Catalyst composition comprising phosphorus-based ligand and hydroformylation process using the same

Patent metadata

Field	Value
Publication number	US-9707552-B1
Application number	US-201515107361-A
Country	US
Kind code	B1
Filing date	Oct 19, 2015
Priority date	Jul 13, 2015
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

Abstract

Disclosed are a catalyst composition containing a phosphorous-based ligand and a hydroformylation process using the same. More specifically, disclosed are a catalyst composition containing a monodentate phosphite ligand, a monodentate phosphine ligand and a transition metal catalyst, wherein the total content of the entire ligand including the monodentate phosphite ligand and the monodentate phosphine ligand is 1 to 33 moles, based on 1 mole of the transition metal catalyst, and a hydroformylation method using the same.
The present invention has an effect of providing a catalyst composition which reduces an N/I (ratio of normal to iso) selectivity of aldehydes produced by hydroformylation of an olefin-based compound and exhibits superior catalytic activity and stability, and a hydroformylation method of an olefin-based compound using the catalyst composition.

First claim

What is claimed is:

1. A catalyst composition comprising:
a monodentate phosphite ligand represented by the following Formula 1;
a monodentate phosphine ligand represented by the following Formula 2; and
a transition metal catalyst represented by the following Formula 3,
wherein the total content of the entire ligand including the monodentate phosphite ligand and the monodentate phosphine ligand is 1 to 33 moles, based on 1 mole of the transition metal catalyst,

wherein R 1 , R 2 , R 3 , R′ 1 , R′ 2 and R′ 3 each independently represent: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms group; a substituted or unsubstituted aryl group having 6 to 36 carbon atoms; a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted heteroaryl group having 4 to 36 carbon atoms; or a substituted or unsubstituted heterocyclic group having 4 to 36 carbon atoms,
wherein the heteroalkyl group, the heteroaryl group and the heterocyclic group contain one or more atoms selected from the group consisting of N, O and S, and
when R 1 , R 2 , R 3 , R′ 1 , R′ 2 and R′ 3 are substituted by a substituent, the substituent is nitro (—NO 2 ), fluorine (—F), chlorine (—Cl), bromine (—Br) or an alkyl group having 1 to 20 carbon atoms,
M(L 1 ) x (L 2 ) y (L 3 ) 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),
L 1 , L 2 and L 3 each independently represent one selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) and acetylacetonato (AcAc), and
x, y and z each independently represent 0 to 5, with the proviso that all of x, y and z are not zero.

2. The catalyst composition according to claim 1 , wherein the content of each of the monodentate phosphite ligand and the monodentate phosphine ligand is 0.5 to 32.5 moles, based on 1 mole of the transition metal catalyst.

3. The catalyst composition according to claim 1 , wherein a mix ratio of the monodentate phosphite ligand and the monodentate phosphine ligand is 5:1 to 1:5, based on weight.

4. The catalyst composition according to claim 1 , wherein the monodentate phosphite ligand comprises one or more selected from the group consisting of triphenyl phosphite, tris(2,6-triisopropyl)phosphite, tris(2,6-di-tert-butyl-4-methoxyphenyl)phosphite, tris(2-tert-butyl-4-methylphenyl)phosphite and tris(2,4-di-tert-butylphenyl)phosphite (TDTBPP).

5. The catalyst composition according to claim 1 , wherein the monodentate phosphine ligand comprises one or more selected from the group consisting of tri-m-tolylphosphine (TMTP), tri-p-tolylphosphine (TPTP), diphenyl(p-tolyl)phosphine (DPPTP), cyclohexyldiphenylphosphine (CHDP), tris(2,6-dimethoxyphenyl)phosphine (TDMPP), tris(4-methoxyphenyl)phosphine (TMPP), trimesitylphosphine (TMSTP), tris-3,5-xylylphosphine (TXP), tricyclohexylphosphine (TCHP), tribenzylphosphine (TBP), benzyl diphenylphosphine (BDPP) and diphenyl-n-propylphosphine (DPMPP).

6. The catalyst composition according to claim 1 , wherein the transition metal catalyst comprises one or more selected from the group consisting of cobalt carbonyl [Co 2 (CO) 8 ], acetylacetonatodicarbonyl rhodium [Rh(AcAc)(CO) 2 ], acetylacetonatocarbonyltriphenylphosphine rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium [HRh(CO)(TPP) 3 ], acetylacetonatodicarbonyl iridium [Ir(AcAc)(CO) 2 ] and hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP) 3 ].

7. The catalyst composition according to claim 1 , further comprising one or more solvents selected from the group consisting of propane aldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, hexanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane.

8. The catalyst composition according to claim 1 , wherein the content of the transition metal catalyst is 1 to 1,000 ppm, based on the catalyst composition.

9. A hydroformylation method of an olefin-based compound comprising reacting an olefin-based compound with a synthetic gas (CO/H 2 ) of carbon monoxide and hydrogen in the presence of the catalyst composition according to claim 1 , to prepare aldehyde.

10. The hydroformylation method according to claim 9 , wherein the olefin-based compound is a compound represented by the following Formula 4:

wherein R 4 and R 5 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), trifluoromethyl (—CF 3 ) or an aryl group having 6 to 20 carbon atoms and having 0 to 5 substituents,
wherein the substituent of the aryl group is nitro (—NO 2 ), fluorine (—F), chlorine (—Cl), bromine (—Br), methyl, ethyl, propyl or butyl.

11. The hydroformylation method according to claim 9 , wherein the olefin-based compound comprises one or more selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and styrene.

12. The hydroformylation method according to claim 9 , wherein a normal/iso ratio of the produced aldehyde is 1.5 to 3.0.

13. The hydroformylation method according to claim 9 , wherein a mix ratio of carbon monoxide and hydrogen in the synthetic gas (CO/H 2 ) is 5:95 to 70:30, on a mole basis.

Assignees

• Lg Chemical Ltd
• Lg Chemical Ltd

Inventors

• Kim Mi Young
• Choi min ji
• Eom Sung Shik
• Ko Dong Hyun
• Jung Da Won
• Kim Tae Yun

Classifications

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title

• B01J31/2404 Primary

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J31/2234

  Beta-dicarbonyl ligands, e.g. acetylacetonates · CPC title

• C07C45/50

  by oxo-reactions · CPC title

• B01J31/2495 Primary

  Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands · CPC title