IP Library › Granted Patent US 12,487,521
Granted Patent B2
US 12,487,521 · App. 17/396,514 · Granted Dec 2, 2025

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

Inventors: Patrick Campbell (Oakland, CA); Eric Duoss (Dublin, CA); James Oakdale (Castro Valley, CA)
Assignee: Lawrence Livermore National Security, LLC
G03F7/0037B33Y70/00G03F7/008G03F7/012G03F7/025G03F7/027G03F7/038G03F7/0755G03F7/20
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Quick Facts
Patent No.
US 12,487,521
App. No.
17/396,514
Granted
Dec 2, 2025
Kind
B2
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.

Claims (54)

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 polymerizable compound comprises at least one click-chemistry compatible functional group,

wherein the at least one click-chemistry compatible functional group is distinct from one or more functional groups that convey photo polymerizable capability on the photo polymerizable compound; and

exposing one or more portions of the additive manufacturing resin including the one or more pore-forming compounds to light to form the three-dimensional structure; and

removing the one or more pore-forming compounds for rendering the three-dimensional structure porous;

wherein the light includes a wavelength configured to cause some or all of the one or more photo polymerizable compounds in the additive manufacturing resin to polymerize; and

wherein one or more surfaces of at least some pores of the three-dimensional structure are functionalized with one or more of the at least one click-chemistry compatible functional group.

18 . The method as recited in claim 17 , wherein the one or more pore-forming compounds comprise either uncrosslinked polystyrene beads, one or more salts, or any combination thereof.

19 . 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 at least one click-chemistry compatible functional group configured to participate in a click-chemistry reaction,

wherein the at least one click-chemistry compatible functional group is distinct from one or more functional groups that convey photo polymerizable capability on the photo polymerizable compound,

