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

Patent metadata

Field	Value
Publication number	US-2021364915-A1
Application number	US-202117396514-A
Country	US
Kind code	A1
Filing date	Aug 6, 2021
Priority date	Aug 31, 2016
Publication date	Nov 25, 2021
Grant date	—

Abstract

According to one exemplary embodiment, a method includes exposing one or more portions of an additive manufacturing resin to light; where the light includes a wavelength configured to cause a photo polymerizable compound in the additive manufacturing resin to polymerize; and the one or more portions of the additive manufacturing resin are defined by a three-dimensional pattern. Moreover, a method of forming an additive manufacturing resin suitable for fabricating a click-chemistry compatible composition of matter includes: reacting a compound comprising a terminal alkyne group or a terminal azide group with a protecting reagent to form a protected reactive diluent precursor, reacting the precursor with a second compound to form a protected reactive diluent; and mixing the protected reactive diluent with a photo polymerizable compound.

First claim

What is claimed is:

1 . A method, comprising:
exposing one or more portions of an additive manufacturing resin to light; wherein the light includes a wavelength configured to cause a photo polymerizable compound in the additive manufacturing resin to polymerize; and wherein the one or more portions of the additive manufacturing resin are defined by a three-dimensional pattern.

2 . The method as recited in claim 1 , wherein the photo polymerizable compound comprises at least one click-chemistry compatible functional group.

3 . The method as recited in claim 1 , wherein polymerizing the photo polymerizable compound in the additive manufacturing resin forms a solid structure defined according to the three-dimensional pattern, and the method further comprises:
submerging at least a portion of the solid structure in the additive manufacturing resin; and exposing to the light either or both of:
first portion(s) of the additive manufacturing resin, wherein the first portions of the additive manufacturing resin are at least partially in contact with some or all of the submerged portion of the solid structure; and/or
other portions of the additive manufacturing resin; and
wherein exposing the first portion(s) of the additive manufacturing resin and/or the other portions of the additive manufacturing resin to the light extends the solid structure according to the three-dimensional pattern.

4 . The method as recited in claim 1 , comprising adding one or more pore-forming compounds to the additive manufacturing resin prior to the exposing, wherein the one or more pore-forming compounds are each independently configured to create pores in a solid structure defined by the three-dimensional pattern.

5 . The method as recited in claim 1 , wherein the exposing comprises projection micro stereolithography.

6 . The method as recited in claim 1 , wherein polymerizing the photo polymerizable compound in the additive manufacturing resin forms a solid structure defined by the three-dimensional pattern;
wherein one or more surfaces of the solid structure comprise one or more exposed click-chemistry compatible functional groups; and wherein the method further comprises: reacting some or all of the exposed click-chemistry compatible functional groups with an organic additive.

7 . The method as recited in claim 6 , wherein the organic additive comprises a plurality of click-chemistry compatible functional groups having a composition other than a composition of the exposed click-chemistry compatible functional groups included in the one or more surfaces of the solid structure.

8 . The method as recited in claim 6 , wherein the reacting renders the one or more surfaces of the solid structure hydrophobic.

9 . The method as recited in claim 6 , wherein the reacting renders the one or more surfaces of the solid structure hydrophilic.

10 . The method as recited in claim 6 , wherein the reacting forms a self-assembled monolayer on the one or more surfaces of the solid structure.

11 . The method as recited in claim 6 , wherein at least some of the organic additive is tethered to silica dioxide nanoparticles.

12 . The method as recited in claim 6 , wherein the organic additive comprises a pharmacophore.

13 . The method as recited in claim 6 , wherein the reacting is performed in the presence of a catalyst.

14 . The method as recited in claim 13 , wherein the catalyst comprises one or more compounds selected from the group consisting of: copper (I), ruthenium, silver, gold, iridium, nickel, zinc, lanthanum, and combination(s) thereof.

15 . A method of forming an additive manufacturing resin suitable for fabricating a click-chemistry compatible composition of matter, the method comprising:
reacting a compound comprising a terminal alkyne group or a terminal azide group with a protecting reagent to form a protected reactive diluent precursor, the precursor comprising the terminal alkyne group or the terminal azide group; reacting the precursor with a second compound comprising a photo polymerizable group to form a protected reactive diluent; and mixing the protected reactive diluent with a photo polymerizable compound to form the additive manufacturing resin.

16 . The method as recited in claim 15 , wherein the photo polymerizable compound comprises a polyethylene-glycol backbone functionalized with at least one photo polymerizable moiety selected from a group consisting of: acrylates, epoxides, and thiol-enes.

17 . The method as recited in claim 15 , wherein the photo polymerizable compound comprises a hexanediol backbone functionalized with at least one photo polymerizable moiety selected from a group consisting of: acrylates, epoxides, and thiol-enes.

18 . The method as recited in claim 15 , wherein the protecting reagent comprises a protecting group selected from a group consisting of: a trimethylsilyl, a triethylsilyl, a t-butyl dimethylsilyl, a triisopropylsilyl, and a 2-(2-hydroxypropyl)alkyne.

19 . The method as recited in claim 15 , wherein reacting the compound comprising the terminal alkyne group or the terminal azide group with the protecting reagent attaches a protecting group to the terminal alkyne group or the terminal azide group.

20 . The method as recited in claim 15 , wherein reacting the compound comprising the terminal alkyne group or the terminal azide group with the protecting reagent comprises:
reacting the compound comprising the terminal alkyne group or the terminal azide group with an organolithium reagent; and treating, with an acid, a product of reacting the compound comprising the terminal alkyne group or the terminal azide group with the organolithium reagent.

Assignees

• L Livermore Nat Security Llc

Inventors

• Campbell Patrick
• Duoss Eric
• Oakdale James

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• G03F7/025

  Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds (G03F7/075 takes precedence) · CPC title

• G03F7/0037 Primary

  Production of three-dimensional images · CPC title

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title

• G03F7/012

  Macromolecular azides; Macromolecular additives, e.g. binders {(G03F7/0085 takes precedence)} · CPC title