Process for stabilizing hydrocyanation catalyst

Patent metadata

Field	Value
Publication number	US-9296768-B2
Application number	US-201314404037-A
Country	US
Kind code	B2
Filing date	May 24, 2013
Priority date	Jun 1, 2012
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

The invention provides a method of forming a phosphonate diester compound from a ligand hydrolysis product (LHP) of a phosphite ligand used in a nickel-phosphite hydrocyanation catalyst, such as for conversion of 3-pentenenitrile to adiponitrile, which serves to eliminate acidic LHP compound for a hydrocyanation reaction milieu where the acidic LHP can catalyze further catalyst ligand destruction. The invention further provides phosphonate disester compounds prepared by alkylation of diarylphosphite LHP in the presence of a nickel-phosphite catalyst comprising a bidentate ligand, and a continuous hydrocyanation process for production of adiponitrile wherein catalyst ligand breakdown is inhibited through inactivation of ligand hydrolysis products towards further breakdown. A method of stabilizing a hydrocyanation catalyst is provided.

First claim

What is claimed is:

1. A method of forming a phosphonate diester compound of formula (I)

wherein
each Ar is independently an unsubstituted or a mono-substituted or a multi-substituted aryl group, wherein any aryl group can be substituted with independently selected (C1-C4)alkyl, hydroxyl, a phosphite ester group, or phosphonate ester group; or,
the two Ar groups are bonded to each other to provide an unsubstituted or substituted biaryl derivative, wherein the biaryl derivative is unsubstituted or is independently mono-substituted or multi-substituted with independently selected (C1-C4)alkyl, hydroxyl, a phosphite ester group, or a phosphonate ester group; and,
R is a 2-butenyl, 3-butenyl, 2-cyanobutyl, 3-cyanobutyl, or 4-cyanobutyl group;
the method comprising contacting in a reaction zone a diaryl phosphite compound of formula (III),

wherein Ar is as defined for the compound of formula (I), a pentenenitrile, hydrogen cyanide, a Lewis acid, and water, in the presence of a nickel catalyst comprising a bidentate phosphite ligand of formula (IV)

wherein R 1 and R 2 are each independently an unsubstituted or a substituted monovalent aryl, and each of R 3 -R 10 is independently selected from the group consisting of hydrogen, (C1-C10) alkyl, and (C1-C10)alkoxy, or wherein two adjacent R 3 -R 10 groups together form an optionally substituted fused aryl ring, under conditions suitable for hydrocyanation of the pentenenitrile to occur.

2. The method of claim 1 wherein for the bidentate phosphite ligand of formula (IV), R 1 and R 2 are both mono-ortho-substituted aryls, wherein the R 1 and R 2 aryl groups are each ortho-substituted with one respective (C1-C10)alkyl or (C1-C10)alkoxy group, provided that respective meta- and para-positions of the R 1 and R 2 aryls can be unsubstituted or substituted.

3. The method of claim 1 wherein for the bidentate phosphite ligand of formula (IV), R 6 and R 10 are not hydrogen.

4. The method of claim 1 , wherein for the bidentate phosphite ligand of formula (IV), at least one of R 3 , R 4 , and R 5 , and at least one of R 7 , R 8 , and R 9 , is not hydrogen.

5. The method of claim 1 , wherein for the bidentate phosphite ligand of formula (IV), R 5 and R 6 together form an optionally (C1-C10)alkyl-substituted or a (C1-C10)alkoxy-substituted fused phenyl ring, and wherein R 9 and R 10 together form an optionally (C1-C10)alkyl-substituted or a (C1-C10)alkoxy-substituted fused phenyl ring.

6. The method of claim 1 , wherein for the bidentate phosphite ligand of formula (IV), R 1 and R 2 are both mono-ortho-substituted aryls and the aryls are ortho-substituted with a (C1-C10)alkyl or a (C1-C10)alkoxy, R 6 and R 10 are a (C1-C10)alkyl or a (C1-C10)alkoxy, and at least one of R 3 -R 5 , and at least one of R 7 -R 9 , is a (C1-C10)alkyl or a (C1-C10)alkoxy.

7. The method of claim 1 wherein the pentenenitrile is 3-pentenenitrile.

8. The method of claim 1 wherein R 1 and R 2 are 2,4-xylyl.

9. The method of claim 1 wherein R 3 and R 7 are isopropyl, R 4 and R 8 are hydrogen, or R 5 , R 6 , R 9 and R 10 are methyl, or any combination thereof.

10. The method of claim 1 wherein the bidentate phosphite ligand of formula (IV) is

or is

Assignees

• Invista North America Sarl
• Invista North America Sarl

Inventors

• Tenn Iii William J

Classifications

• C07F15/04 Primary

  Nickel compounds · CPC title

• C07F9/4006 Primary

  Esters of acyclic acids which can have further substituents on alkyl · CPC title

• C07F9/145

  with hydroxyaryl compounds · CPC title

• C07F9/65744

  condensed with carbocyclic or heterocyclic rings or ring systems · CPC title

• B01J31/2221

  At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title