Process for the preparation of di- and polyamines from the diphenylmethane series

• US 9,815,769 B2
• Filed: 04/22/2014
• Issued: 11/14/2017
• Est. Priority Date: 04/24/2013
• Status: Active Grant

• Current Assignee: Covestro Deutschland AG
• Original Assignee: Covestro Deutschland AG
• Inventors: Knauf, Thomas, Wershofen, Stefan, Gruner, Klaus-Gerd, Torruella, Esteve Obis
• Primary Examiner(s): Jackson, Shawquia
• Application Number:
  US14/785,498
• Publication Number:
  US 20160068474A1
• Time in Patent Office: 1,302 Days
• 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
• CPC Class Codes: C07C 263/10 by reaction of amines with carbonyl halides, e.g. with phosgene
• CPC Class Codes: C07C 265/14 containing at least two isocyanate groups bound to the same carbon skeleton
• CPC Class Codes: C08G 73/0266 Polyanilines or derivatives thereof

Abstract

The present invention provides a process for preparing di- and polyamines from the diphenylmethane series by converting aniline and formaldehyde in the absence of an acid catalyst to give aminal and water, removing the aqueous phase and further processing the organic aminal phase to give the di- and polyamines of the diphenylmethane series, in which use of a coalescence aid in the phase separation of the process product obtained in aminal reaction reduces the proportion of water and hence also of water-soluble impurities in the organic phase containing the aminal. The di- and polyamines of the diphenylmethane series obtained by acid-catalyzed rearrangement and workup after further processing of the aminal phase are outstanding suitably for preparation of the corresponding isocyanates.

Claims

1. A process for the preparation of di- and polyamines of the diphenylmethane series, comprising:

a) converting aniline and formaldehyde in the absence of an acidic catalyst to a reaction mixture comprising aminal and water, where the formaldehyde to be used comprises at most 2.0% by mass of methanol;

b) removing water at least in part from the reaction mixture obtained in step a), giving an organic phase comprising the aminal;

c) converting the organic aminal-comprising phase obtained in step b), in the presence of an acidic catalyst, to a reaction mixture comprising di- and polyamines of the diphenylmethane series; and

d) neutralizing the reaction mixture comprising di- and polyamines of the diphenylmethane series obtained in step c) and then subjecting the reaction mixture to a work-up comprising washing and distillation;

wherein

in step a) at least one auxiliary reagent from at least one of the groups (i) to (v) or at least one auxiliary reagent from exclusively group (vi) is added in the mass fractions stated in each case, the mass fractions referring to the total mass of all of the feed substances used in step a) including the mass of the auxiliary reagents added;

(i) 0.05% by mass to 3.0% by mass of aliphatic alcohols having 1 to 6 carbon atoms,

(ii) 0.0001% by mass to 3.0% by mass of alkali metal halides,

(iii) 0.0001% by mass to 0.030% by mass of alkali metal hydroxides,

(iv) 0.0001% by mass to 1.0% by mass of carboxylic acids having 1 to 4 carbon atoms,

(v) 0.0001% by mass to 1.0% by mass of salts of carboxylic acids having 1 to 4 carbon atoms,

(vi) 0.1% by mass to 3.0% by mass of cycloaliphatic alcohols having 5 to 7 carbon atoms, where the mass fraction of the auxiliary reagent of group (vi) is selected such that this is greater than 0.5% by mass, based on the total mass of the aniline used in step a) and of the auxiliary reagent of group (vi).

2. The process of claim 1, in which

the auxiliary reagent of group (i) is selected from the group consisting of methanol and a methanol-containing process stream,

the auxiliary reagent of group (ii) is selected from the group consisting of sodium chloride, potassium chloride and aqueous process streams of these salts,

the auxiliary reagent of group (iii) is selected from the group consisting of sodium hydroxide and potassium hydroxide,

the auxiliary reagent of group (iv) is formic acid,

the auxiliary reagent of group (v) is selected from the group consisting of sodium formate and potassium formate,

the auxiliary reagent of group (vi) is cyclohexanol.

3. The process of claim 1, in which only auxiliary reagents of groups (i), (ii), (iii) and (vi) are used and in which

the auxiliary reagent of group (i) is selected from the group consisting of methanol and a methanol-containing process stream,

the auxiliary reagent of group (ii) is selected from the group consisting of sodium chloride and a sodium chloride-containing aqueous process stream,

the auxiliary reagent of group (iii) is an aqueous sodium hydroxide solution,

the auxiliary reagent of group (vi) is cyclohexanol.

4. The process of claim 1, in which only auxiliary reagents of the groups (i), (ii) and (iii) are used, and in which

the auxiliary reagent of group (i) is selected from the group consisting of methanol and a methanol-containing process stream,

the auxiliary reagent of group (ii) is selected from the group consisting of sodium chloride and a sodium chloride-containing aqueous process stream,

the auxiliary reagent of group (iii) is an aqueous sodium hydroxide solution.

5. The process of claim 1, comprising

introducing the at least one auxiliary reagent separately from the starting materials aniline and formaldehyde′

to the conversion of step a)

or

adding the at least one auxiliary reagent to at least one of the starting materials aniline and formaldehyde of step a) before they are mixed

or

adding the at least one auxiliary reagent after mixing aniline and formaldehyde.

6. A process for the preparation of di- and polyisocyanates of the diphenylmethane series comprising phosgenation of di- and polyamines of the diphenylmethane series prepared by the process of claim 1.

7. The process of claim 1, in which only auxiliary reagents of groups (ii), (iii) and (vi) are used.