Process for making higher ethylene amines

Patent metadata

Field	Value
Publication number	US-11214549-B2
Application number	US-201816630283-A
Country	US
Kind code	B2
Filing date	Jul 3, 2018
Priority date	Jul 10, 2017
Publication date	Jan 4, 2022
Grant date	Jan 4, 2022

Abstract

Urea derivatives, methods for preparing ethylene amines, and methods of polymer manufacturing are provided. An exemplary method for preparing ethylene amines with n ethylene units and n+1 amine groups wherein n is at least 4, or urea derivatives of said ethylene amines, includes reacting an ethanolamine-functional compound, an amine-functional compound, and a carbon oxide delivering agent, wherein the ethanolamine-functional compound is of the formula HO—(C2H4-NH-)qH, q is at least 1, the amine-functional compound is of the formula H2N—(C2H4-NH-)rH, r is at least 1, the sum q+r is at least 4 and wherein optionally one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their cyclic carbamate derivative, or linear or cyclic urea derivative.

First claim

The invention claimed is:

1. A method for preparing ethylene amines with n ethylene units and n+1 amine groups wherein n is at least 4, or urea derivatives of said ethylene amines, the method comprising:
reacting an ethanolamine-functional compound, an amine-functional compound, and a carbon oxide delivering agent, wherein the ethanolamine-functional compound is of the formula HO—(C 2 H 4 —NH—) q H, q is at least 1, the amine-functional compound is of the formula H 2 N—(C 2 H 4 —NH—) r H, r is at least 1, the sum q+r is at least 4.

2. The method according to claim 1 wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is from about 1:0.1 to about 1:10.

3. The method according to claim 1 , wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than about 1:1.

4. The method according to claim 1 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than about 1.5:1.

5. The method according to claim 1 wherein the ethanolamine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using a carbamate precursor or derivative of the ethanolamine-functional compound.

6. The method according to claim 1 wherein the amine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using a urea precursor or derivative of the amine-functional compound.

7. The method according to claim 1 wherein the carbon oxide delivering agent is at least partly added as carbon dioxide or urea.

8. The method according to claim 1 further comprising converting the obtained ethylene urea at least partly into its corresponding ethylene amine via hydrolysis.

9. The method according to claim 1 wherein the sum q+r is 4 or 5.

10. The method according to claim 1 wherein the ethanolamine-functional compound and the amine functional compound are respectively:
monoethanolamine (MEA)+triethylenetetramine (TETA); aminoethylethanolamine (AEEA)+diethylenetriamine (DETA); or hydroxyethyldiethylenetriamine (HE-DETA)+ethylenediamine (EDA) to react to the ethylene amine tetraethylenepentamine (TEPA) or a urea derivative thereof, or
wherein the ethanolamine-functional compound and the amine functional compound are respectively:
monoethanolamine (MEA)+tetraethylenepentamine (TEPA); aminoethylethanolamine (AEEA)+triethylenetetramine (TETA); hydroxyethyldiethylenetriamine (HE-DETA)+diethylenetriamine (DETA); or hydroxyethyltriethylenetetramine (HE-TETA)+ethylenediamine (EDA) to react to the ethylene amine pentaethylenehexamine (PEHA) or urea derivative thereof.

11. The method of claim 9 , wherein one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their cyclic carbamate derivative, or linear or cyclic urea derivative.

12. The method of claim 1 wherein a selected urea derivative of pentaethylenehexamine is selected from the group of 2-monourea tetraethylene pentamine, of the formula

and di-urea derivatives of tetraethylene pentamines.

13. The method of claim 1 wherein a selected urea derivative of pentaethylenehexamine is selected from the group of mono-urea derivatives of pentaethylene hexamine selected from the group of

and di- and tri-urea derivatives of pentaethylene hexamine.

14. The method of claim 1 wherein one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their cyclic carbamate derivative, wherein the cyclic carbamate derivative is selected from the carbamate of aminoethylethanolamine (CAEEA), amino ethyl aminoethanol carbamate (AE AE carbamate), carbamate of hydroxyethyldiethylene triamine (CHE-DETA).

15. The method of claim 1 wherein one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their linear urea derivative.

16. The method of claim 1 wherein one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their cyclic urea derivative.

17. The method of claim 1 wherein one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their linear or cyclic urea derivative.

18. The method of claim 1 wherein one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their urea derivative selected from ethylene urea (EU), the cyclic urea of triethylene tetramine (UTETA), the internal cyclic diurea of triethylene tetramine (DUTETA), the urea of diethylene triamine (UDETA), the urea on the first amine of triethylene tetramine (U1TETA), and the 1,3-diurea of triethylene tetramine (DUTETA).

Assignees

• Nouryon Chemicals Int Bv

Inventors

• Kantzer Eike Nicolas
• Lake Karl Fredrik
• Ten Kate Antoon Jacob Berend
• Raaijmakers Michiel Jozef Thomas
• Veneman Rens
• Edvinsson Rolf Krister
• Ehlers Ina
• Sarning Michael Bertil Einar
• Berg Robert Kristoffer
• Van Dam Hendrik

Classifications

• C07C209/16 Primary

  with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings · CPC title

• C07C209/78

  from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines · CPC title

• C07D233/34 Primary

  Ethylene-urea · CPC title

• C07C211/14

  Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines · CPC title

• C07C209/62

  by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds (C07C209/24 takes precedence) · CPC title