Process for the preparation of triazine carbamates

Patent metadata

Field	Value
Publication number	US-10071972-B2
Application number	US-201515505337-A
Country	US
Kind code	B2
Filing date	Sep 7, 2015
Priority date	Sep 9, 2014
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

This invention relates to a process for the preparation of triazine carbamates by reacting a mixture of an aminotriazine A having at least two amino groups per molecule, an organic carbonate C, and a base B selected from the group consisting of alkoxides, and arylalkoxides of metals M, which may be alkali or earth alkali metals, and a solvent S which is a monohydric alcohol solvent R 2 OH or a mixture of solvents that comprises a monohydric alcohol R 2 OH, and a monohydric alcohol R 3 OH, or a mixture of solvents that comprises a monohydric alcohol R 2 OH with a further solvent selected from the group consisting of ether, alcohol, and hydrocarbon solvents, and adding to the products of the said reaction, an acid or a solution of an acid in a solvent.

First claim

The invention claimed is:

1. A process for the preparation of one or more triazine carbamates comprising reacting a mixture of
an aminotriazine A having at least two amino groups per molecule,
an organic carbonate C, and
a base B which is an alkoxide M(OR 1 ) a of a metal M which is selected from the group consisting of alkali metals (a =1) and earth alkali metals (a =2), or mixtures thereof with a further alkoxide)M(OR 0 ) a , where R 0 and R 1 are different from each other,

in the presence of a solvent S,
wherein the solvent S is
a monohydric alcohol solvent R 2 OH, or
a mixture of solvents that comprises a mass fraction of at least 10% of a monohydric alcohol R 2 OH, and a monohydric alcohol solvent R 3 OH, where R 2 and R 3 are different from each other, or
a mixture of solvents that comprises a mass fraction of at least 10% of a monohydric alcohol R 2 OH with a further solvent selected from the group consisting of multifunctional alcohols having two or more hydroxyl groups per molecule, and from two to twelve carbon atoms, ether, and hydrocarbon solvents, or
a mixture of solvents that comprises a mass fraction of at least 10% of a monohydric alcohol R 3 OH with a further solvent selected from the group consisting of ether and hydrocarbon solvents,

wherein R 0 and R 1 and R 2 and R 3 are each independently selected from the group consisting of alkyl groups having from one to twenty carbon atoms and each are linear, branched or cyclic,
wherein at least one of the alkyl groups R 1 and R 2 if present, and R 3 if present, and R 0 if present, is a tertiary alkyl group, and
wherein there is at least one alkyl group R i selected from the group consisting of R 0 , R 1 ,R 2 , and R 3 wherein i is one of 0, 1, 2, and 3, for which the following relations are true:
R i ≠R j for all j selected from the group consisting of 0, 1, 2, and 3 with the condition that i≠j, and
n(R i )≤[n(R 0 )+n(R 1 )+n(R 2 )+n(R 3 )]·0.02,
where n(R) is the amount of substance, with the SI unit “mol”, of an alkyl group R which stands for any of R 0 , R 1 , R 2 , and R 3 .

2. The process of claim 1 wherein R 1 is a tertiary alkyl group.

3. The process of claim 1 wherein R 3 is a tertiary alkyl group.

4. The process of claim 1 wherein R 1 and R 3 are tertiary alkyl groups.

5. The process of claim 1 wherein the aminotriazine A has at least two primary amino groups, and is selected from the group consisting of melamine, formoguanamine, acetoguanamine, benzoguanamine and caprinoguanamine, an N-alkylmelamine, and an N,N-dialkylmelamine, wherein, in the N-alkylmelamine and the N,N-dialkylmelamine, the alkyl groups are the same or are different, and the alkyl groups individually have from one to twenty carbon atoms, and are linear or branched, if the number of carbon atoms is three or more, or cyclic, if the number of carbon atoms is three or more.

6. The process of claim 1 wherein the base comprises metal alkoxides which are prepared in situ from corresponding metals or metal compounds by heating a mixture of a metal, or a metal compound, with an alcohol having from one to twenty carbon atoms, optionally in the presence of an entrainment agent, wherein the metal compounds are individually selected from the group consisting of metal hydrides, metal oxides, metal hydroxides, metal amides, metal alkoxides, and organometal compounds.

7. The process of claim 1 wherein the organic carbonate C has the structure R 4 O—CO—OR 5 , where R 4 and R 5 are the same or are different, and are individually selecteld from the group consisting of alkyl radicals having from one to twenty carbon atoms, and are linear or branched if the number of carbon atoms is three or more, or cyclic if the number of carbon atoms is three or more, or are together form an alkane diyl radical having from two to twenty carbon atoms, and are linear or branched, if the number of carbon atoms is three or more, or cyclic, if the number of carbon atoms is three or more.

8. The process of claim 1 wherein the aminotriazine A is selected from the group consisting of melamine, acetoguanamine, and benzoguanamine.

9. The process of claim 1 which comprises after reaction of the mixture of
an aminotriazine A having at least two amino groups per molecule,
an organic carbonate C, and
a base B selected from the group consisting of alkoxides of metals M in the solvent S,
an additional step of adding, to the products of the said reaction, an acid or a solution of an acid in a solvent S′ which is the same as the solvent S or is different therefrom, or adding the products of the reaction to an acid or a solution of an acid in a solvent S′ which is the same as the solvent S or is different therefrom.

10. The process of claim 1 where the base is a tert-butoxide of an alkali metal.

11. The process of claim 10 where the alkali metal is selected from the group consisting of lithium, sodium and potassium.

12. The process of claim 1 where the base is a mixture of n-butoxides and tert-butoxides of an alkali metal.

13. The process of claim 1 wherein the solvent S comprises n-butanol.

14. The process of claim 13 where the solvent S additionally comprises tert-butanol.

15. The process of claim 13 where the solvent S additionally comprises xylene.

16. The process of claim 9 where the acid is selected from the group consisting of nitric acid, sulphuric acid, phosphoric acid, formic acid, and acetic acid.

17. The process of claim 9 wherein the acid dissolved in a solvent S′ is selected from the group consisting of n-butanol, tert-butanol, and water.

18. The process of claim 1 wherein R 2 or R 3 is a tertiary alkyl group.

Assignees

• Allnex Ip Sarl
• Allnex Netherlands Bv

Inventors

• Flood Lawrence

Classifications

• C07D251/24 Primary

  to three ring carbon atoms · CPC title

• C07D251/18

  with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines · CPC title

• C07D251/54 Primary

  Three nitrogen atoms · CPC title

• C07D251/70

  Other substituted melamines · CPC title