Multistep process for the preparation of diisocyanates

Patent metadata

Field	Value
Publication number	US-11174222-B2
Application number	US-201816645880-A
Country	US
Kind code	B2
Filing date	Sep 12, 2018
Priority date	Sep 26, 2017
Publication date	Nov 16, 2021
Grant date	Nov 16, 2021

Abstract

Provided is a process for preparing an organic diisocyanate of the formula: OCN—R—NCO (1), wherein R represents a bivalent hydrocarbon radical containing 3 to 20 carbon atoms, the carbon atoms being arranged in a way that the two nitrogen atoms are separated from each other by at least 3 carbon atoms, the process comprising, Step (I) preparing a diurethane of the formulawherein R is the same as in formula (1), R′ and R″ independently represent organic radicals selected from the group consisting of 4 to 36 carbon atoms, 4 to 74 hydrogen atoms, 0 to 12 oxygen atoms that have the oxidation state −2, and 0 to 1 halogen atoms from a diarylurethane of the formula,wherein R is the same as in formula (1), Ar and Ar′ independently represent a substituted or unsubstituted aryl or heteroaryl radical selected from the group containing a total of 4 to 20 carbon atoms by transesterification, Step (II) subjecting the diurethane of the formula (2) to a cleavage reaction to form the hydroxy compounds R′—OH and R″—OH and the organic diisocyanate of the formula (1), Step (III) separating the diisocyanate of the formula (1) from the hydroxy compounds R′—OH and R″—OH by distillation, wherein the hydroxy compounds R′—OH and R″—OH have higher standard boiling points than the standard boiling point of the diisocyanate OCN—R—NCO and the sum of the molecular weights of the radicals Ar and Ar′ is lower than the sum of the molecular weights of the radicals R′ and R″.

First claim

The invention claimed is:

1. A process for preparing an organic diisocyanate of the general formula (1)
OCN—R—NCO  (1)

wherein
R represents a bivalent hydrocarbon radical containing 3 to 20 carbon atoms, the carbon atoms being arranged such that the two nitrogen atoms are separated from each other by at least 3 carbon atoms,
comprising the following steps:
(I) preparing a diurethane of the general formula (2),

wherein
R is the same as in general formula (1),
R′ and R″ independently represent organic radicals consisting of 4 to 36 carbon atoms, 4 to 74 hydrogen atoms, 0 to 12 oxygen atoms that have the oxidation state −2, and 0 to 1 halogen atoms from a diarylurethane of the general formula (3),

wherein
R is the same as in general formula (1),
Ar and Ar′ independently represent a substituted or unsubstituted aryl or heteroaryl radical containing a total of 4 to 20 carbon atoms by transesterification reaction,

(II) subjecting the diurethane of the general formula (2) to a cleavage reaction to form the hydroxy compounds R′—OH and R″—OH and the organic diisocyanate of the general formula (1),
(III) separating the diisocyanate of the general formula (1) from the hydroxy compounds R′—OH and R″—OH by distillation,
wherein,
the hydroxy compounds R′—OH and R″—OH have higher standard boiling points than the standard boiling point of the diisocyanate OCN—R—NCO, and
the sum of the molecular weights of the radicals Ar and Ar′ is lower than the sum of the molecular weights of the radicals R′ and R″.

2. The process according to claim 1 , wherein the diarylurethane of the formula (3) is prepared from organic diamines, carbonic acid derivatives and aromatic hydroxy compounds.

3. The process according to claim 2 , wherein the organic diamine is selected from the group consisting of 2,4-toluylendiamine, 2,6-toluylendiamine, 2,2′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine, 1,3-diaminobenzene, 1,4-diaminobenzene, m-xylylenediamine, p-xylylendiamine, 1,4-butanediamine, neopentanediamine, 1,5-pentanediamine, 1,5-diamino-2-methylpentane, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-diamino-2,5-dimethylhexane, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 1,4-cyclohexanediamine, 2,4-hexahydrotoluenediamine, 2,6-hexahydrotoluenediamine, isomers of hexahydroxylylendiamine, isomers of bis-(aminomethyl)norbornane, and mixtures of the aforementioned.

