Process for the hydroformylation of olefins using a cobalt precatalyst and a diphosphine ligand

Abstract

Process for the hydroformylation of olefins using a cobalt precatalyst and a diphosphine ligand.

Claims

1. Process comprising the process steps of: a) adding an olefin; b) adding a cobalt precatalyst; c) adding a ligand (L) having the structure (I): ##STR00005## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected from: H,(C.sub.1-C.sub.12)-alkyl, -(C.sub.6-C.sub.20)-aryl; wherein the ligand is added in a molar ratio to cobalt of L/Co = < 0.95/1; d) supplying of syngas; e) heating the reaction mixture from a) to d), to convert the olefin into an aldehyde.

2. Process according to claim 1, where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected from: -(C.sub.1-C.sub.12)-alkyl, -(C.sub.6-C.sub.20)-aryl.

3. Process according to claim 1, where R.sup.1, R.sup.2 are —Ph.

4. Process according to claim 1, where R.sup.1, R.sup.3 are —Ph.

5. Process according to claim 1, where the ligand has the structure (1): ##STR00006## .

6. Process according to claim 1, wherein the ligand is added in a molar ratio to cobalt of L/Co = < 0.90/1.

7. Process according to claim 1, wherein the ligand is added in a molar ratio to cobalt of L/Co = < 0.80/1.

8. Process according to claim 1, wherein the Co precatalyst is initially charged in the form of a solution.

9. Process according to claim 8, wherein the olefin is added to the initially charged Co precatalyst solution.

10. Process according to claim 1, wherein the syngas is supplied in process step d) at a pressure within a range from 1 to 8 MPa (10 to 80 bar).

11. Process according to claim 1, wherein the heating of the reaction mixture in process step e) is to a temperature within a range from 80° C. to 180° C.

12. Process according to claim 1, wherein the cobalt precatalyst is [Co(acac)(C.sub.4H.sub.8O.sub.2).sub.4].sup.+[BF.sub.4].sup.- (V1).

13. Process according to claim 1, wherein the olefin is selected from: ethene, propene, 1-butene, cis-2-butene, trans-2-butene, mixture of cis- and trans-2-butene, raffinate 1, raffinate 2, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 1-methylcyclohexene, tetramethylethene, 1-octene, 2-octenes, cyclooctene, di-n-butene, diisobutene, undecenes, dodecenes, triisobutene, tri-n-butene.

Description

[0040] The invention shall be elucidated in more detail hereinbelow with reference to a working example.

HYDROFORMYLATION OF 1-OCTENE WITH [CO(ACAC)(C.SUB.4.H.SUB.8.O.SUB.2.)](BF.SUB.4.)

[0041] ##STR00003##

##STR00004##

1: 1,2-Bisdiphenylphosphinoethane DPPE

(V1): [Co(acac)(C.SUB.4.H.SUB.8.O.SUB.2.)](BF.SUB.4.)

[0042] A solution of the Co precatalyst (V1) and diphosphine (1) in diglyme (24 mL) was introduced into a 150 mL Premex autoclave with sparging stirrer and pressurized with 32 bar of syngas. The solution was heated to 160° C. and the pressure readjusted to 50 bar. After 5 minutes, the temperature was lowered to 140° C. The olefin (4.74 mL) was then added to the catalyst solution by means of a pressure pipette and the reaction solution (1 M olefin) stirred at 50 bar and 140° C. The reaction mixture was then cooled to room temperature and the pressure released. The yields were determined by gas chromatography.

[0043] Reaction conditions:

[0044] [Co]: 2.6 mM, T: 140° C., p(syngas): 50 bar, t: 1 h, precatalyst: V1

TABLE-US-00001 Hydroformylation of 1-octene Ligand Precatalyst P/Co L/Co T (°C) t (h) Yield (%) (1) V1 2:1 1:1 140 1 35.9 (1)* V1 0.23:1 0.115:1 140 1 69.9 * process according to the invention

[0045] With the ligand-cobalt ratio (L/Co) according to the invention, it was possible to increase the yield.

[0046] As demonstrated by the working example, the object is achieved by the process according to the invention.