Process for preparing an aromatic polyamine mixture

Patent metadata

Field	Value
Publication number	US-11028042-B2
Application number	US-201716071309-A
Country	US
Kind code	B2
Filing date	Jan 12, 2017
Priority date	Jan 20, 2016
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

A process for preparing an aromatic polyamine mixture including 4,4′-methylenedi(phenylamine) and higher homologues of MDA is provided. The process includes steps of (i) reaction of aniline with formaldehyde by means of an acid catalyst to form a crude product mixture (I), (ii) neutralization of the crude product mixture (I) and removal of the salts formed; (iii) isolation of aniline; (iv) distillation of the resulting crude product mixture so as to separate off (iv-1) a mixture (II) of MDA isomers (II-1) containing from 8 to 20% by weight of 4,4′-methylenedi(phenylamine) and not more than 0.3% by weight of secondary components (II-2) and (iv-2) a low boiler mixture of at least 55% by weight of secondary components (II-2) and MDA isomers (II-1); and (v) recirculation of the mixture (II).

First claim

The invention claimed is:

1. A process for preparing an aromatic polyamine mixture comprising 4,4′-methylenedi(phenylamine) and higher homologues of methylenedi(phenylamine), the process comprising
(i) reacting aniline with formaldehyde in the presence of an acid catalyst to form a crude product mixture (I) in a plant which comprises a mixing zone (a), a condensation zone (b), a rearrangement zone (c) and optionally an after-reaction zone (d);
(ii) neutralizing the crude product mixture (I) obtained in (i) and removing salts thus formed, to obtain a crude product mixture (II);
(iii) separating aniline from the crude product mixture (II) obtained in (ii), to obtain separated aniline and a crude product mixture (III), and optionally recirculating the separated aniline to the mixing zone (a); then
(iv) distilling the crude product mixture (III) obtained in (iii) wherein the distilling comprises
(iv-1) isolating a mixture (II) consisting of methylenedi(phenylamine) isomers (II-1) and secondary components (II-2) which are different therefrom, where, based on (II-1), a proportion of 4,4′-methylenedi(phenylamine) is from 8 to 20% by weight and, based on (II), a proportion of secondary components (II-2) is not more than 0.3% by weight, and
(iv-2) isolating a low boiler mixture which consists of secondary components (II-2) and methylenedi(phenylamine) isomers (II-1) and in which a proportion of the secondary components (II-2) is at least 55% by weight; and

(v) recirculating the mixture (II) to one of the zones (a) to (d),
wherein the aromatic polyamine mixture has a content of 4,4′-methylenedi(phenylamine) and higher homologues of methylenedi(phenylamine) of greater than 85% by weight.

2. The process according to claim 1 , wherein, in the distilling (iv), the isolating (iv-2) is carried out simultaneously with the isolating (iv-1) in a column having a dividing wall or a side stream offtake.

3. The process according to claim 1 , wherein, in the distilling (iv),
the isolating (iv 2) is effected from an overhead stream from a first distillation column,
a bottom stream obtained is fed to a further successive distillation column and
the mixture (II) is separated off from the overhead stream from the further distillation column.

4. The process according to claim 1 , wherein a dividing wall or side stream column which has from 2 to 15 theoretical plates in an upper region between a side stream and an overhead stream and from 10 to 20 theoretical plates in a lower region between a bottom stream and the side stream is used for the distilling (iv).

5. The process according to claim 1 , wherein the distilling (iv) is carried out in
a first distillation column having from 2 to 15 theoretical plates for the isolating (iv-2) and
a further distillation column having from 10 to 20 theoretical plates for the isolating (iv-1).

6. The process according to claim 1 , wherein the distilling (iv) is carried out at
a pressure at a top of a distillation column of from 1 to 10 mbar and a temperature of from 120 to 210° C. for separating off the low boiler mixture and
a side stream pressure of from 1 to 10 mbar and a temperature of from 170 to 230° C. for separating off the mixture (II).

7. The process according to claim 5 , wherein, in the first distillation column, the distilling (iv) is carried out at a pressure at a top of the first distillation column of from 1 to 10 mbar and at a temperature of from 120 to 210° C., and
in the further distillation column, the distilling (iv) is carried out at a pressure at a top of the further distillation column of from 1 to 10 mbar and at a temperature of from 170 to 230° C.

8. The process according to claim 1 , wherein the low boiler mixture is discharged from the process.

9. The process according to claim 1 , wherein the mixture (II) is recirculated to the mixing zone (a).

10. The process according to claim 1 , wherein the aromatic polyamine mixture is separated as a bottom stream from a column in the distilling (iv).

Assignees

• Basf Se

Inventors

• Ladnak Viktor
• Tauro Silvia
• Heinen Kerstin
• Thiele Kai
• Metzner Klaus-Peter
• Mattke Torsten

Classifications

• C07C211/50

  with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton · CPC title

• C07C209/86

  Separation · CPC title

• C07C209/78 Primary

  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

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• B01D3/141

  where at least one distillation column contains at least one dividing wall · CPC title