Preparation of polyalkylene-polyamines by reductive amination

Abstract

An alkylene-diamine, a hydroxyalkylene-amine, and hydrogen are reacted in presence of a heterogenous catalyst containing copper to produce polyalkylene-polyamines.

Claims

1: A process to produce polyalkylene-polyamines, the process comprising: reacting an alkylene-diamine, a hydroxyalkylene-amine, and hydrogen in presence of a heterogenous catalyst comprising copper, to obtain the polyalkylene-polyamines.

2: The process according to claim 1, wherein the alkylene-diamine is a compound of formula I
H.sub.2N—X—NH.sub.2, with X representing a linear or branched alkylene group with 2 to 10 carbon atoms.

3: The process according to claim 2, wherein the alkylene-diamine of formula I is 1,2 propylenediamine of the following formula ##STR00008##

4: The process according to claim 1, wherein the hydroxyalkylene-amine is a compound of formula II
HO—Y—NH.sub.2, with Y representing a linear or branched alkylene group with 2 to 10 carbon atoms.

5: The process according to claim 4, wherein the hydroxyalkylene-amine of formula II is 1-amino propan-2-ol of the following formula ##STR00009##

6: The process according to claim 1, wherein the polyalkylene-polyamines obtained comprise dimethyl-diethylene-triamines selected from the group consisting of ##STR00010## and any mixture thereof.

7: The process according to claim 1, wherein the catalyst comprises at least 30% by weight of copper, based on all catalytically active metals in the catalyst, calculated as elementary metals.

8: The process according to claim 1, wherein the catalyst is a supported catalyst and a support is selected from the group consisting of calcium carbonate, silicon dioxide, zirconium dioxide, and aluminum oxide.

9: The process according to claim 1, wherein the alkylene-diamine, the hydroxyalkylene-amine, and hydrogen are reacted in presence of ammonia.

10: The process according to claim 1, wherein the process is performed continuously.

Description

EXAMPLES

Example 1 to 12

[0057] An autoclave was charged with 20 g of a supported catalyst in form of a fixed-bed catalyst or with 10 g of Raney catalyst (washed with THF) under an atmosphere of nitrogen. 32 g 1-aminopropan-2-ol (˜90:10 mixture with 2-aminopropan-1-ol), shortly MIPOA, and 60 g propane-1,2-diamine, shortly 1,2-PDA were added, the autoclave was sealed and pressurized with hydrogen to 10 bar. In Examples 8 to 10 also 5 g ammonia were added to the reaction mixture. The reaction mixture was stirred and heated to the temperature (T) listed in the Table below. After the temperature was reached, the pressure was adjusted with hydrogen to the pressure (P) listed in the Table below and the mixture was stirred for 12 h. A sample was taken after 6 h and analyzed by GC. The process has been performed with different catalysts. Results (GC area-%) are listed in the Table below.

[0058] Examples 3,4,11 and 12 are comparison examples. The catalyst material used for Examples 1 and 5 contained 10% by weight of cobalt, calculated as CoO, 10% by weight of nickel, calculated as NiO, and 4% by weight of copper, calculated as CuO, remainder Al.sub.2O.sub.3, which corresponds to a content of copper of 18% by weight based on the total weight of all catalytically active metals of the catalyst (only considering the metal fraction of the compounds of the active mass). The catalyst material used for Examples 2 and 6 to 8 contained 51% by weight of copper, calculated as CuO, remainder Al.sub.2O.sub.3, (since the active mass of this catalyst comprises no further metals in addition to copper, the content of copper based on the total weight of all catalytically active metals of the catalyst is 100%). The catalyst material used for Examples 9 and 10 contained 45% by weight of copper, calculated as CuO and 46% by weight of chromium, calculated as Cr.sub.2O.sub.3, remainder BaO promoter, which corresponds to a content of copper of 53% by weight based on the total weight of all catalytically active metals of the catalyst (only considering the metal fraction of the compounds of the active mass).

TABLE-US-00001 TABLE catalysts and results of examples 1 to 12 sum of residual 1,2 PDA + sum of Sum of MIPOA piperazine DMDETA Ratio example catalyst T (° C.) P (bar) (%) (%) (%) DMDETA:piperazine  1 Co—Ni—Cu 200 200 23 65 3 0.05 on Al.sub.2O.sub.3  2 Cu 200 200 44 11 31 2.8 on Al.sub.2O.sub.3  3 Raney Ni 200 200 8 74 0 0  4 Raney Co 200 200 1 73 0.2 0.0003  5 Co—Ni—Cu 180 200 46 33 13 0.4 on Al.sub.2O.sub.3  6 Cu 180 200 75 2 19 9.5 on Al.sub.2O.sub.3  7 Cu 180 120 77 3 17 5.7 on Al.sub.2O.sub.3  8 Cu 180 120 73 3 20 6.7 on Al.sub.2O.sub.3  9 Cu/Cr 180 120 77 3 16 5.3 10 Cu/Cr 200 200 65 8 20 2.5 11 Raney Ni 180 200 32 43 5 0.12 12 Raney Co 180 200 31 57 1 0.02

[0059] Raney Co was obtained from Grace (Grace 2724), Raney Ni was obtained from BASF (H1-50), the catalysts on Al.sub.2O.sub.3 support were BASF products.

Example 13

Continuous Process for the Preparation of DMDETA

[0060] A tubular reactor was filled with 600 mL of a Cu catalyst (as used for Example 6). For catalyst activation, the catalyst was heated to a temperature of 180° C. to 200° C. under a stream of nitrogen at atmospheric pressure. Hydrogen was carefully dosed into the nitrogen stream at atmospheric pressure to control the exotherm of the activation. Eventually, pure hydrogen was passed over the catalyst at atmospheric pressure and at a temperature of 200° C. for 6 h. After catalyst activation, the reactor was pressurized to 200 bar with H.sub.2 and fed continuously with 100 g/h 1-aminopropan-2-ol (˜90:10 mixture with 2-aminopropan-1-ol), 200 g/h propane-1,2-diamine, 80 g/h NH.sub.3 and 100 NL/h H.sub.2 at a temperature of 180 to 220° C. The product stream was depressurized to atmospheric pressure and collected. The collected crude product was purified by distillation under reduced pressure to obtain an ˜6:87:6 isomeric mixture of N.sup.1-(2-aminopropyl)propane-1,2-diamine, N.sup.1-(1-aminopropan-2-yl)propane-1,2-diamine and N.sup.2-(1-aminopropan-2-yl)propane-1,2-diamine in >99% purity (GC-area-%, sum of isomers).