Methods of preparing polyhemiaminals and polyhexahydrotriazines

Patent metadata

Field	Value
Publication number	US-9243107-B2
Application number	US-201314050995-A
Country	US
Kind code	B2
Filing date	Oct 10, 2013
Priority date	Oct 10, 2013
Publication date	Jan 26, 2016
Grant date	Jan 26, 2016

Abstract

Polyhexahydrotriazine (PHT) film layers are formed by a process comprising heating a first mixture comprising i) a solvent, ii) paraformaldehyde, and iii) a diamine monomer comprising two primary aromatic amine groups at a temperature of about 20° C. to less than 150° C. This heating step forms a stable polyhemiaminal (PHA) in solution, which can be cast on a surface of a substrate, thereby forming an initial film layer comprising the PHA. The initial film layer is heated at a temperature of 180° C. to about 280° C., thereby converting the PHA film layer to a PHT film layer. Young's moduli of about 8 GPA to about 14 GPA have been observed for the PHT film layers.

First claim

What is claimed is:

1. A method, comprising:
forming a reaction mixture comprising a i) solvent, ii) paraformaldehyde, and iii) a monomer comprising two primary aromatic amine groups; and
heating the reaction mixture at a temperature of 150° C. to about 280° C., thereby forming a polyhexahydrotriazine (PHT).

2. A method, comprising:
forming a first mixture comprising a i) solvent, ii) paraformaldehyde, and iii) a monomer comprising two primary aromatic amine groups;
heating the first mixture at a temperature of about 20° C. to about 120° C., thereby forming a second mixture comprising a polyhemiaminal (PHA);
casting the second mixture on a surface of a substrate, thereby forming an initial film layer disposed on the surface, the initial film layer comprising the PHA and the solvent; and
heating the initial film layer at a temperature of 150° C. to about 280° C., thereby forming a second film layer comprising a polyhexahydrotriazine (PHT).

3. The method of claim 2 , wherein the solvent is selected from the group consisting of N-methylpyrollidone (NMP), propylene carbonate (PC), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), propylene glycol methyl ether acetate (PGMEA), dimethylformamide (DMF), and combinations thereof.

4. The method of claim 2 , wherein the monomer is selected from the group consisting of 4,4′-oxydianiline (ODA), 4,4′-methylenedianiline (MDA), p-phenylenediamine (PD), 4,4′-(9-fluorenylidenyl)dianiline (FDA), and combinations thereof.

5. The method of claim 2 , wherein said heating the initial film layer is performed at a temperature of about 150° C. to about 220° C.

6. The method of claim 2 , wherein the first mixture further comprises a diluent monomer comprising one primary aromatic amine group.

7. The method of claim 6 , wherein the diluent monomer is N,N-dimethyl-p-phenylenediamine (DPD), and the PHT comprises a plurality of N,N-dimethyl-p-phenylene groups:

wherein the aromatic carbon represented as bonded to an asterisk of the diluent group is covalently linked to a nitrogen of a hexahydrotriazine group.

8. The method of claim 2 , wherein the film layer comprising the PHT has a Young's modulus of about 8 GPa to about 14 GPA.

Assignees

• IBM

Inventors

• Hedrick James L
• Horn Hans W
• Jones Gavin O
• O'Brien Jeannette M
• Virwani Kumar R

Classifications

• C08G65/00 Primary

  Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule · CPC title

• C09D171/00 Primary

  Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain (based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06); Coating compositions based on derivatives of such polymers · CPC title

• C08G12/08 Primary

  aromatic · CPC title

• C08G65/333

  containing nitrogen · CPC title

• C08G65/33306

  acyclic · CPC title