Process to convert cyclic alkylene ureas into their corresponding alkylene amines

Patent metadata

Field	Value
Publication number	US-10428010-B2
Application number	US-201716074494-A
Country	US
Kind code	B2
Filing date	Feb 10, 2017
Priority date	Feb 12, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

The present invention relates to a process to convert cyclic alkylene ureas into their corresponding alkylene amines wherein the process is performed by reaction with an amine compound, and wherein the amine compound comprises a primary amine, a cyclic secondary amine or a tertiary bicyclic amine.

First claim

The invention claimed is:

1. Process to convert cyclic alkylene ureas into their corresponding alkylene amines wherein the process is performed by reaction with an amine compound, and wherein the amine compound is chosen from the group of primary amines, cyclic secondary amines or bicyclic tertiary amines;
wherein the cyclic alkylene urea reacts to the corresponding alkylene amine in accordance with below reaction

wherein R 1 and R 2 each independently are chosen from the group of hydrogen, an alkylene amine group of the formula X—R 3 —(NH—R 3 —) p —, or an alkoxy group of formula X—R 3 —(O—R 3 —) n —, or a group combining such alkylene amine and alkoxy units p and n, wherein optionally one or more units ˜N—R 3 —N˜ may be present as either one of the rings

and wherein each R 3 independently is alkylene or substituted alkylene, X may be hydroxyl, amine, a linear or branched C1-C20 hydroxyalkyl or a linear or branched C1-C20 aminoalkyl group, n and p independently are 0 or at least 1, wherein when n and/or p is at least 1 the linear or branched C1-C20 hydroxyalkyl or C1-C20 aminoalkyl croup optionally contains one or more piperazine or alkylene urea groups.

2. Process of claim 1 wherein the amine compound is a compound that can bind the carbonyl group from the cyclic alkylene urea to give another linear or cyclic alkylene urea or linear or cyclic alkylene carbamate.

3. Process of claim 2 wherein the amine compound is a smaller alkylene amine or alkanol amine than the one derived from the starting cyclic alkylene urea after the conversion.

4. Process of claim 2 wherein the amine compound is an alkylene amine or an alkanol amine compound that is larger than the one derived from the starting cyclic alkylene urea after the conversion.

5. Process of claim 3 wherein the amine compound is ethylenediamine (EDA), N-methylethylenediamine (MeEDA), diethylenetriamine (DETA), ethanolamine (MEA), aminoethylethanolamine (AEEA), piperazine (PIP), N-aminoethylpiperazine (AEP), N-diethyldiamine-2-imidazolidinone (U1TETA), N, N′-diaminoethylpiperazine (DAEP), N, N′-diaminoethyl-2-imidazolidinone (U2TETA), a polyethyleneimine (PEI) or an alkylene amine on a solid carrier.

6. Process of claim 1 wherein the reaction is done in the presence of a polar liquid.

7. Process of claim 1 wherein the amine compound is ethylenediamine (EDA), N-methylethylenediamine (MeEDA), diethylenetriamine (DETA), ethanolamine (MEA), aminoethylethanolamine (AEEA), piperazine (PIP), N-aminoethylpiperazine (AEP), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,4-diazabicyclo[2.2.2]octan-2-yl)methanol, triethylenetetramine (TETA), N-diethyldiamine-2-imidazolidinone (U1TETA), N, N′-diaminoethylpiperazine (DAEP), N, N′-diaminoethyl-2-imidazolidinone (U2TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and the mono cyclic ureas of TEPA and PEHA (i.e. U1TEPA, U2TEPA, U1 PEHA, U2PEHA, U3PEHA) and the dicyclic urea isomers of PEHA, a polyethyleneimine (PEI) or an alkylene amine on a solid carrier, and the reaction is done in the presence of water.

8. Process of claim 1 wherein the reaction is done at a temperature of at least 150° C.

9. Process of claim 1 wherein the amine compound is added to the process in a molar amount of between 0.15 and 25 equivalent based on the total molar amount of cyclic alkylene urea.

10. Process of claim 1 containing a subsequent step wherein any urea compound formed from reaction between the amine compound and the cyclic urea compound is hydrolyzed with water to release its carbonyl group to provide carbon dioxide or an ionic derivative thereof.

11. Process of claim 10 wherein the carbon dioxide or ionic derivative thereof are recycled back into the process or separated off.

12. Process of claim 1 wherein the amine compound or any urea compound formed from reaction between the amine compound and the cyclic urea compound are recycled back into the process or separated off.

13. Process of claim 4 wherein the amine compound is ethylenediamine (EDA), N-methylethylenediamine (MeEDA), diethylenetriamine (DETA), ethanolamine (MEA), aminoethylethanolamine (AEEA), piperazine (PIP), N-aminoethylpiperazine (AEP), N-diethyldiamine-2-imidazolidinone (U1TETA), N, N′-diaminoethylpiperazine (DAEP), N, N′-diaminoethyl-2-imidazolidinone (U2TETA), a polyethyleneimine (PEI) or an alkylene amine on a solid carrier.

14. Process of claim 1 wherein n and p independently are at most 20.

15. Process of claim 6 wherein the polar liquid is water.

Assignees

• Akzo Nobel Chemicals Int Bv
• Nouryon Chemicals Int Bv

Inventors

• Edvinsson Rolf Krister
• Kantzer Eike Nicolas
• Larsson Per Fredrik Olmo
• Lake Karl Fredrik
• Ten Kate Antoon Jacob Berend
• Schröder Ulf
• Malmberg Johan Salman

Classifications

• C07D233/36

  with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms · CPC title

• C07C209/62 Primary

  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

• C07C211/14

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

• C07C211/18

  containing at least two amino groups bound to the carbon skeleton · CPC title