Preparation of high molecular weight, branched, acyclic polyalkyleneamines and mixtures thereof

• US 9,783,486 B2
• Filed: 11/24/2014
• Issued: 10/10/2017
• Est. Priority Date: 12/02/2013
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Inventors: King, Stephen W., Onam, Sadeka
• Primary Examiner(s): Zucker, Paul A
• Assistant Examiner(s): Luderer, Mark
• Application Number:
  US15/038,984
• Publication Number:
  US 20160376221A1
• Time in Patent Office: 1,051 Days
• CPC Class Codes: B01J 23/8896 Rhenium
• CPC Class Codes: C07C 209/02 by substitution of hydrogen atoms by amino groups
• CPC Class Codes: C07C 209/64 by disproportionation
• CPC Class Codes: C07C 211/14 Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines
• CPC Class Codes: C08G 73/0206 Polyalkylene(poly)amines
• CPC Class Codes: C08G 73/0213 Preparatory process

Abstract

A process for preparing high molecular weight, branched, acyclic polyalkyleneamines comprising transaminating a reaction mixture that includes at least a first polyalkyleneamine component that contains at least two non-tertiary amine groups separated from one another by a ternary or higher carbon atom and a second polyalkyleneamine component having the formula wherein x, y, and z are the same or different and are integers of from 1 to 10; a, b, c, d, e, and f are the same or different and are H or hydrocarbyl of from 1 to 10 carbon atoms; A, B, C, D, E, are the same or different and are H or hydrocarbyl of from 1 to 10 carbon atoms; provided that at least two of the amine groups are primary or secondary.

Claims

1. A method of making a high molecular weight, branched, acyclic polyalkyleneamine-containing product comprising the steps of:

(a) providing a reaction composition comprising a first linear polyalkyleneamine that has at least two non-tertiary amine groups separated by at least a ternary carbon atom spacing and at least one second polyalkyleneamine having the formula

2. The method of claim 1 wherein the first polyalkyleneamine has at least two non-tertiary amine groups separated from one another by a ternary or greater carbon group.

3. The method of claim 1, wherein the first polyalkyleneamine is selected from 1,3-diaminopropane (1,3-DAP), 1,3-pentanediamine;

1,3-butanediamine;

2,2-dimethyl-1,3-propanediamine;

2,2-diethyl-1,3-propanediamine;

1,3-diamino-2-phenylpropane;

2-(aminomethyl)-2-methyl-1,3-propanediamine; and

combinations thereof.

4. The method of claim 1, wherein the second polyalkylene amine is tris(2-aminoethyl)amine (TAEA), tris(2-aminopropyl)amine, tris(3-aminopropyl)amine, and combinations thereof.

5. The method of claim 1, wherein the reaction composition comprises a mixture of 1,3-diaminopropane (DAP) and TAEA.

6. The method of claim 1, wherein the catalyst is a hydrogenation/dehydrogenation catalyst.

7. The method of claim 1, wherein the catalyst is supported on a substrate.

8. The method of claim 7, wherein the substrate comprises an acidic mixed metal oxide comprising a transitional alumina and a second metal oxide.

9. The method of claim 8, wherein the transitional alumina comprises delta alumina, and may optionally further comprise one or more of gamma, theta or alpha alumina.

10. The method of claim 8, wherein the second metal oxide is selected from silicon, lanthanum, magnesium, zirconium, boron, titanium, niobium, tungsten and cerium.

11. The method of claim 1, wherein the catalyst comprises:

(a) a support portion comprising an acidic mixed metal oxide comprising a transitional alumina and a second metal oxide; and

(b) a catalyst portion comprising nickel and rhenium, wherein;

the second metal oxide has a weight percentage that is less than the weight percentage of alumina,

(c) the catalyst portion is 25 weight percent or less of the catalyst composition,

(d) the catalyst portion comprises nickel in an amount in the range of 2 to 20 weight percent, based upon total catalyst composition weight.

12. The method of claim 8, wherein the metal oxide is selected from one or more of magnesium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, boron, germanium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, iron, tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, rhenium, osmium, iridium, and platinum.

13. The method of claim 12, wherein the catalyst comprises a Ni/Re catalyst.

14. The method of claim 1, wherein the molar content of the first polyalkyleneamine comprises at least about 80% of the reaction mixture.

15. A mixture of predominately high molecular weight branched, acyclic polyalkyleneamine congener products obtained according to claim 11.