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

Patent metadata

Field	Value
Publication number	US-12487521-B2
Application number	US-202117396514-A
Country	US
Kind code	B2
Filing date	Aug 6, 2021
Priority date	Aug 31, 2016
Publication date	Dec 2, 2025
Grant date	Dec 2, 2025

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 comprising one or more photo polymerizable compounds to light to form a three-dimensional structure, the one or more photo polymerizable compounds having crosslinking groups for crosslinking and click-chemistry compatible functional groups configured to participate in click-chemistry reactions, the click-chemistry compatible functional groups having a different chemical composition than the crosslinking groups; wherein the light includes a wavelength configured to cause crosslinking of some or all of the crosslinking groups of the one or more photo polymerizable compounds in the additive manufacturing resin to thereby polymerize the one or more photo polymerizable compounds, and wherein one or more surfaces of the three-dimensional structure are functionalized with one or more of the click-chemistry compatible functional groups.

2 . The method as recited in claim 1 , wherein the exposing comprises projection microstereolithography.

3 . The method as recited in claim 1 , wherein the method further comprises: reacting some or all of the one or more click-chemistry compatible functional groups with an organic additive; and
wherein either: at least some of the organic additive is tethered to silica nanoparticles; the organic additive comprises a pharmacophore; the organic additive comprises a plurality of click-chemistry compatible functional groups having a composition other than a composition of the one or more click-chemistry compatible functional groups functionalized to the one or more surfaces of a multiplicity of pores of the three-dimensional structure; or any combination thereof.

4 . The method as recited in claim 1 , wherein the method further comprises: reacting some or all of the one or more click-chemistry compatible functional groups with an organic additive; and
wherein either: the reacting renders the one or more surfaces of the three-dimensional structure hydrophobic; the reacting renders the one or more surfaces of the three-dimensional structure hydrophilic; the reacting renders the one or more surfaces of the three-dimensional structure anti-corrosive; the reacting forms a self-assembled monolayer on the one or more surfaces of the three-dimensional structure; the reacting is performed in the presence of a catalyst comprising one or more compounds selected from the group consisting of: copper (I), ruthenium, silver, gold, iridium, nickel, zinc, lanthanum; or any combination thereof.

5 . The method as recited in claim 1 , wherein the additive manufacturing resin comprises at least one reactive diluent independently comprising
at least one of the one or more click-chemistry compatible functional groups; wherein the at least one of the one or more click-chemistry compatible functional groups of the at least one reactive diluent is functionalized with a protecting group to protect the at least one reactive diluent from participating in click-chemistry reactions; and wherein the protecting comprises either: a trialkylsilyl group, a 2-(2-hydroxypropyl)alkyne group, or any combination thereof.

6 . The method as recited in claim 5 , further comprising deprotecting the at least one of the one or more click-chemistry compatible functional groups of the at least one reactive diluent; and
reacting some or all of the one or more click-chemistry compatible functional groups with an organic additive.

7 . The method as recited in claim 5 , further comprising deprotecting the at least one of the one or more click-chemistry compatible functional groups of the at least one reactive diluent; wherein the deprotecting comprises submerging and/or washing the three-dimensional structure in a solution containing at least one deprotecting agent comprising either a fluoride, silver nitrate, a strong base, or any combination thereof.

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

9 . The method as recited in claim 1 , further comprising adding one or more photoabsorbers to the additive manufacturing resin prior to the exposing.

10 . The method as recited in claim 1 , further comprising adding one or more photoreductants to the additive manufacturing resin prior to the exposing.

11 . The method as recited in claim 1 , wherein polymerizing the one or more photo polymerizable compounds comprises either: crosslinking one or more epoxide-based compounds in the additive manufacturing resin, crosslinking one or more vinyl ethers in the additive manufacturing resin, crosslinking one or more N-vinyl carbazole(s) in the additive manufacturing resin, or any combination thereof.

12 . The method as recited in claim 1 , wherein the one or more photo polymerizable compounds comprise one or more groups of either: one or more epoxides, one or more silicones, one or more thiol-enes, one or more R-substituted acryloyl halides, one or more vinyl ethers, one or more acrylates, one or more methacrylates, one or more N-vinyl carbazoles, or any combination thereof, wherein R is one or more moieties selected from the group consisting of: methyl, hydrogen, alkyl, and/or aryl.

13 . The method as recited in claim 1 , wherein the one or more photo polymerizable compounds independently comprise one or more linker groups.

14 . The method as recited in claim 13 , wherein the one or more linker groups independently comprise either: aliphatic groups, polyethylene groups, aromatic groups, dimethyl siloxane groups, ester groups, amide groups, amine groups, ether groups, urea groups, carbamate groups, carbonate groups, sulfone groups, R-substituted aliphatic groups, R-substituted polyethylene groups, R-substituted aromatic groups, R-substituted dimethyl siloxane groups, R-substituted ester groups, R-substituted amide groups, R-substituted amine groups, R-substituted ether groups, R-substituted urea groups, carbamate groups, R-substituted carbonate groups, R-substituted sulfone groups, or any combination thereof; wherein R is one or more moieties selected from the group consisting of: methyl, hydrogen, alkyl, and/or aryl.

15 . The method as recited in claim 1 , wherein the click-chemistry compatible functional groups are protected in the resin.

16 . The method as recited in claim 15 , comprising deprotecting the click-chemistry compatible functional groups.

17 . A method, comprising:
adding one or more pore-forming compounds to an additive manufacturing resin comprising one or more photo polymerizable compounds, wherein the one or more pore-forming compounds are each independently configured to create pores in a three-dimensional structure defined by a three-dimensional pattern, wherein the photo polyme

Assignees

• L Livermore Nat Security Llc

Inventors

• Campbell Patrick
• Duoss Eric
• Oakdale James

Classifications

• G03F7/20

  Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) · CPC title

• G03F7/012

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

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• G03F7/0755

  Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence) · CPC title