Patent EA-001483-B1 (EA)
Title: Method of stabilizing a metal-organopolyphosphite ligand complex in processes catalyzed complex catalyst
Inventor: LEUNG TAK WAI
IPC: C07C45/50
Filed: 1996-12-05
Abstract: 1. A method of stabilizing a metal-organopolyphosphite ligand complex catalyst against deactivation in processes of hydroformylation which comprise reacting one or more reactants in the presence of a metal-organopolyphosphite ligand complex catalyst and optionally free organopolyphosphite ligand to produce a reaction product fluid comprising one or more products, which method comprises conducting said process in the presence of one or more free heterocyclic nitrogen compounds sufficient to prevent and/or lessen deactivation of the metal-organopolyphosphite ligand complex catalyst, wherein said one or more free heterocyclic nitrogen compounds are selected from the group consisting of diazole, triazole, diazine and triazine. 2. The method of claim 1 characterised in that the process of hydroformylation comprises reacting one or more olefinic unsaturated compounds with carbon monoxide and hydrogen in the presence of a metal-organopolyphosphite ligand complex catalyst and optionally free organopolyphosphite ligand to produce a reaction product fluid comprising one or more aldehydes, wherein at least a part of said process of hydroformylation is carried out in conditions, which are sufficient to influence, at least partially, deactivation of the metal-organopolyphosphite ligand complex catalyst. 3. The process of claim 2 characterised in that the process of hydroformylation is a continuous liquid recycle hydroformylation process. 4. The process of claim 2 characterised in that the hydroformylation process comprises (i) reacting in at least one reaction zone one or more olefinic unsaturated compounds with carbon monoxide and hydrogen in the presence of a metal-organopolyphosphite ligand complex catalyst and optionally free organopolyphosphite ligand to produce a reaction product fluid, comprising one or more aldehydes and (ii) separating in at least one separation zone or in said at least one reaction zone the one or more aldehydes from said reaction product fluid, and wherein at least a portion of said process is conducted at a carbon monoxide partial pressure sufficiently low to effect at least some deactivation of the metal-organopolyphosphite ligand complex catalyst. 5. The process of claim 4 characterised in that the process of hydroformylation is a continuous liquid recycle process. 6. The process of claims 1-5 characterised in that at least one free heterocyclic nitrogen compound is diazole which is imidazole, pyrazole or indazole. 7. The process of claims 1-5 characterised in that at least one free heterocyclic nitrogen compound is triazole which is 1,3,3-triazole, 1,2,4-triazole, 2,1,3-triazole or 4,1,2-triazole. 8. The process of claims 1-5 characterised in that at least one free heterocyclic nitrogen compound is diazine which is 1,2-diazine, 1,3-diazine or 1,4-diazine. 9. The processes of claim 6 wherein the diazole is a benzimidazole. 10. The processes of claim 9 wherein the benzimidazole is represented by formula:   wherein R<20>, R<21>, R<22>, R<23>, R<24> and R<25> are identical or different and each represents a hydrogen atom or a monovalent substituent, with the proviso that R<20> and R<21> are not both monovalent hydrocarbon radicals at the same time. 11. The processes of claim 7 wherein the triazole is represented by formula:   wherein R<8>, R<10> and R<11> are identical or different and each represents a hydrogen atom or a monovalent substituent, and adjacent substituents R<8> and R<11>, or R<10> and R<11>, may optionally be taken together to form a substituted or unsubstituted divalent radical which together with the two atoms of the formula to which said adjacent substituents are bonded form a cyclic ring. 12. The process of claim 11 wherein the triazole is benzotriazole. 13. The process of claims 1-5 wherein said metal-organopolyphosphite ligand complex catalyst is homogeneous or heterogeneous. 14. The process of claims 1-5 wherein said metal-organopolyphosphite ligand complex catalyst comprises rhodium complexed with an organopolyphosphite ligand represented by the formula:   wherein X represents a substituted or unsubstituted _n_-valent organic bridging radical containing from 2 to 40 carbon atoms, each R<1> is the same or different and represents a divalent organic radical containing from 4 to 40 carbon atoms, each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, wherein _a_ and _b_ can be the same or different and each have a value of from 0 to 6, with the proviso that the sum of _a_+_b_ is from 0 to 6 and _n_ equals _a_+_b_. 15. The process of claim 14 wherein said metal-organopolyphosphite ligand complex catalyst comprises rhodium complexed with an organopolyphosphite ligand represented by the formula selected from the following:   wherein X represents a substituted or unsubstituted divalent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R<1> is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, and each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms. 16. The process of claims 2-5 wherein at carbon monoxide partial pressures sufficiently low to effect at least some deactivation of the metal-organopolyphosphite ligand complex catalyst, the one or more free heterocyclic nitrogen compounds (i) have a coordination strength with respect to the metal of said metal-organopolyphosphite ligand complex catalyst sufficient to compete with carbon monoxide to effect at least some coordination with the metal of said metal-organopolyphosphite ligand complex catalyst, and (ii) have a coordination strength with respect to the metal of said metal-organopolyphosphite ligand complex catalyst sufficient not to compete with coordination of the organopolyphosphite ligand with the metal of said metal-organopolyphosphite ligand complex catalyst. 17. The process of claims 2-5 wherein at carbon monoxide partial pressures sufficiently low to effect at least some deactivation of the metal-organopolyphosphite ligand complex catalyst one or more free heterocyclic nitrogenous compounds (i) have a coordination strength with respect to the metal of said metal-organopolyphosphite ligand complex catalyst sufficient to effect at least some coordination with the metal of said metal-organopolyphosphite ligand complex catalyst, and (ii) have a coordination strength with respect to the metal of said metal-organopolyphosphite ligand complex catalyst less than the organopolyphosphite ligand of said metal-organopolyphosphite ligand complex catalyst. 18. The process of claims 1-11 wherein said reaction product fluid contains phosphorus acidic compounds, at least a portion of which are bonded by said one or more free heterocyclic nitrogen-containing compounds.