Composition for improved nickel-ligand solubility

Patent metadata

Field	Value
Publication number	US-9687835-B2
Application number	US-201314649648-A
Country	US
Kind code	B2
Filing date	Dec 6, 2013
Priority date	Dec 7, 2012
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

In the hydrocyanation reaction of butadiene proceeding through pentenenitriles to adiponitrile, catalysis by complexes of zerovalent nickel with bidentate phosphorus-based ligands of the NiL 2 A type wherein L 2 is a bidentate ligand and A is an unsaturated compound, can be rate-limited by the solubility of the catalytic complex. The present invention concerns solvent compositions for the nickel-ligand complex comprising mixtures of unsaturated nitriles that provide for increased metal solubility, particularly in the absence of a Lewis acid promoter, resulting in higher hydrocyanation reaction rates in an industrial-scale process for production of important nylon manufacturing intermediates. The mixed nitrile solvent compositions can include mixtures of pentenenitriles and/or methylbutenenitriles. The mixtures of mixed unsaturated nitriles can be, at least in part, from recycle streams from the hydrocyanation reaction for which the nickel-bidentate ligand complexes are used as catalysts.

First claim

What is claimed is:

1. A method of preparing a composition comprising a catalytic ML 2 A-type nickel-ligand complex, the method comprising:
contacting a nickel metal and a solution of a bidentate phosphorus-based ligand in a mixed unsaturated nitrile solvent system comprising more than one pentenenitrile, more than one methylbutenenitrile, or a mixture of at least one pentenenitrile and at least one methylbutenenitrile, in the absence of a Lewis acid promoter, to form the composition comprising the catalytic ML 2 A-type nickel ligand complex;
wherein
M is nickel metal, L 2 is a single mole equivalent of a bidentate phosphorus-based ligand, and A is an unsaturated compound, and
the ML 2 A-type nickel-ligand complex is dissolved in the mixed unsaturated nitrile solvent system.

2. The method of claim 1 wherein the mixed unsaturated nitrile solvent system comprises at least any two of 2-pentenenitrile and 3-pentenenitrile and 2-methyl-3-butanenitrile and 2-methyl-2-butenenitrile and 4-pentenenitrile.

3. The method of claim 1 wherein the mixed nitrile solvent comprises a mixture of about one part 2-penetenenitrile and two parts 3-pentenenitrile by weight.

4. The method of claim 1 , wherein the mixed unsaturated nitrile solvent system is at least in part from a recycle stream of a hydrocyanation reaction process for adiponitrile production.

5. The method of claim 1 , wherein at least some of the mixture of unsaturated nitriles is from a recycle stream in a hydrocyanation reaction process.

6. The method of claim 1 wherein the bidentate ligand is of formula (XII)

wherein R 12 , R 13 , R 22 and R 23 are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 -R Y10 is independently selected from the group consisting of hydrogen, (C 1 -C 10 ) alkyl, and (C 1 -C 10 )alkoxy, or wherein two adjacent R Y3 -R Y10 groups together form an optionally substituted fused aryl ring.

7. The method of claim 6 , wherein R 12 , R 13 , R 22 , and R 23 are each independently phenyl substituted at a respective single ortho-position with a (C 1 -C 10 )alkyl or (C 1 -C 10 )alkoxy, wherein respective meta- and para-positions of the R 12 , R 22 , R 22 , and R 23 phenyls can each independently be unsubstituted or be independently substituted with (C 1 -C 10 )alkyl, (C 3 -C 10 )cycloalkyl, (C 1 -C 10 )alkoxy, (C3-C 10 )cycloalkoxy, (C 3 -C 10 )cycloalkyl(C 1 -C 10 )alkyl, (C 3 -C 10 )cycloalkoxy(C 1 -C 10 )alkyl, (C3-C 10 )cycloalkyl(C 1 -C 10 )alkoxy, or (C 3 -C 10 )cycloalkoxy(C 1 -C 10 )alkoxy;
R Y6 and R Y10 are independently (C 1 -C 10 )alkyl or (C 1 -C 10 )alkoxy, and R Y3 , R Y4 , R Y5 , R Y7 , R Y8 , and R Y9 , are independently H, (C 1 -C 10 )alkyl, or (C 1 -C 10 )alkoxy, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (C 1 -C 10 )alkyl or (C 1 -C 10 )alkoxy.

