 may be, for example, 10:1 to 1:5, 5:1 to 1:3, or 5:1 to 1:2. Within this range, a selection ratio of normal aldehyde to iso aldehyde (n/i ratio) is lowered.
Each of the monocoordinated phosphine ligands represented by Formulas 1 and 2 may be included in an amount of, for example, 0.5 to 80 moles, 1 to 60 moles, or 1 to 40 moles based on 1 mole of a transition metal in the transition metal catalyst. Within this range, superior catalytic activity and stability are exhibited.
The transition metal catalyst may be, for example, a catalyst represented by Formula 3 below:
M(L1)x(L2)y(L3)z [Formula 3]
wherein M may be, for example, one selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), and osmium (Os), L1, L2 and L3 may be each independently, for example, one selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP), and acetylacetonato (AcAc), and x, y and z may be each independently, for example, 0 to 5, with the provision that x, y and z are not simultaneously 0.
In a specific embodiment, the transition metal catalyst may be one or more selected from the group consisting of cobalt carbonyl [Co2(CO)8], acetylacetonato dicarbonyl rhodium [Rh(AcAc)(CO)2], rhodium acetylacetonato carbonyl triphenylphosphine [Rh(AcAc)(CO)(TPP)], hydrido carbonyl tri(triphenylphosphine)rhodium [HRh(CO) (TPP)3], acetylacetonato dicarbonyl iridium [Ir(AcAc)(CO)2], and hydrido carbonyl tri(triphenylphosphine)iridium [HIr(CO) (TPP)3]. In this case, superior catalytic activity is exhibited.
The transition metal catalyst may be included, for example, in a content of 1 to 1,000 ppm, 10 to 800 ppm, or 50 to 500 ppm based on the catalyst composition. Within this range, a hydroformylation rate is excellent.
The catalyst composition may further include, for example, one or more solvents selected from the group consisting of propane aldehyde, butyraldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, texanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and heptane. In this case, superior catalytic activity is exhibited.
A method of hydroformylating the olefinic compound according to the present invention is not specifically limited so long as the method is a general hydroformylation method. In a specific embodiment, the method may include a step of preparing an aldehyde by reacting an olefinic compound with a synthetic gas of carbon monoxide and hydrogen (CO/H2) in the presence of the catalyst composition.
The olefinic compound may be, for example, a compound represented by Formula 4 below:
wherein R4 and R5 may be each independently hydrogen, a C1 to C20 alkyl group, fluorine (—F), chlorine (—Cl), bromine (—Br), trifluoromethyl (—CF3), or a C6 to C20 aryl group substituted with 0 to 5 substituents, and the aryl group may be substituted with nitro (—NO2), fluorine (—F), chlorine (—Cl), bromine (—Br), methyl, ethyl, propyl, or butyl.
In a specific embodiment, the olefinic compound may be one or more selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and styrene.
A mix ratio in moles of carbon monoxide:hydrogen in the synthetic gas (CO/H2) may be, for example, 5:95 to 70:30, 40:60 to 60:40, or 45:55 to 55:45. Within this range, the gases in the reaction are not accumulated, whereby the catalyst exhibits superior reactivity.
In the hydroformylation method, a reaction temperature of the olefinic compound and the synthetic gas (CO/H2) in the presence of the catalyst composition may be 20 to 180° C., 50 to 150° C., or 75 to 125° C. Within this range, stability and activity of the catalyst are maintained during the hydroformylation.
In another embodiment, in the hydroformylation method, a reaction pressure of a reactor may be 1 to 700 bar, 1 to 300 bar, or 5 to 30 bar. Within this range, superior catalytic activity is exhibited.
The method of hydroformylating the olefinic compound may be represented by, for example, Reaction Formula 1 below:
In a specific embodiment, the transition metal catalyst represented by Formula 3 and the two different monocoordinated phosphine ligands represented by Formulas 1 and 2 are dissolved in the solvent, thereby preparing a mixture solution of the transition metal catalyst and the ligands. The resultant mixture is fed along with the olefinic compound represented by Formula 4 and the synthetic gas (CO/H2) into a general reactor, followed by elevating temperature and applying pressure while stirring such that hydroformylation occurs. As a result, an aldehyde may be produced.
An aldehyde prepared according to the method of hydroformylating an olefinic compound may have a selection ratio of normal aldehyde to iso aldehyde of, for example, 2.5 or less, 1.0 to 2.5, or 1.2 to 2.0.
