Click-chemistry compatible structures, click-chemistry functionalized structures, and materials and methods for making the same

Patent metadata

Field	Value
Publication number	US-10732502-B2
Application number	US-201615253654-A
Country	US
Kind code	B2
Filing date	Aug 31, 2016
Priority date	Aug 31, 2016
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

Abstract

According to various embodiments, systems, methods, and computer program products for click-chemistry compatible structures, additive manufacturing resins for forming the same, and method of formation of such structures and resins, as well as techniques for functionalizing click-chemistry compatible structures are disclosed. The inventive structures generally include a plurality of photo polymerized molecules structurally arranged according to a three-dimensional pattern, while surfaces of the structure are functionalized with one or more click-chemistry compatible molecules each having one or more click-chemistry compatible functional groups. The structures may be formed from single- or dual-component resins, each having unique synthetic pathways. The resulting structures may be functionalized for utility in a wide range of applications by leveraging click chemistry to further functionalize the structure with organic additives also compatible with click-chemistry reaction schemes.

First claim

What is claimed is:

1. A click-chemistry compatible structure, comprising:
a plurality of photo polymerized molecules structurally arranged according to a multi-layer three-dimensional pattern; and
wherein surfaces of the structure are functionalized with one or more click-chemistry compatible molecules each having one or more click-chemistry compatible functional groups.

2. The structure as recited in claim 1 , wherein the click-chemistry compatible functional groups are configured to engage in a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction.

3. The structure as recited in claim 1 , wherein at least some of the click-chemistry compatible functional groups comprise a terminal azide group.

4. The structure as recited in claim 3 , wherein at least some other of the click-chemistry compatible functional groups comprise a terminal alkyne group.

5. The structure as recited in claim 1 , wherein the photo polymerized molecules are each independently selected from the group consisting of: crosslinked hexane diol diacrylate (HDDA), crosslinked polyethylene glycol diacrylate (PEGDA), crosslinked pentaerythritol triacrylate (PETA), crosslinked ethylene glycol dimethacrylate (EGDMA) and combinations thereof.

6. The structure as recited in claim 1 , wherein at least some of the click-chemistry compatible molecules are functionalized with one or more organic additives selected from a group consisting of:
an antibiotic;
an antibacterial compound; and
silica dioxide nanoparticles.

7. The structure as recited in claim 1 , wherein at least some of the click-chemistry compatible functional groups are functionalized to form a self-assembled monolayer (SAM), wherein the SAM comprises either or both of: an azide-terminated poly(polyethylene glycol) methacrylate derivative; and an alkyne-terminated poly(polyethylene glycol) methacrylate derivative.

8. The structure as recited in claim 1 , wherein the structure is porous.

9. The structure as recited in claim 1 , wherein the structure is characterized by features having a size in a range from about three-hundred nanometers to about one thousand microns.

10. The structure as recited in claim 1 , wherein a bulk of the structure comprises the photo polymerized molecules; and
wherein the surfaces functionalized with the one or more click-chemistry compatible molecules also comprise the photo polymerized molecules.

11. The structure as recited in claim 1 , wherein the three-dimensional pattern comprises an octahedral truss.

12. The structure as recited in claim 1 , wherein the click-chemistry compatible functional groups are protected from participating in a click-chemistry reaction via one or more protecting groups functionalized to the click-chemistry compatible functional groups; and
wherein the one or more protecting groups are each independently selected from the group consisting of: a triethylsilyl (TES), a t-butyldimethylsilyl (TBS) group, a triisopropylsilyl (TIPS) group, a 2-(2-hydroxypropyl) group, and combinations thereof.

13. A method of forming the structure as recited in claim 1 , the method comprising:
exposing, according to the three-dimensional pattern, portions of an additive manufacturing resin to a wavelength of light configured to cause a photo polymerizable compound in the additive manufacturing resin to polymerize into a solid layer of the structure; and
wherein the additive manufacturing resin comprises at least one compound having a click-chemistry compatible functional group.

14. A method of functionalizing the structure as recited in claim 1 , the method comprising:
reacting the structure with an organic additive;
wherein the organic additive comprises one or more click-chemistry compatible functional groups other than the click-chemistry compatible functional groups of the click-chemistry compatible molecules functionalized on the surfaces of the structure;
wherein the click-chemistry compatible molecules functionalized on the surfaces of the structure are structurally configured to react with the one or more click-chemistry compatible functional groups of the organic additive and thereby attach the organic additive to the structure via the click-chemistry compatible molecules functionalized on the surfaces of the structure; and
wherein the click-chemistry compatible functional groups of the click-chemistry compatible molecules functionalized on the surfaces of the structure are each independently selected from a group consisting of: a terminal alkyne and a terminal azide.

15. The method as recited in claim 14 , wherein the organic additive is selected from a group consisting of:
an antibiotic;
an antibacterial compound; and
silica dioxide nanoparticles.

16. The method as recited in claim 14 , the reacting comprising functionalizing at least some of the click-chemistry compatible functional groups functionalized on the surfaces of the structure to form a self-assembled monolayer (SAM).

17. An additive manufacturing resin suitable for fabricating a click-chemistry compatible structure, the resin comprising a click-chemistry compatible oligomer, wherein the click-chemistry compatible oligomer comprises:
one or more click-chemistry compatible functional groups; and
one or more photo polymerizable moieties; and

wherein the click-chemistry compatible functional groups are protected from participating in a click-chemistry reaction via one or more protecting groups functionalized to the click-chemistry compatible functional groups.

18. The additive manufacturing resin of claim 17 , wherein the oligomer is both click-chemistry compatible and exhibits a photo polymerizable capability;
wherein the click-chemistry compatibility of the oligomer and the photo polymerizable capability of the oligomer are respectively conveyed via different functional groups of the oligomer; and
wherein the one or more photo polymerizable moieties each independently comprise a functional group selected from the group consisting of: an acrylate, an epoxide, a thiol-ene, a vinyl ether, and an N-vinyl carbazole.

19. The additive manufacturing resin of claim 18 , wherein the one or more photo polymerizable moieties each independently comprise either the vinyl ether or the N-vinyl carbazole.

20. The additive manufacturing resin as recited in claim 17 , further comprising: a second click-chemistry compatible oligomer, and a third click-chemistry compatible oligomer;
wherein the click-chemistry compatible oligomer comprises a click-chemistry compatible functional group and an acrylate group;
wherein the second click-chemistry compatible oligomer comprises a second click-chemistry compatible functional group and an epoxide group; and
wherein the third click-chemistry compatible oligomer comprises a third click-chemistry compatible functional group and a thiol-ene group.

Assignees

• L Livermore Nat Security Llc

Inventors

• Campbell Patrick
• Duoss Eric
• Oakdale James

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• G03F7/0085

  characterised by the non-macromolecular additives · CPC title

• C08F2/60

  Polymerisation by the diene synthesis · CPC title

• A61K47/58

  obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. poly[meth]acrylate, polyacrylamide, polystyrene, polyvinylpyrrolidone, polyvinylalcohol or polystyrene sulfonic acid resin · CPC title

• C08F2/50

  with sensitising agents · CPC title