8. The method of claim 1 , wherein the bidentate ligand is of formula (V):

or is of formula (XIII):

9. The method of claim 1 , wherein a concentration of the nickel-ligand complex dissolved in the mixed nitrile solvent composition is greater than a concentration of the nickel-ligand complex dissolved in a single nitrile solvent composition comprising a single pentenenitrile or a single methylbutenenitrile, under comparable conditions.

10. The method of claim 1 wherein a concentration of the nickel-ligand complex in the mixed nitrile solvent composition is greater than a concentration of the nickel-ligand complex in a single unsaturated nitrile solvent, under comparable conditions.

11. The method of claim 1 wherein the concentration of the nickel-ligand complex in the mixed nitrile solvent is at least about 5% higher than can be achieved for the nickel-ligand complex under comparable conditions in a single unsaturated nitrile solvent, under comparable conditions.

12. The method of claim 1 , wherein the nickel metal and the bidentate phosphorus-based ligand in the mixed unsaturated nitrile solvent composition are contacted at a temperature of 25-70° C.

13. The method of claim 1 , further comprising:
placing the composition comprising the catalytic ML 2 A-type nickel-ligand complex, butadiene, and hydrogen cyanide contained in a reactor suitable for carrying out a hydrocyanation reaction, to form a hydrocyanation reaction milieu, the reaction milieu being free of a Lewis acid promoter.

14. The method of claim 13 , further comprising:
recharging the hydrocyanation reaction milieu during a hydrocyanation reaction process with a recharge solvent system comprising the ML 2 A-type nickel-ligand complex, the recharge solvent system comprising a mixture of unsaturated nitriles, the mixture comprising more than one pentenenitrile, more than one methylbutenenitrile, or a mixture of at least one pentenenitrile and at least one methylbutenenitrile.

15. The method of claim 14 , wherein at least a portion of the recharge solvent system comprising the mixture of unsaturated nitriles is from a recycle stream of a hydrocyanation reaction process.

16. The method of claim 1 , further comprising:
carrying out a hydrocyanation reaction, comprising contacting an unsaturated hydrocyanation reaction substrate, hydrogen cyanide, and the composition comprising a catalytic ML 2 A-type nickel-ligand complex, under conditions suitable to bring about reaction of the substrate and the hydrogen cyanide.

17. The method of claim 16 , wherein the unsaturated hydrocyanation reaction substrate is the unsaturated compound A.

18. The method of claim 16 wherein the unsaturated hydrocyanation reaction substrate comprises at least any two of 2-pentenenitrile and 3-pentenenitrile and 2-methyl-3-butanenitrile and 2-methyl-2-butenenitrile and 4-pentenenitrile.

19. The method of claim 16 wherein the mixed nitrile solvent comprises a mixture of about one part 2-pentenenitrile and two parts 3-pentenenitrile by weight.

20. The method of claim 16 wherein the conditions comprise a reaction temperature of 80-140° C.

21. The method of claim 16 , wherein the ML 2 A-type nickel-ligand complex in a solvent system comprising a mixture of unsaturated nitriles is prepared using a recycle stream from a hydrocyanation reaction.

Assignees

• Invista North America Sarl

Inventors

• Vos Thomas E

Classifications

• B01J37/00

  Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J31/1865

  Phosphonites (RP(OR)2) , their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof · CPC title

• B01J2231/322

  Hydrocyanation · CPC title

• B01J31/185 Primary

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