Now, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are provided for illustrative purposes only. Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention. Therefore, it is obvious that the modifications, additions and substitutions are within the scope of the present invention.
0.122 g (0.3 mmol) of rhodium acetylacetonato carbonyl triphenylphosphine (Rh(AcAc)(CO)(TPP), ROPAC), as a catalyst, and ligands (L1 and L2) were dissolved in a valeraldehyde solvent such as a total amount of a resultant solution reached 100 g (Rh 250 ppm). Here, the amounts of the used ligands (L1 and L2) are summarized in a unit of % by weight in Table 1 below. The resultant solution was fed into a 600 ml autoclave reactor. A mixed gas including propylene and a synthetic gas (CO/H2) that were mixed in a mole ratio of 1:1:1 (propylene:CO:H2) was injected into the reaction solution, and an interior pressure of the reactor was maintained at 8 bar. Reaction was carried out at 90° C. for one hour while stirring.
[Test Example]
A selection ratio of normal aldehyde to iso aldehyde (n/i ratio), catalytic activity, and stability of a catalyst composition prepared according to each of Example 1 to 4 and Comparative Example 1 to 8 were measured according to the following methods. Results are summarized in Table 1 below.
Measurement methods
Catalytic stability (normal stability (aging), %): Was calculated according to Mathematical Equation 2 below to represent change in catalytic activity as a percentage. Particularly, a synthetic gas including CO and H2 mixed in a mole ratio of 1:1 was injected into a reaction solution of each of examples and comparative examples and stirring was performed at 120° C. for 15 hours. Subsequently, a mixed gas including propylene and synthetic gas (CO/H2) mixed in a mole ratio of 1:1:1 (propylene:CO:H2) was injected into the resultant mixture, and stirring was performed at 90° C. for one hour while maintaining an interior pressure of a reactor at 8 bar such that reaction occurred. Subsequently, catalytic activity was measured. The measured catalytic activity was compared to that of Comparative Example 1 (fresh).
Catalytic stability (aging)=Total weight of normal and iso butyraldehydes of example or comparative example after 15 hours/total weight of 1.5 ormal and iso butyraldehydes of Comparative Example 1 (fresh)×100 [Mathematical Equation 2]
As shown in Table 1, it can be confirmed that, in the cases of the catalyst compositions according to Examples 1 to 4 prepared according to the present invention, a selection ratio of normal aldehyde to iso aldehyde (n/i ratio) is maintained at 2.5 or less and superior catalytic activity and stability are exhibited (see
On the other hand, it can be confirmed that, in the cases of the catalyst compositions according to Comparative Examples 1 to 4 including only one ligand type, i.e., tri-o-tolylphosphine (TOTP), catalytic activity is rapidly decreased over time, and thus, catalytic stability is very poor (see
Further, it can be confirmed that, in the case of the catalyst composition according to Comparative Example 7 using tri-o-tolylphosphine (TOTP) and triphenylphosphine (TPP) together and the case of the catalyst composition according to Comparative Example 8 using cyclohexyldiphenylphosphine (CHDP) and triphenylphosphine (TPP) together, a selection ratio of normal aldehyde to iso aldehyde (n/i ratio) rapidly increases.
From these results, it can be confirmed that, when a transition metal catalyst is simultaneously applied with two different kinds of monocoordinated phosphine ligands respectively having specific structures according to the present invention, the expressive ligands may be used in an appropriate amount, which is preferable in terms of cost and commerciality. In addition, due to application of the catalyst composition of the present invention, a selection ratio of normal aldehyde to iso aldehyde (n/i ratio), which is generated during hydroformylation of an olefinic compound, may be remarkably lowered while maintaining the activity and stability of a catalyst.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2015-0139571 | Oct 2015 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2016/011067 | 10/4/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/061745 | 4/13/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6153800 | Gelling et al. | Nov 2000 | A |
| 8178729 | Karvinen | May 2012 | B2 |
| 20080281128 | Karvinen et al. | Nov 2008 | A1 |
| Number | Date | Country |
|---|---|---|
| 10-2007-0116109 | Dec 2007 | KR |
| 10-2010-0092399 | Aug 2010 | KR |
| 10-1095775 | Dec 2011 | KR |
| 10-2013-0131516 | Dec 2013 | KR |
| 10-2015-0015904 | Feb 2015 | KR |
| Number | Date | Country | |
|---|---|---|---|
| 20180272326 A1 | Sep 2018 | US |
