Synthesis of dynamic covalent 3D constructs

Patent metadata

Field	Value
Publication number	US-9676891-B2
Application number	US-201414466494-A
Country	US
Kind code	B2
Filing date	Aug 22, 2014
Priority date	Aug 22, 2014
Publication date	Jun 13, 2017
Grant date	Jun 13, 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

What is claimed is:

1. A method of forming a star polymer material, comprising:
providing a diamine monomer having 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;
providing a monoamine terminated precursor;
exposing the diamine monomer and the monoamine terminated precursor to an aldehyde material by forming a mixture comprising the diamine monomer, the monoamine terminated precursor, the aldehyde material, and a solvent;
heating the mixture at a temperature of about 50° C. to about 280° C. for about 1 minute to about 24 hours; and
forming a star polymer material comprising a polyhemiaminal or polyhexahydrotriazine material.

2. The method of claim 1 , wherein the diamine monomer comprises 1,4-Bis(aminomethyl)benzene.

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

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

5. The method of claim 4 , wherein the monoamine terminated precursor comprises an amine terminated polyether material.

6. The method of claim 5 , wherein the monoamine terminated precursor comprises monoamine poly(ethylene glycol).

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

8. A method of forming a star polymer material, comprising:
preparing a star polymer material comprising reacting a diamine monomer with a monoamine terminated precursor, an aldehyde material, and a solvent to form a mixture, heating the mixture at a temperature of about 50° C. to about 280° C. for about 1 minute to about 24 hours, wherein the star polymer material comprises a hexahydrotriazine material having a plurality of trivalent hexahydrotriazine groups having the structure

and
a plurality of divalent bridging groups having the structure

each divalent bridging group bonded to two of the trivalent hexahydrotriazine groups, wherein L′ is a divalent linking group.

9. A method of forming a star polymer material, comprising:
providing 1,4-Bis(aminomethyl)benzene;
providing a monoamine terminated precursor;
exposing the 1,4-Bis(aminomethyl)benzene 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.

10. The method of claim 9 , wherein the polyhemiaminal or polyhexahydrotriazine material comprises an aromatic bridging group.

11. The method of claim 9 , wherein the monoamine terminated precursor comprises a monomer, oligomer, polymer, or combinations thereof.

12. The method of claim 11 , wherein the monoamine terminated precursor comprises an amine terminated polyether material.

13. The method of claim 12 , wherein the monoamine terminated precursor comprises monoamine poly(ethylene glycol).

14. The method of claim 9 , wherein forming the star polymer further comprises:
forming the mixture, comprising the 1,4-Bis(aminomethyl)benzene and the monoamine terminated precursor, the mixture having 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, the aldehyde material, 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.

15. The method of claim 9 , wherein the exposing the 1,4-Bis(aminomethyl)benzene 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

• C08G73/0638

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

• C08G12/06

  Amines · CPC title

• 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