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

Patent metadata

Field	Value
Publication number	US-2016376221-A1
Application number	US-201415038984-A
Country	US
Kind code	A1
Filing date	Nov 24, 2014
Priority date	Dec 2, 2013
Publication date	Dec 29, 2016
Grant date	—

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.

First claim

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

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; and
(b) subjecting the reaction composition to a transamination reaction in the presence of a hydrogenation/dehydrogenation catalyst to obtain the high molecular weight, branched, acyclic polyalkyleneamine-containing mixture.

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 .

Assignees

• Dow Global Technologies Llc

Inventors

• King Stephen W
• Onam Sadeka

Classifications

• C07C209/02

  by substitution of hydrogen atoms by amino groups · CPC title

• B01J23/8896

  Rhenium · CPC title

• C08G73/0213

  Preparatory process · CPC title

• C08G73/0206

  Polyalkylene(poly)amines · CPC title

• C07C211/14 Primary

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