Process for making benzoxazines

Patent metadata

Field	Value
Publication number	US-9902706-B2
Application number	US-201514919186-A
Country	US
Kind code	B2
Filing date	Oct 21, 2015
Priority date	Oct 27, 2014
Publication date	Feb 27, 2018
Grant date	Feb 27, 2018

Abstract

A synthesis process for making a benzoxazine compound containing at least one benzoxazine unit from aromatic amine containing at least one primary amino group, at least one phenolic compound with at least one ortho-hydrogen, and alkyl formcel. In one embodiment, the aromatic amine is reacted with alkyl formcel to generate an alkoxymethyl intermediate compound. Subsequently, the intermediate compound is reacted with a phenol to generate the benzoxazine compound. In another embodiment, the benzoxazine compound is formed by reacting aromatic amine with alkyl formcel and phenol in one reaction step. Also disclosed is a method for isolating the alkoxymethyl compound formed by reacting aromatic amine with alkyl formcel. The isolated alkoxymethyl compound is useful as a reactant in a subsequent reaction.

First claim

What is claimed is:

1. A process for making one or more benzoxazine compound(s) comprising reacting an aromatic amine comprising at least one primary amino group with alkyl formcel and at least one phenolic compound, which comprises at least one hydrogen at an ortho position relative to —OH group.

2. The process of claim 1 , wherein the aromatic amine is selected from structures represented by Formulas I, II and III:

wherein a=1 or 2; and b=0-50;
in Formula III, X and Y are linking groups that are independently selected from a direct bond, O, S, SO 2 , P═O, (Ph)P═O, OP(P═O)O—, CFO, substituted or unsubstituted alkylene, substituted or unsubstituted alkylidene, oxoalkylene, substituted or unsubstituted cycloaliphatic or aromatic group, where Ph is phenyl; Z is H or NH 2 ; R 5 , R 6 , R 7 and R 8 are same or different and are independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, alkynyl or alkoxy of C1 to C20 carbon atoms, carboxyl, cyano, aryl, aralkyl or aryloxy group, and optionally, R 5 and R 6 taken together and/or R 7 and R 8 taken together being a part of a saturated or unsaturated fused carbocyclic ring, which optionally contains O, N or S atoms in the ring;
in Formula II, when a=1, X is as define for Formula III, and when a=2, X is one of the following:

3. The process of claim 1 , wherein the phenol is selected from structures represented by the following Formulas IV, V and VI:

wherein a=1 or 2; and b=0-50;
in Formula VI, X and Y are linking group that are independently selected from a direct bond, O, S, SO 2 , P═O, (Ph)P═O, OP(P═O)O—, C═O, substituted or unsubstituted alkylene, substituted or unsubstituted alkylidene, oxoalkylene, substituted or unsubstituted cycloaliphatic or aromatic group, where Ph is phenyl; Z′ is H or OH; R 5 , R 6 , R 7 and R 8 are same and/or different and independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, alkynyl or alkoxy of C1 to C20 carbon atoms, carboxyl, cyano, aryl, aralkyl or aryloxy group, and optionally when R 5 and R 6 and/or R 7 and R 8 taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N or S atoms in the ring, with the proviso that each phenolic OH has at least one ortho hydrogen in the aromatic ring;
in Formula V, when a=1, X is as define for Formula VI, and when a=2, X is one of the following:

4. The process according to claim 1 , comprising (i) reacting the aromatic amine with alkyl formcel to generate an alkoxymethyl intermediate, and then, (ii) further reacting the alkoxymethyl intermediate with the phenolic compound to form a reaction product comprising the benzoxazine compound.

5. The process of claim 4 , wherein the alkoxymethyl intermediate is represented by
Formula VII:

where x=0-10 and y=1-10; R′=H or R; R=C1-C12 straight chain, branched chain, acyclic or cyclic, saturated or unsaturated group; and Ar is the aromatic residue part of the amine of Formulas I, II or III.

6. The process of claim 1 , wherein the reaction is carried out by mixing the aromatic amine, the alkyl formcel, and the phenolic compound and then heating the resulting mixture.

7. The process of claim 1 , wherein the alkyl formcel comprises ROCH 2 OH, where R is selected from C1-C12 straight chain, branched chain, acyclic or cyclic, saturated or unsaturated hydrocarbyl group.

8. The process of claim 1 , wherein the aromatic amine is an aromatic mono-amine.

9. The process of claim 1 , where the aromatic amine is an aromatic diamine.

10. The process of claim 1 , wherein the aromatic amine contains more than two primary amino groups.

11. The process of claim 1 , wherein the phenol compound is a mono-phenol with one —OH group.

12. The process of claim 1 , wherein the phenol compound is a polyphenol with two or more —OH groups.

13. The process of claim 1 , wherein the phenol compound is selected from:

14. The process of claim 1 , wherein the phenol compound is selected from

15. The process of claim 1 , wherein the phenol compound is selected from:

16. The process of claim 1 , wherein the phenol compound is selected from polyphenolic compounds represented by the following formulas:

where n=1-50.

17. The process of claim 1 , wherein the amine compound is selected from:

18. The process of claim 1 , wherein the amine compound is selected from:

19. The process of claim 1 , wherein the amine compound is selected from:

20. The process of claim 1 , wherein the relative amounts of aromatic amine, alkyl formcel, and phenol are such that, for each mole of aromatic amine, there are about 1.5 to about 20 moles, and about 0.8 to about 1.25 mole of monohydric phenol or about 0.4 to about 0.625 mole of a dihydric phenol (or bisphenol).

21. The process of claim 4 , wherein the reaction of the alkoxymethyl intermediate compound with the phenol is carried out in a batch process or a continuous process.

22. The process of claim 1 , wherein the reaction is carried out in the presence of a solvent selected from: alcohols, dilakyl ketone, aliphatic hydrocarbons, aromatic hydrocarbons, dialkyl ethers, cyclic ethers and combination thereof.

23. The process of claim 1 , wherein the reaction is carried out in the presence of a solvent selected from: methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dioxane, tetrahydrofuran, n-heptane, n-octane, toluene or xylenes.

24. The process of claim 1 , wherein the benzoxazine compound(s) produced by the process comprise(s) a monofunctional benzoxazine, a di-functional benzoxazine, a polybenzoxazine containing more than two benzoxazine units, or a combination thereof.

25. A reaction product composition produced by the process according to claim 1 .

Assignees

• Cytec Ind Inc

Inventors

• Gupta Ram B
• Cohen Martin
• Gupta Manav

Classifications

• C07C317/34

  having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring · CPC title

• C07C317/36

  with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms · CPC title

• C07D265/16 Primary

  with only hydrogen or carbon atoms directly attached in positions 2 and 4 · CPC title

• C07D413/14

  containing three or more hetero rings · CPC title

• C07C315/04

  by reactions not involving the formation of sulfone or sulfoxide groups · CPC title