3D printing with PHT based materials

Patent metadata

Field	Value
Publication number	US-9957345-B2
Application number	US-201414461813-A
Country	US
Kind code	B2
Filing date	Aug 18, 2014
Priority date	Aug 18, 2014
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

This application describes methods of forming an object. The methods described include flowing a polyhemiaminal (PHA), polyhexhydrotriazine (PHT), or polyoctatriazacane (POTA) precursor mixture to a nozzle of a 3D printer, heating the PHA, PHT, or POTA precursor to a temperature of at least 50° C., dispensing the PHA, PHT, or POTA precursor in a pattern; and, hardening the PHA, PHT, or POTA precursor into a polymer. The PHA and PHT polymers are formed by reacting a primary diamine with a formaldehyde-type reagent. The POTA polymer is formed by reacting a primary diamine with a formaldehyde-type reagent and formic acid. The objects formed using the methods described herein may be made of a single polymer, a single polymer type using multiple diamine monomers, or a mixture of PHA, PHT, and/or POTA polymers with different desired physical properties.

First claim

We claim:

1. A method of forming an object, comprising:
flowing a polyhemiaminal (PHA), polyhexahydrotriazine (PHT), or polyoctatriazacane (POTA) precursor mixture to a nozzle of a 3D printer;
heating the PHA, PHT, or POTA precursor to a temperature of at least 50° C.;
dispensing the PHA, PHT, or POTA precursor in a pattern; and
hardening the PHA, PHT, or POTA precursor into a polymer.

2. The method of claim 1 , wherein dispensing the PHA, PHT, or POTA precursor in a pattern comprises forming a first film of the PHA, PHT, or POTA precursor on a substrate and forming a second film of the PHA, PHT, or POTA precursor on the first film.

3. The method of claim 2 , wherein the precursor comprises a PHA, and the PHA is a crosslinked polymer comprising i) a plurality of trivalent hemiaminal groups of formula (1):

covalently linked to ii) a plurality of bridging groups of formula (2):
K′ *) y′   (2),

wherein y′ is 2 or 3, and K′ is a divalent or trivalent radical comprising at least one 6-carbon aromatic ring.

4. The method of claim 2 , wherein the precursor comprises a PHT, and the PHT is a crosslinked polymer comprising i) a plurality of trivalent hexahydrotriazine groups of formula (8):

covalently linked to ii) a plurality of bridging groups of formula (2):
K′ *) y′   (2),

wherein y′ is 2 or 3, and K′ is a divalent or trivalent radical comprising at least one 6-carbon aromatic ring.

5. The method of claim 2 , wherein the precursor comprises a POTA, and the POTA is a polymer having a plurality of octatriazacane groups of formula (10):

6. The method of claim 2 , wherein the precursor comprises a primary diamine and a formaldehyde-type reagent.

7. The method of claim 6 , wherein the precursor further comprises formic acid.

8. The method of claim 1 , wherein flowing the PHA, PHT, or POTA precursor mixture to a nozzle of a 3D printer comprises flowing a first mixture comprising a formaldehyde-type reagent through a first pathway and flowing a second mixture comprising a primary diamine through a second pathway.

9. The method of claim 1 , wherein heating the PHA, PHT, or POTA precursor to a temperature of at least 50° C. comprises supplying heat to the nozzle.

10. A method of forming an object, comprising:
flowing a first mixture comprising a formaldehyde-type reagent through a first pathway;
flowing a second mixture comprising a primary diamine through a second pathway;
mixing the first and second mixtures to form a PHA, PHT, or POTA precursor;
flowing the PHA, PHT, or POTA precursor to a nozzle of a 3D printer;
supplying heat to the nozzle of the 3D printer to heat the PHA, PHT, or POTA precursor to a temperature of at least 50° C.;
dispensing the PHA, PHT, or POTA precursor in a pattern onto a substrate to form a precursor object comprising a PHA, PHT, or POTA cross-linked polymer; and
hardening the PHA, PHT, or POTA precursor into a polymer by heating the precursor object to a temperature of at least 50° C.

11. The method of claim 10 , wherein the precursor object comprises a PHA, and the PHA is a crosslinked polymer comprising i) a plurality of trivalent hemiaminal groups of formula (1):

covalently linked to ii) a plurality of bridging groups of formula (2):
K′ *) y′   (2),

wherein y′ is 2 or 3, and K′ is a divalent or trivalent radical comprising at least one 6-carbon aromatic ring.

12. The method of claim 10 , wherein the precursor object comprises a PHT, and the PHT is a crosslinked polymer comprising i) a plurality of trivalent hexahydrotriazine groups of formula (8):

covalently linked to ii) a plurality of bridging groups of formula (2):
K′ *) y′   (2),

wherein y′ is 2 or 3, and K′ is a divalent or trivalent radical comprising at least one 6-carbon aromatic ring.

13. The method of claim 10 , wherein the precursor object comprises a POTA, and the POTA is a polymer having a plurality of octatriazacane groups with the structure of formula (10):

covalently bonded to divalent linking groups having the general structure *-K-*, where K′ comprises an aromatic group.

14. The method of claim 10 , wherein the precursor object comprises two or more of a PHA, a PHT, and a POTA.

15. The method of claim 10 , wherein hardening the PHA, PHT, or POTA precursor into a polymer comprises heating the precursor object to a temperature of at least 120° C.

16. The method of claim 1 , further comprising removing a PHT portion of the polymer by applying a solvent, a light source, or a combination thereof.

17. The method of claim 10 , further comprising removing a PHT portion of the polymer by applying a solvent, a light source, or a combination thereof.

Assignees

• IBM

Inventors

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

Classifications

• B29K2061/20

  Aminoplasts · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29C67/0055

  Operations & Transport · mapped topic

• C08G12/08 Primary

  aromatic · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title