Synthesis of dynamic covalent 3D constructs

Patent metadata

Field	Value
Publication number	US-9809673-B2
Application number	US-201715423323-A
Country	US
Kind code	B2
Filing date	Feb 2, 2017
Priority date	Aug 22, 2014
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

Methods and materials for preparing a covalent 3D nano-object are provided. A diamine or triamine monomer and a monoamine terminated precursor may be reacted to form a star polymer material. A cross-linking polymerization process may in a nanogel core with the monoamine terminated precursor covalently linked to the nanogel core. The covalent 3D nano-object may comprise HT, PHT, HA, and/or PHA materials.

First claim

The invention claimed is:

1. A method of forming a star polymer material, comprising:
providing a triamine monomer;
providing a monoamine terminated precursor;
exposing the triamine monomer and the monoamine terminated precursor to an aldehyde material; and
forming a star polymer material comprising a polyhemiaminal or polyhexahydrotriazine material, wherein the polyhemiaminal or polyhexahydrotriazine material comprises an aromatic bridging group.

2. The method of claim 1 , wherein the triamine monomer comprises an aliphatic material.

3. The method of claim 2 , wherein the triamine monomer comprises tris(2-aminoethyl) amine.

4. The method of claim 1 , wherein the polyhemiaminal or polyhexahydrotriazine material comprises an aromatic bridging group.

5. The method of claim 1 , wherein the monoamine terminated precursor comprises a monomer, oligomer, polymer, or combinations thereof.

6. The method of claim 5 , wherein the monoamine terminated precursor comprises an amine terminated polyether material.

7. The method of claim 6 , wherein the monoamine terminated precursor comprises monoamine poly(ethylene glycol).

8. The method of claim 1 , wherein the star polymer material is formed by a process comprising:
forming a mixture comprising one or more monomers comprising two aromatic primary amine groups having the general structure H 2 N—Ar-L′-Ar—N—H 2 , wherein Ar denotes a benzene ring group and L′ is a divalent linking group, and a solvent; and
heating the mixture at a temperature of about 50° C. to about 280° C. for about 1 minute to about 24 hours.

9. The method of claim 1 , wherein the exposing the triamine monomer and the monoamine terminated precursor to an aldehyde material comprises forming a cross-linked polyhemiaminal or polyhexahydrotriazine nanogel core with the monoamine terminated precursor covalently linked to the nanogel core.

10. A method of forming a star polymer material, comprising:
reacting a triamine monomer with a monoamine terminated precursor comprising a polyether amine terminated with a functional group, to form a polyhemiaminal; and
heating the polyhemiaminal to form a star polymer material comprising a hexahydrotriazine material having a plurality of trivalent hexahydrotriazine groups having the structure

and
a plurality of bridging groups having the structure
K′ *) y′ , wherein y′ is 3, and K′ is a trivalent radical, wherein the trivalent radical comprises at least one 6-carbon aromatic ring.

11. The method of claim 10 , wherein the trivalent radical comprises at least one 6-carbon aromatic ring.

12. The method of claim 10 , wherein the plurality of bridging groups is selected from the group consisting of

13. A method of forming a star polymer material, comprising:
providing tris(2-aminoethyl) amine;
providing a monoamine terminated precursor;
exposing the tris(2-aminoethyl) amine and the monoamine terminated precursor to an aldehyde material to form a mixture;
heating the mixture; and
forming a star polymer material comprising a polyhemiaminal or polyhexahydrotriazine material, wherein the polyhemiaminal or polyhexahydrotriazine material comprises an aromatic bridging group.

14. The method of claim 13 , wherein the polyhemiaminal or polyhexahydrotriazine material comprises an aromatic bridging group.

15. The method of claim 13 , wherein the monoamine terminated precursor comprises a monomer, oligomer, polymer, or combinations thereof.

16. The method of claim 15 , wherein the monoamine terminated precursor comprises an amine terminated polyether material.

17. The method of claim 16 , wherein the monoamine terminated precursor comprises monoamine poly(ethylene glycol).

18. The method of claim 13 , wherein forming the star polymer further comprises:
adding to the mixture a monomer having the general structure H 2 N—Ar-L′-Ar—N—H 2 , wherein Ar denotes a benzene ring group and L′ is a divalent linking group, and a solvent; and
heating the mixture at a temperature of about 50° C. to about 280° C. for about 1 minute to about 24 hours.

19. The method of claim 13 , wherein the exposing the tris(2-aminoethyl) amine and the monoamine terminated precursor to an aldehyde material comprises forming a cross-linked polyhemiaminal or polyhexahydrotriazine nanogel core with the monoamine terminated precursor covalently linked to the nanogel core.

Assignees

• IBM

Inventors

• Boday Dylan J
• Garcia Jeannette M
• Hedrick James L
• Wojtecki Rudy J

Classifications

• C08G12/08

  aromatic · CPC title

• C08G12/043 Primary

  with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 · CPC title

• C08G12/06

  Amines · CPC title

• C08G73/0638

  with at least three nitrogen atoms in the ring · CPC title