4. The process according to claim 2 , wherein the carbonic acid derivative is urea, diarylcarbamate or dialkylcarbonate.

5. The process according to claim 2 , wherein the aromatic hydroxy compound is selected from the group consisting of phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, 2,5-xylenol, 2,4-xylenol, 2,3-xylenol, 3,4-xylenol, 3,5-xylenol, mesitol, o-ethylphenol, m-ethylphenol, p-ethylphenol, isomers of propylphenol, and isomers of butylphenol.

6. The process according to claim 1 , wherein the diarylurethane of the general formula (3) is selected such that the corresponding aromatic hydroxy compounds Ar—OH and Ar′—OH have a standard boiling point lower than the diisocyanate OCN—R—NCO.

7. The process according to claim 1 , wherein the hydroxy compounds R′—OH and R″—OH in the transesterification are used in an amount that the combined number of OH groups from R′—OH and R″—OH is higher than that of the urethane groups in the reaction mixture.

8. The process according to claim 1 , wherein the hydroxy compounds R′—OH and R″—OH are aromatic hydroxy compounds.

9. The process according to claim 1 , wherein the hydroxy compounds R′—OH and R″—OH are selected from the group consisting of lauryl, stearyl, cetyl and oleyl alcohol.

10. The process according to claim 1 , wherein a Lewis acidic catalyst is used in the transesterification.

11. The process according to claim 1 , wherein the cleavage reaction is a thermolytic cleavage carried out in a thin film evaporator.

12. The process according to claim 1 , wherein a catalyst is used in the cleavage reaction.

13. A process according to claim 1 for preparing an organic diisocyanate of the general formula (1)
OCN—R—NCO  (1)

wherein
R represents a bivalent hydrocarbon radical derived from 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate or isophoronediisocyanate by removing the two isocyanate groups, comprising the following steps:
(I) preparing a diurethane of the general formula (2),

wherein
R is the same as in general formula (1),
R′ represents a hydrocarbon-substituted or unsubstituted aryl radical consisting of 6 to 20 carbon atoms and 5 to 33 hydrogen atoms that is bound to the urethane group of the diurethane of the general formula (2) via a carbon atom that is part of an aromatic ring system and
R″ is the same as R′,

from a diarylurethane of the general formula (3),

wherein
R is the same as in general formula (1) and
Ar represents a hydrocarbon-substituted or unsubstituted aryl radical containing a total of 6 to 15 carbon atoms and having a lower molecular weight than the radical R′ and
Ar′ is the same as Ar

by transesterification reaction

(II) subjecting the diurethane of the general formula (2) to a cleavage reaction to form the aromatic hydroxy compounds R′—OH and R″—OH and the organic diisocyanate of the general formula (1),
(III) separating the diisocyanate of the general formula (1) from the aromatic hydroxy compounds R′—OH and R″—OH by distillation,
wherein
the aromatic hydroxy compounds R′—OH and R″—OH have a higher standard boiling point than the standard boiling point of the diisocyanate OCN—R—NCO, and
the aromatic hydroxy compounds Ar—OH and Ar′—OH, formally derived from Ar or Ar′ respectively by adding a hydroxy group, has a lower standard boiling point than the standard boiling point of the diisocyanate OCN—R—NCO.

14. A process according to claim 1 for preparing hexamethylene diisocyanate as diisocyanate of the general formula (1)
OCN—R—NCO  (1)

comprising the following steps:
(I) preparing N,N′-hexanediyl-di(carbamic acid(4-cumylphenyl)ester) as diurethane of the general formula (2)

by a transesterification reaction of 1,6-hexamethylene-O,O′-diphenylurethane as diarylurethane of the general formula (3)

with p-cumylphenol,

(II) subjecting N,N′-hexanediyl-di(carbamic acid(4-cumylphenyl)ester) as diurethane of the general formula (2) to a thermal cleavage reaction to form p-cumylphenol and hexamethylene diisocyanate (HDI)
(III) separating the HDI from the p-cumylphenol by distillation.

Assignees

• Covestro Deutschland Ag

Inventors

• Merkel Michael

Classifications

• C07C263/04 Primary

  from or via carbamates or carbamoyl halides · CPC title