Dual cure resins containing microwave absorbing materials and methods of using the same

Patent metadata

Field	Value
Publication number	US-10500786-B2
Application number	US-201715626787-A
Country	US
Kind code	B2
Filing date	Jun 19, 2017
Priority date	Jun 22, 2016
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

Abstract

Provided herein according to some embodiments is a method of forming a three-dimensional intermediate object with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a microwave absorbing material, (ii) a light polymerizable liquid first component, and (iii) a second solidifiable component that is different from said first component. Optionally, but in some embodiments preferably, the method includes supporting the three-dimensional intermediate with a separate support media prior to solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object; and then optionally separating said support media when present from said three-dimensional object.

First claim

That which is claimed is:

1. A method of forming a three-dimensional object, comprising:
(a) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;
(b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a microwave absorbing material, (ii) a light polymerizable liquid first component, and (iii) a second solidifiable component that is different from said first component; and
(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from said first component and also advancing said carrier away from said build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object and containing said second solidifiable component carried in said scaffold in unsolidified and/or uncured form; then
(d) supporting said three-dimensional intermediate with a separate support media;
(e) solidifying and/or curing, said second solidifiable component in said three-dimensional intermediate to form said three-dimensional object in said support media; and then
(f) separating said support media from said three-dimensional object,
wherein said support media is a solid particulate and is inert and/or water soluble.

2. The method of claim 1 , wherein said support media is flowable.

3. The method of claim 1 , wherein said support media comprises a microwave absorbing material.

4. The method of claim 1 , wherein said support media is comprised of an inorganic salt.

5. The method of claim 4 , wherein said inorganic salt is selected from the group consisting of sodium chloride, sodium bicarbonate, sodium carbonate, sodium sulfate, sodium sulfite, sodium iodide, sodium bromide, magnesium sulfate, magnesium carbonate, magnesium bromide, magnesium iodide, calcium chloride, calcium carbonate, calcium bromide, calcium sulfate, calcium iodide, potassium carbonate, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, ammonium sulfate, ammonium chloride, ammonium bromide, ammonium iodide, and combinations thereof.

6. The method of claim 1 , wherein said separating step is carried out by dissolving or solubilizing said support media with water.

7. The method of claim 1 , wherein said solidifying and/or curing step (e) is carried out by heating and/or microwave irradiating.

8. The method of claim 1 , wherein said three-dimensional intermediate is collapsible, compressible, or elastic.

9. The method of claim 1 , wherein said filling and irradiating steps (b) and (c) are carried out by continuous liquid interface production (CLIP).

10. The method of claim 1 , wherein said second solidifiable component comprises:
(i) a polymerizable liquid solubilized in or suspended in said first component;
(ii) a polymerizable solid suspended in said first component;
(iii) a polymerizable solid solubilized in said first component; or
(iv) a polymer solubilized in said first component.

11. The method of claim 1 , wherein said polymerizable liquid comprises:
from 1 or 10 percent by weight to 40, 90 or 99 percent by weight of said first component; and
from 1, 10 or 60 percent by weight to 90 or 99 percent by weight of said second solidifiable component.

12. The method of claim 1 , wherein said solidifying and/or curing step (e) is carried out subsequent to said irradiating step (c) and is carried out by:
(i) heating said second solidifiable component;
(ii) irradiating said second solidifiable component with light at a wavelength different from that of the light in said irradiating step (c);
(iii) contacting said second polymerizable component to water; and/or
(iv) contacting said second polymerizable component to a catalyst.

13. The method of claim 1 , wherein:
said second solidifiable component comprises precursors to a polyurethane, polyurea, or copolymer thereof, a silicone resin, an epoxy resin, a cyanate ester resin, or a natural rubber; and
said solidifying and/or curing step is carried out by heating.

14. The method of claim 1 , wherein:
said second solidifiable component comprises precursors to a polyurethane, polyurea, or copolymer thereof, and
said solidifying and/or curing step is carried out by contacting said second solidifiable component to water.

15. The method of claim 1 , wherein said solidifying and/or curing step (e) is carried out under conditions in which said solid polymer scaffold degrades and forms a constituent necessary for the polymerization of said second solidifiable component.

16. The method of claim 1 , wherein:
said second solidifiable component comprises precursors to a polyurethane, polyurea, or copolymer thereof, a silicone resin, a ring-opening metathesis polymerization resin, a click chemistry resin, or a cyanate ester resin, and
said solidifying and/or curing step is carried out by contacting said second solidifiable component to a polymerization catalyst.

17. The method of claim 1 ,
wherein said light polymerizable liquid first component comprises monomers and/or prepolymers that are polymerized by exposure to actinic radiation or light, and
solidifying said second solidifiable component comprises contacting to heat, water, water vapor, light at a different wavelength than that at which said first component is polymerized, catalysts, evaporation of a solvent from the polymerizable liquid, exposure to microwave irradiation, or a combination thereof.

18. The method of claim 17 , wherein said monomers and/or prepolymers comprises reactive end groups selected from the group consisting of acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and combinations thereof.

19. The method of claim 17 , wherein said second solidifiable component comprising monomers and/or prepolymers comprises reactive end groups selected from the group consisting of: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate/hydroxyl, isocyanate/amine, isocyanate/carboxylic acid, cyanate ester, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si—H, Si—Cl/hydroxyl, Si—Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide, click chemistry reactive groups, alkene/sulfur, alkene/thiol, alkyne/thiol, hydroxyl/halide, isocyanate/water, Si—OH/hydroxyl, Si—OH/water, Si—OH/Si—H, Si—OH/Si—OH, perfluorovinyl, diene/dienophiles, olefin metathesis polymerization groups, olefin polymerization groups for Ziegler-Natta catalysis, and ring-opening polymerization groups and mixtures thereof.

20. The method of claim 1 , wherein:
said three-dimensional object is comprised of polyurethane, polyurea, or copolymer thereof; and
said polymerizable liquid is comprised of at least one of: (i) a blocked or reactive blocked prepolymer, (ii) a blocked of reactive blocked diisocyante, or (iii) a blocked or reactive blocked diisocyanate chain extender.

21. The method of claim 20 , wherein said polymerizable liquid comprises:
(a) a mixture of (i) a blocked or reactive blocked prepolymer, (ii) a chain extender, (iii) a photoinitiator, (iv) optionally a polyol and/or a polyamine, (v) optionally a reactive diluent, (vi) optionally a pigment or dye, and (v

Assignees

• Carbon Inc

Inventors

• Rolland Jason P

Classifications

• B29C2035/0855

  using microwave · CPC title

• B29C64/277

  using multiple radiation means, e.g. micromirrors or multiple light-emitting diodes [LED] · CPC title

• B29K2105/0002

  monomers or prepolymers · CPC title

• B29C2035/0827

  using UV radiation · CPC title

• B29C2035/0833

  using actinic light · CPC title