# US 10,501,486 B2 · Stabilized organophosphorous compounds

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- Number: US 10,501,486 B2
- Document ID: US10501486B2
- Status: Granted
- Kind: B2
- Application number: 15/310,031
- Filed: 2015-04-20
- Published: 2017-08-24
- Granted: 2019-12-10
- Earliest claimed: 2014-05-14
- Assignees: Dow Technology Investments LLC
- Applicants: Dow Technology Investments LLC
- Inventors: George R. Phillips; Glenn A. Miller; Marinus A. Bigi; Michael A. Brammer
- Web page: https://patentgrep.com/patent/US10501486B2

## CPC

- C07F 9/65746: {the molecule containing more than one cyclic phosphorus atom}
- B01J 31/185: {Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof}
- C07C 45/50: by oxo-reactions
- C07D 233/56: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2531/822: Rhodium
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

A hydroformylation process wherein the hydrolyzable organophosphorous ligand component of the catalyst is supplied as a stabilized ligand composition comprising a hydrolyzable organophosphorous ligand and, per 100 moles compound, from 0.05 to 13 acid-neutralizing equivalents of an acid scavenger.

## Claims

### Claim 1

A process comprising: (a) contacting CO, H2, and at least one olefin in a reaction zone of a hydroformylation system under hydroformylation conditions sufficient to form at least one aldehyde product in the presence of a catalyst comprising, as components, a transition metal and a hydrolyzable organophosphorous ligand, (b) providing the ligand as a ligand composition comprising the ligand and from 0.05 to 13 acid-neutralizing equivalents of an acid scavenger per 100 moles ligand, and (c) prior to providing the ligand composition, storing the ligand composition under a substantially oxidizer-free atmosphere, under vacuum, or both.

### Claim 2 (depends on 1)

The process of claim 1 wherein the ligand composition is stored for a period of at least 30 days.

### Claim 3 (depends on 1)

The process of claim 1 wherein the acid scavenger includes at least one compound selected from: triethanolamine (TEA) and ethoxylates thereof, methyldiethoxyamine, dimethylethoxyamine, ethyldiethoxyamine, tri-3-propoxyamine, tri-(2-(methanol)ethyl)amine, tri-isopropanolamine and propoxylates thereof, 4-hydroxyl-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-iso-butylamine, tri-iso-propylamine, tri-n-hexylamine, tri-n-octylamine, dimethyl-iso-propylamine, dimethyl-hexadecylamine, methyl-di-n-octylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-methyldiphenylamine, N,N-dimethylbenzylamine, N,N-dimethyl-l-naphthylamine, N,N, N′,N′-tetramethylethylene diamine, 1,4-diazabicyclo-[2,2,2]-octane, pyridine, picoline, lutidine, collidine, N-methylpiperidine, N-methylmorpholine, N-2′-hydroxyethylmorpholine, quinoline, iso-quinoline, quinoxaline, acridien, quinuclidine, imidazole, benzimidazole and benztriazole, sodium and/or potassium salts of phosphoric acid, sodium and/or potassium salts of citric acid, sodium and/or potassium salts of maleic acid, and sodium and/or potassium salts of fumaric acid.

### Claim 4 (depends on 1)

The process of claim 1 wherein the acid scavenger includes at least one compound selected from triethanolamine, methyldiethanolamine, dimethylethanolamine, ethyldiethanolamine, tri-3-propoxyamine, tri-(2-(methanol)ethyl)amine, tri-isopropanolamine, triethylamine, pyridine, N,N-dimethylaniline, 4-hydroxyl-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, imidazole, benzimidazole, trisodium phosphate, and di-sodium maleate.

### Claim 5 (depends on 1)

The process of claim 1 wherein the acid scavenger includes TEA.

### Claim 6 (depends on 1)

The process of claim 1 wherein the acid scavenger is TEA.

### Claim 7 (depends on 1)

The process of claim 1 wherein the amount of acid scavenger is from 0.2 to 6 equivalents of the acid scavenger per 100 moles ligand.

### Claim 8 (depends on 1)

The process of claim 1 wherein the amount of acid scavenger is from 0.5 to 2 equivalents of the acid scavenger per 100 moles ligand.

### Claim 9 (depends on 1)

The process of claim 1 wherein the hydrolyzable organophosphorous ligand is primarily in the solid phase.

### Claim 10 (depends on 1)

The process of claim 1 wherein the hydrolyzable organophosphorous ligand is primarily in the liquid phase.

### Claim 11 (depends on 1)

The process of claim 1 wherein the composition consists essentially of a hydrolyzable organophosphorous ligand and, per 100 moles compound, from 0.05 to 13 equivalents of the acid scavenger.

### Claim 12 (depends on 1)

The process of claim 1 wherein an aldehyde-containing stream is taken from the reaction zone and is at least partly forwarded to an extraction zone, and wherein in the extraction zone the acid scavenger is substantially removed from the aldehyde.

### Claim 13

A process for improving the storage stability of a ligand to be used as a catalyst component, the process comprising admixing a hydrolyzable organophosphorous ligand with from 0.05 to 13 equivalents of an acid scavenger per 100 moles of ligand to obtain a mixture of the ligand and the acid scavenger.