Process for preparing diamines and polyamines from the diphenylmethane series

• US 7,528,283 B2
• Filed: 01/24/2007
• Issued: 05/05/2009
• Est. Priority Date: 01/28/2006
• Status: Active Grant

• Current Assignee: Covestro Deutschland AG
• Original Assignee: Bayer Materialscience AG (Covestro AG)
• Inventors: Bolton, Jeffrey, Adamson, Richard, Muller, Heinz-Herbert, Uchdorf, Rudolf, Pohl, Fritz
• Primary Examiner(s): Davis; Brian J
• Application Number:
  US11/657,147
• Publication Number:
  US 20070179316A1
• Time in Patent Office: 832 Days
• Field of Search: None
• US Class Current: 564/331
• CPC Class Codes: C07C 209/78 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 Class Codes: C07C 211/50 with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton

Abstract

The invention provides an improved process for preparing diamines and polyamines from the diphenylmethane series by reacting aniline and formaldehyde in the presence of an acid catalyst, the improvement involving the aniline containing less than about 3 wt. % of diamines and polyamines from the diphenylmethane series, based on the weight of the aniline.

Claims

1. A process for the preparation of diamines and polyamines from the diphenylmethane series comprising reacting aniline which contains less than about 3 wt. % of diamines and polyamines from the diphenylmethane series, based on the weight of the aniline, with formaldehyde in the presence of an acid catalyst.

2. The process according to claim 1, wherein

a) aniline containing less than about 3 wt. % of diamines and polyamines from the diphenylmethane series, based on the weight of the aniline, is reacted with formaldehyde in the presence of an acid catalyst to form a reaction mixture containing diamines and polyamines,

b) the reaction mixture containing diamines and polyamines is neutralized,

c) the neutralized reaction mixture containing diamines and polyamines is separated into an organic phase containing diamines and polyamines and an aqueous phase,

d) the organic phase is optionally washed with water,

e) excess aniline is removed from the organic phase by distillation,

f) part or all of the waste water and condensates accumulating in steps a) to e) are combined, wherein at least the waste water and condensates obtained in steps c) and e) are combined at least in part, and wherein a mixture containing water, diamines and polyamines, aniline and salts of the catalyst used in step a) is obtained,

g) the mixture obtained in step f) undergoes a phase separation wherein an aniline containing diamines and polyamines is obtained, and

h) at least part of the aniline containing diamines and polyamines obtained in the phase separation is returned to the reaction in step a).

3. The process according to claim 2, wherein the aniline contains about 0.001 to about 3 wt. % of diamines and polyamines from the diphenylmethane series, based on the weight of the aniline.

4. The process according to claim 2, wherein the aniline contains about 0.01 to about 1 wt. % of diamines and polyamines from the diphenylmethane series, based on the weight of the aniline.

5. The process according to claim 2, wherein in step f) a mixture containing water and about 0.001 to about 5 wt. % of MDA, about 0.5 to about 60 wt. % of aniline and about 1 to about 25 wt. % of salts of the acid catalyst in step a), based in each case on the weight of the mixture, is obtained.

6. The process according to claim 2, wherein the phase separation in step g) takes place at a temperature of between about 30 and about 120°

C.

7. The process according to claim 2, wherein the phase separation in step g) takes place at a temperature of between about 70 and about 110°

C.

8. The process according to claim 2, wherein in a further extraction stage at a temperature of between about 30 and about 120°

C., the extracted waste water obtained in step g) is extracted with aniline in the weight ratio of aniline to waste water of about 0.05 to about 1;

1, and the extracts obtained are added to the mixture obtained in step f).

9. The process according to claim 8, wherein the temperature is between about 70 and about 110°

C., and the weight ratio of aniline to waste water is from about 0.1 to about 0.3;

1.

10. The process according to claim 8, wherein in the extraction stage the waste water is extracted in a multi-stage process.

11. The process according to claim 8, wherein in the extraction stage the waste water is extracted counter currently.

12. The process according to claim 8, wherein part of the aniline containing MDA obtained in the extraction stage is returned to one or more of steps a) to e).

13. The process according to claim 2, wherein aniline is removed by distillation from the waste water obtained in the phase separation in step g) and wherein at least part of the extracted aniline, in the form of its condensed vapors, is returned to the neutralization stage in step b) and/or to the washing stage in step d).

14. The process according to claim 13, wherein the vapors produced in the distillative separation of the aniline are condensed in a multi-stage process, wherein a fraction containing about 20 to about 95 wt. % of methanol is obtained.

15. The process according to claim 13, wherein the vapors produced in the distillative separation of the aniline are condensed in a multi-stage process, wherein a fraction containing about 60 to about 80 wt. % of methanol is obtained.

16. The process according to claim 12, wherein aniline is removed by distillation from the waste water obtained in the extraction stage and wherein at least part of the extracted aniline, in the form of its condensed vapors, is returned to the neutralization stage in step b) and/or to the washing stage in step d).

17. The process according to claim 16, wherein the vapors produced in the distillative separation of the aniline are condensed in a multi-stage process, wherein a fraction containing about 20 to about 95 wt. % of methanol is obtained.

18. The process according to claim 16, wherein the vapors produced in the distillative separation of the aniline are condensed in a multi-stage process, wherein a fraction containing about 60 to about 80 wt. % of methanol is obtained.