Hydroformylation catalyst

Patent metadata

Field	Value
Publication number	US-9861970-B2
Application number	US-201615372934-A
Country	US
Kind code	B2
Filing date	Dec 8, 2016
Priority date	Sep 9, 2015
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

Abstract

This invention pertains to hydroformylation catalysts containing a mixture of isomeric forms of halo-phosphorus ligands. This invention also describes a procedure for preparing isomers of certain halophosphite ligands, which contain the phosphorus atom in a macrocyclic ring.

First claim

We claim:

1. A catalyst composition comprising a transition metal (M) selected from Group VIIIB and rhenium, and a mixture of halophosphite conformational isomers A and B:

wherein
the lone pair of electrons on the phosphorus atom in isomer A is in a pseudo-equatorial orientation;
the lone pair of electrons on the phosphorus atom in isomer B is in a pseudo-axial orientation;
X is fluorine or chlorine;
R is a divalent group having the formula 1:

R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or a hydrocarbyl group containing 1 to 40 carbon atoms; and
R 6 and R 7 are each independently hydrogen or a hydrocarbyl group containing 1 to 10 carbon atoms with the proviso that at least one of R 6 and R 7 contains at least one carbon atom, and

wherein
(i) the molar ratio of B:A is such that the isomer B forms a complex with the transition metal, and
(ii) the molar ratio of A:M is 5 or less.

2. The catalyst composition comprising claim 1 , wherein the molar ratio of B:A is 20 or greater.

3. The catalyst composition comprising claim 1 , wherein the molar ratio of A:M is 4 or less.

4. The catalyst composition comprising claim 1 wherein X is fluorine.

5. The catalyst composition comprising claim 1 , wherein R is a 2,2′-ethylidene bis(4,6-di-tert-butylphenyl) group.

6. The catalyst composition comprising claim 1 , wherein the transition metal comprises rhodium.

7. A catalyst solution comprising:
a) a hydroformylation solvent, and
b) A catalyst composition comprising a transition metal (M) selected from Group VIIIB and rhenium, and a mixture of halophosphite conformational isomers A and B:

wherein
the lone pair of electrons on the phosphorus atom in isomer A is in a pseudo-equatorial orientation;
the lone pair of electrons on the phosphorus atom in isomer B is in a pseudo-axial orientation;
X is fluorine or chlorine;
R is a divalent group having the formula 1:

8. The catalyst solution comprising claim 7 , wherein the hydroformylation solvent is selected from alkanes, cycloalkanes, alkenes, cycloalkenes, carbocyclic aromatic compounds, esters, ketones, acetals, ethers, and water.

9. A method for separating conformational isomers, the method comprising:
(a) dissolving a feed mixture of halophosphite conformational isomers A and B in a solvent to form a reactant solution:

wherein
the lone pair of electrons on the phosphorus atom in isomer A is in a pseudo-equatorial orientation;
the lone pair of electrons on the phosphorus atom in isomer B is in a pseudo-axial orientation;
X is fluorine or chlorine;
R is a divalent group having the formula 1:

R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or a hydrocarbyl group containing 1 to 40 carbon atoms; and
R 6 and R 7 are each independently hydrogen or a hydrocarbyl group containing 1 to 10 carbon atoms with the proviso that at least one of R 6 and R 7 contains at least one carbon atom;
(b) contacting the reactant solution with an alcohol in the presence of an acid catalyst at conditions effective to form a product mixture having a greater B:A molar ratio than the feed mixture; and
(c) quenching the product mixture with water.

10. The method comprising claim 9 , wherein the molar ratio of B:A in the feed mixture ranges from 1:1 to 0.7:1.

11. The method comprising claim 9 , wherein the molar ratio of B:A in the product mixture is greater than 30:1.

12. The method comprising claim 9 , wherein the molar ratio of B:A in the product mixture is greater than 200:1.

13. The method comprising claim 9 , wherein the solvent comprises toluene.

14. The method comprising claim 13 , wherein the solvent further comprises an alcohol.

15. The method comprising claim 14 , wherein the alcohol comprises ethanol or 2-propanol.

16. The method comprising claim 9 , wherein the acid catalyst comprises p-toluenesulfonic acid.

17. A composition comprising conformational isomers A and B:

wherein
the lone pair of electrons on the phosphorus atom in isomer A is in a pseudo-equatorial orientation;
the lone pair of electrons on the phosphorus atom in isomer B is in a pseudo-axial orientation;
X is fluorine or chlorine;
R is a divalent group having the formula 1:

R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or a hydrocarbyl group containing 1 to 40 carbon atoms; and
R 6 and R 7 are each independently hydrogen or a hydrocarbyl group containing 1 to 10 carbon atoms with the proviso that at least one of R 6 and R 7 contains at least one carbon atom, and

wherein the composition has a B:A molar ratio of greater than 1:1.

18. The composition comprising claim 17 , wherein the molar ratio of B:A is 20 or greater.

19. The composition comprising claim 17 , wherein X is fluorine.

20. The composition comprising claim 17 , wherein R is a 2,2′-ethylidene bis(4,6-di-tert-butylphenyl) group.

Assignees

• Eastman Chem Co

Inventors

• Puckette Thomas Allen
• Shan Xiaopeng
• Rodgers Jody Lee
• Green Brian E

Classifications

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title

• B01J31/185

  Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof · CPC title

• B01J2531/822

  Rhodium · CPC title

• B01J2531/004

  Ligands · CPC title

• B01J2540/22

  comprising fluorine, e.g. trifluoroacetate · CPC title