3D printing of thermoset polymers and composites

Patent metadata

Field	Value
Publication number	US-10920002-B2
Application number	US-201815979029-A
Country	US
Kind code	B2
Filing date	May 14, 2018
Priority date	May 15, 2017
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

The present disclosure provides a novel method of 3D printing using frontal polymerization chemistry. This method enables the printing of tough, high quality thermosets in a short time with the option of adding fiber reinforcement. As such, it facilitates fabrication of mechanically robust 3D-printed devices and structures.

First claim

What is claimed is:

1. A method for fabricating a printed thermoset polymer comprising:
a) extruding a thermoset gel from a dispensing apparatus to provide an extruded thermoset gel, the thermoset gel having a storage modulus of about 10 Pascals to about 10,000 Pascals and comprising a mixture of an organic phosphite, a ruthenium(II) catalyst, a dicyclopentadiene, and an organic solvent; and
b) triggering a frontal polymerization of the extruded thermoset gel, wherein the frontal polymerization propagates and cures the extruded thermoset gel;
wherein a printed thermoset polymer is printed by steps comprising steps a) and b).

2. The method of claim 1 wherein the thermoset gel is cooled below 25° C.

3. The method of claim 1 wherein the dispensing apparatus is cooled below 25° C.

4. The method of claim 1 wherein the extruded thermoset gel is extruded onto a platform that can trigger frontal polymerization.

5. The method of claim 4 wherein the platform is heated.

6. The method of claim 1 wherein the frontal polymerization propagates and cures the extruded thermoset gel instantly to about 60 minutes after the thermoset gel is extruded.

7. The method of claim 6 wherein the frontal polymerization is delayed by a sufficient amount of time to allow a second layer of the extruded thermoset gel to coalesce with a first layer of the extruded thermoset gel.

8. A method for polymerizing a thermoset gel comprising:
a) extruding a thermoset gel onto a platform from a cooled dispensing apparatus to provide an extruded thermoset gel; and
b) heating the platform to trigger a frontal polymerization of the extruded thermoset gel, wherein the frontal polymerization propagates and cures the extruded thermoset gel;
wherein the thermoset gel comprises triethyl phosphite, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), and a dicyclopentadiene;
wherein the thermoset gel is thereby polymerized.

9. The method of claim 8 wherein the thermoset gel comprises an additive to lower the melting point of the dicyclopentadiene.

10. The method of claim 9 wherein the additive is a norbornene.

11. The method of claim 8 wherein the thermoset gel has a storage modulus of about 50 Pascals to about 5,000 Pascals.

12. The method of claim 8 wherein the extruded thermoset gel is a carbon fiber composite.

13. The method of claim 1 wherein the frontal polymerization is triggered by electromagnetic irradiation.

14. The method of claim 13 , wherein the electromagnetic irradiation comprises ultraviolet light.

Assignees

• Univ Illinois

Inventors

• Moore Jeffrey S
• White Scott R
• Robertson Ian D
• Sottos Nancy R
• Aw Jia En

Classifications

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• B33Y10/00 Primary

  Processes of additive manufacturing · CPC title

• C08K5/524

  Esters of phosphorous acids, e.g. of H3PO3 · CPC title

• B29K2105/0014

  Catalysts · CPC title

• B29C70/384

  Fiber placement heads, e.g. component parts, details or accessories · CPC title