Process for preparing diisocyanates based on lysine

Patent metadata

Field	Value
Publication number	US-11739055-B2
Application number	US-202117358541-A
Country	US
Kind code	B2
Filing date	Jun 25, 2021
Priority date	Jun 26, 2020
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

The invention relates to a process for preparing a diisocyanate of the formula (A)

where R is selected from the group consisting of alkyl, aryl, and combinations thereof, comprising the following process steps in the indicated order;
1) providing an intermediate of the formula (B) with a process using lysine and urea

and
where R and each R′ are independently selected from the group consisting of alkyl, aryl, and combinations thereof; and

2) thermolytic cleavage of the intermediate of the formula (B),
thereby affording the diisocyanate of the formula (A),

and also to the diisocyanate directly prepared therewith.

First claim

The invention claimed is:

1. Process for preparing a diisocyanate of the formula (A)

where R is selected from the group consisting of alkyl, aryl, and combinations thereof, comprising the following process steps in the indicated order:
1) Providing an intermediate of the formula (B) with a process using lysine and urea

where R and each R′ are independently selected from the group consisting of alkyl, aryl, and combinations thereof; and
2) thermolytic cleavage of the intermediate of the formula (B),
thereby affording the diisocyanate of the formula (A); and
wherein the process further includes one of the following series of process steps prior to process step 1):
either a.1) providing of lysine;
a.2) reacting the lysine with urea to form a urea adduct of the formula (C)

and
a.3) reacting the urea adduct of the formula (C) with an alcohol to form the intermediate of the formula (B);

or b.1) providing of lysine;
b.2) reacting the lysine with a base to form a lysine salt of the formula (Z);

where X is a counterion;
b.3) reacting the lysine salt of the formula (Z) with urea to form a urea salt of the formula (Y);

where X is a counterion;
b.4) reacting the urea salt of the formula (Y) with an alcohol to form a carbamate of the formula (X)

where each R′ is independently selected from the group consisting of alkyl, aryl, and combinations thereof, and X is a counterion;
b.5) reacting the carbamate of the formula (X) with an acid to form the carboxylic acid of the formula (W)

where each R′ is independently selected from the group consisting of alkyl, aryl, and combinations thereof; and
b.6) reacting the carboxylic acid of the formula (W) with an alcohol to form the intermediate of the formula (B);

or c.1) providing of lysine;
c.2) reacting the lysine with a base to form a lysine salt of the formula (Z);

where X is a counterion;
c.3) reacting the lysine salt of the formula (Z) with urea to form a urea salt of the formula (Y);

where X is a counterion;
c.4) reacting the urea salt of the formula (Y) with an alcohol to form the intermediate of the formula (B).

2. Process according to claim 1 , wherein R is selected from the group consisting of C1-C8 alkyl.

3. Process according to claim 1 , wherein the thermolytic cleavage is mediated by a mediator.

4. Process according to claim 1 , wherein the process includes a further process step 3) after and/or during process step 2):
3) purifying the diisocyanate of the formula (A).

5. Process according to claim 1 , wherein the molar ratio of the urea in step a.2) is within a range from 1:1 to 5:1 based on the primary amine groups of the lysine, and the molar ratio of the urea in step b.3) or c.3) is within a range from 1:1 to 5:1 based on the primary amine groups of the lysine salt of the formula (Z).

6. Process according to claim 1 , wherein the pressure during the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is for at least part of the time within a range from ≥1 bar.

7. Process according to claim 6 , wherein the pressure during the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is within the specified range for 1 to 20 hours.

8. Process according to claim 1 , wherein the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is carried out at least at a temperature from 150 to 300° C.

9. Process according to claim 8 , wherein the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is conducted within the specified temperature range for a period of 1 to 20 hours.

10. Process according to claim 1 , wherein the molar ratio of the alcohol in step a.3) based on the urea adduct of the formula (C) is within a range from 2:1 to 100:1, the molar ratio of the alcohol in step b.6) based on the carboxylic acid of the formula (W) is within a range from 2:1 to 100:1, and the molar ratio of the alcohol in step c.4) based on the urea salt of the formula (Y) is within a range from 2:1 to 100:1.

11. Process according to claim 1 , wherein the reaction in process steps a.2), b.3) and c.3) is carried out in a polar solvent.

12. Process according to claim 2 , wherein R is selected from the group consisting methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

13. Process according to claim 3 , wherein the thermolytic cleavage is mediated by a metal-based catalyst.

14. Process according to claim 13 , wherein the metal-based catalyst is a tin(II) salt.

15. Process according to claim 4 , wherein the diisocyanate of the formula (A) is purified by fractional distillation.

16. Process according to claim 6 , wherein the pressure during the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is for at least part of the time within a range from 1 to 25 bar.

17. Process according to claim 7 , wherein the pressure during the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is within the specified range 4 to 6 hours.

18. Process according to claim 8 , wherein the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is carried out at least at a temperature from 190 to 220° C.

19. Process according to claim 9 , wherein the reaction with the alcohol in process step a.3), b.4), b.6), c.4) is conducted within the specified temperature range for a period of 4 to 6 hours.

20. Process according to claim 11 , wherein the polar solvent is water.

Assignees

• Evonik Operations Gmbh

Inventors

• Spyrou Emmanouil
• Loesch Holger
• Kreischer Susanne
• Diesveld Andrea
• Thesing Andrea
• Nitz Jörg-Joachim

Classifications

• C07C263/06 Primary

  from or via ureas · CPC title

• C07C269/04

  from amines with formation of carbamate groups · CPC title

• C07C263/04 Primary

  from or via carbamates or carbamoyl halides · CPC title

• C07C273/1863

  from urea · CPC title

• C07C269/00

  Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups [IMAGE cpc-sch-C07C-0964.gif], the nitrogen atom not being part of nitro or nitroso groups · CPC title