Process for producing pentenenitriles

Patent metadata

Field	Value
Publication number	US-9932298-B2
Application number	US-201314649593-A
Country	US
Kind code	B2
Filing date	Dec 5, 2013
Priority date	Dec 7, 2012
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

The invention provides methods useful in the industrial scale process for hydrocyanation of butadiene to adiponitrile for recycle of unwanted byproduct 2-methyl-3-butenenitrile (2M3BN) by conversion to process intermediate pentenenitrile. The invention provides a process for generating catalysts useful for carrying out the hydrocyanation of butadiene to adiponitrile, the process comprising contacting the 2M3BN and a solution of a nickel-ligand catalyst in cis-2-pentenenitrile (cis-2PN), trans-2-pentenenitrile (trans-2PN), or a mixture thereof. The improved methods of the invention can provide improved catalyst solubility for bidentate ligands without a requirement for a Lewis acid catalyst promoter such as zinc chloride to be present.

First claim

What is claimed is:

1. A process for hydrocyanation of butadiene to adiponitrile, the process comprising:
hydrocyanating butadiene to form adiponitrile, the hydrocyanating comprising contacting 2-methyl-3-butenenitrile and a hydrocyanation catalyst system in a solvent system consisting essentially of cis-2-pentenenitrile, trans-2-pentenenitrile, or a mixture thereof, in the absence of a Lewis acid promoter, wherein an unwanted byproduct of the hydrocyanating of the 2-methyl-3-butenenitrile is converted in situ to a process intermediate pentenenitrile that undergoes further hydrocyanation to provide the adiponitrile, the hydrocyanation catalyst system comprising a soluble complex of nickel and a bidentate ligand of formula (III),

wherein X 12 , X 13 , X 14 , X 22 , X 23 , and X 24 each independently is oxygen;
wherein R 12 , R 13 , R 22 , and R 23 , each independently is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R 12 , R 13 , R 22 , or R 23 , each aryl ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cyclo alkyl, (C1-C10)alkoxy, (C3-C10)cyclo alkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, one or more of pairs R 12 and R 13 or R 22 and R 23 are mutually directly bonded, such that the R 12 X 12 and R 13 X 13 groups, or the R 22 X 22 and R 23 X 23 groups, or both, together with the respective phosphorus atom to which each pair of groups is bonded, forms a respective ring; and
Y is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl.

2. The process of claim 1 , wherein the solvent system consists essentially of cis-2-pentenenitrile.

3. The process of claim 1 , wherein the bidentate ligand is present in a ratio of 1:4 by weight relative to the solvent system.

4. The process 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, (C1-C10) alkyl, and (C1-C10)alkoxy, or wherein two adjacent R Y3 -R Y10 groups together form an optionally substituted fused aryl ring.

5. The process of claim 4 wherein R 12 , R 13 , R 22 , and R 23 are each independently phenyl substituted at a respective single ortho-position with a (C1-C10)alkyl or (C1-C10)alkoxy, wherein respective meta- and para-positions of the R 12 , R 13 , R 22 , and R 23 phenyls can each independently be unsubstituted or be independently substituted with (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, or (C3-C10)cyclo alkoxy(C1-C10)alkoxy;
R Y6 and R Y10 are independently (C1-C10)alkyl or (C1-C10)alkoxy, and R Y3 , R Y4 , R Y5 , R Y7 , R Y8 , and R Y9 , are independently H, (C1-C10)alkyl, or (C1-C10)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 (C1-C10)alkyl or (C1-C10)alkoxy.

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

or is of formula (XIII):

7. The process of claim 1 , wherein the catalyst system is free of ZnCl 2 .

8. The process of claim 1 , wherein the solvent system consists essentially of cis-2-pentenenitrile.

9. The process of claim 1 , wherein the bidentate ligand is present in a ratio of 1:4 by weight relative to the solvent system.

10. The process of claim 1 , wherein the contacting is performed in the presence of hydrogen cyanide.

11. The process of claim 1 , wherein the contacting is performed at a temperature of 80° C. to 140° C.

12. The process of claim 1 , wherein the contacting is performed at a temperature of 100° C. to 130° C.

13. The process of claim 1 , further comprising preparing the hydrocyanation catalyst system, comprising:
contacting nickel metal and the bidentate ligand of formula (III) in an organic solvent system consisting essentially of cis-2-pentenenitrile, trans-2-pentenenitrile, or a mixture thereof, under conditions suitable to bring about reaction of the bidentate ligand and the nickel metal to provide an effective concentration of the nickel-ligand complex dissolved in the organic solvent system.

14. The process of claim 13 , wherein the conditions to bring about reaction of the bidentate ligand and the nickel metal comprise a temperature of 25-75° C.

15. The process of claim 14 , wherein the conditions to bring about reaction of the bidentate ligand and the nickel metal comprise a temperature of 65° C.

Assignees

• Invista North America Sarl

Inventors

• Vos Thomas E

Classifications

• B01J2531/847

  Nickel · CPC title

• B01J2531/90

  Catalytic systems characterized by the solvent or solvent system used · CPC title

• B01J31/185

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

• C07C253/10 Primary

  to compounds containing carbon-to-carbon double bonds · CPC title

• C07C255/04

  containing two cyano groups bound to the carbon skeleton · CPC title