wherein the light includes a wavelength configured to cause crosslinking 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 the at least one click-chemistry compatible functional group.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 24, 2021
From: CAMPBELL, PATRICK; DUOSS, ERIC; OAKDALE, JAMES
To: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
Reel/Frame 057272/0562 →
Continuity (2)
Division 15253640 · Aug 31, 2016
Related Publication 20210364915A1 · Nov 25, 2021
References Cited (77)
US 2982941A · Chun · 1961 [cited by applicant]
US 3254115A · Cohen et al. · 1966 [cited by applicant]
US 4575330A · Hull · 1986 [cited by examiner]
US 4752498A · Fudim · 1988 [cited by examiner]
US 4891438A · Ahad · 1990 [cited by applicant]
US 5756261A · Takehana et al. · 1998 [cited by applicant]
US 6764636B1 · Allanic · 2004 [cited by examiner]
US 9458357B2 · Bellan · 2016 [cited by examiner]
US 10732502B2 · Campbell et al. · 2020 [cited by applicant]
US 10962879B2 · Campbell et al. · 2021 [cited by applicant]
US 11106131B2 · Campbell et al. · 2021 [cited by applicant]
US 20020028854A1 · Allanic · 2002 [cited by examiner]
US 20070141524A1 · Brennan · 2007 [cited by examiner]
US 20070219218A1 · Yu et al. · 2007 [cited by applicant]
US 20080200631A1 · Haring et al. · 2008 [cited by applicant]
US 20090098467A1 · Lowe et al. · 2009 [cited by applicant]
US 20110033887A1 · Fang · 2011 [cited by examiner]
US 20130137252A1 · Iida et al. · 2013 [cited by applicant]
US 20130273135A1 · Brooks · 2013 [cited by examiner]
US 20160009863A1 · Yakacki · 2016 [cited by examiner]
US 20160137839A1 · Rolland · 2016 [cited by examiner]
US 20180059540A1 · Campbell et al. · 2018 [cited by applicant]
US 20180059541A1 · Campbell et al. · 2018 [cited by applicant]
US 20180329296A1 · Campbell et al. · 2018 [cited by applicant]
CN 103408746A · 2013 [cited by applicant]
CN 104086749A · 2014 [cited by applicant]
CN 102964545B · 2015 [cited by examiner]
CN 105504331A · 2016 [cited by examiner]
EP 119017A2 · 1984 [cited by applicant]
WO WO2006053031A2 · 2006 [cited by examiner]
WO 2015084753A1 · 2015 [cited by applicant]
Li et al., “Silica nanoparticles functionalized via click chemistry and ATRP for enrichment of Pb(II) ion”, Nanoscale Research Lett., vol. 7(1)485 (7 pages) (2012). [cited by examiner]
Yu et al., “Thiol-ene Photocrosslinked Hybrid Vesicles Based on the co-assembly of POSS and Poly(ether amine) (PEA),” Supporting Information, The Royal Society of Chemistry, Electronic Supplementary Material (ESI) for C… [cited by applicant]
Kantheti et al., “The impact of 1,2,3-triazoles in the design of functional coatings,” RSC Advances, vol. 5, No. 5, 2015, pp. 3687-3708. [cited by applicant]
Bentiss et al., “Electrochemical Study of Substituted Triazoles Adsorption on Mild Steel,” Industrial & Engineering Chemistry Research, vol. 39, No. 10, 2000, pp. 3732-3736. [cited by applicant]
Ho et al., “Quorum sensing inhibitory activities of surface immobilized antibacterial dihydropyrrolones via click chemistry,” Biomaterials, vol. 35, No. 7, 2014, pp. 2336-2345. [cited by applicant]
Wang et al., “The promotion of antimicrobial activity on silicon substrates using a ‘click’ immobilized short peptide,” Chemical Communications, vol. 50, No. 8, 2014, pp. 975-977. [cited by applicant]
Yang et al., “Barnacle Cement as Surface Anchor for ‘Clicking’ of Antifouling and Antimicrobial Polymer Brushes on Stainless Steel,” Biomacromolecules, vol. 14, No. 6, 2013, pp. 2041-2051. [cited by applicant]
Sun et al., “Triazole-forming waterborne polyurethane composites fabricated with silane coupling agent functionalized nano-silica,” Journal of Colloid and Interface Science, vol. 361, No. 2, 2011, pp. 483-490. [cited by applicant]
Hein et al., “Copper-catalyzed azide-alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides,” Chemical Society Reviews, vol. 39, No. 4, 2010, pp. 1302-1315. [cited by applicant]
Zheng et al., “Design and optimization of a light-emitting diode projection micro-stereolithography three-dimensional manufacturing system,” Review of Scientific Instruments, vol. 83, No. 12, 2012, pp. 1-7. [cited by applicant]
Quick et al., “Rapid Thiol-Yne-Mediated Fabrication and Dual Postfunctionalization of Micro-Resolved 3D Mesostructures,” Advanced Functional Materials, vol. 25, No. 24, 2015, pp. 3735-3744. [cited by applicant]
Becer et al., “Click Chemistry beyond Metal-Catalyzed Cycloaddition,” Angew. Chem. Int. Ed., vol. 48, 2009, pp. 4900-4908. [cited by applicant]
Wang et al., “Metal-catalyzed azide-alkyne “click” reactions: Mechanistic overview and recent trends,” Coordination Chemistry Reviews, vol. 316, Jun. 2016, pp. 1-20. [cited by applicant]
Campbell et al., U.S. Appl. No. 15/253,654, filed Aug. 31, 2016. [cited by applicant]
Campbell et al., U.S. Appl. No. 15/253,640, filed Aug. 31, 2016. [cited by applicant]
Restriction Requirement from U.S. Appl. No. 15/253,654, dated Oct. 19, 2017. [cited by applicant]
Restriction Requirement from U.S. Appl. No. 15/253,640, dated Nov. 15, 2017. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 15/253,640, dated Mar. 21, 2018. [cited by applicant]
Zhang et al., “Multiblock sequence-controlled glycopolymers via Cu(0)-LRP following efficiency thiol-halogen, thiol-epoxy and CuAAC reactions,” Polymer Chemistry, vol. 5, 2014, pp. 3876-3883 & Supporting Information, 19… [cited by applicant]
Murtezi et al., “Synthesis of clickable hydrogels and linear polymers by type II photoinitiation,” Polymer International, vol. 64, 2014, pp. 588-594. [cited by applicant]
Krieg et al., “Tailor Made Side-Chain Functionalized Macromolecules by a Combination of Controlled Radical Polymerization and Click Chemistry,” Macromolecular Symposia, vol. 275-276, 2009, pp. 73-81. [cited by applicant]
Li et al., “Low temperature cross-linked, high performance polymer gate dielectrics for solution-processed organic field-effect transistors”, Polymer Chemistry, vol. 6, 2015, pp. 5884-5890. [cited by applicant]
Green et al., “Protection for the Alkyne-CH”, Protective Groups in Organic Synthesis, Third Edition, Chapter 8, 1999, pp. 654-659. [cited by applicant]
Slavin et al., “Synthesis of glycopolymers via click reactions,” European Polymer Journal, vol. 47, 2011, pp. 435-446. [cited by applicant]
Grogna et al., “Stealth macromolecular platforms for the design of MRI blood pool contrast agents,” Polymer Chemistry, vol. 2, 2011, pp. 2316-2327. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 15/253,654, dated Apr. 30, 2018. [cited by applicant]
Lutz et al., “Efficient construction of therapeutics, bioconjugates, biomaterials and bioactive surfaces using azide-alkyne “click” chemistry,” Advanced Drug Delivery Reviews, vol. 60, 2008, pp. 958-970. [cited by applicant]
Bebensee et al., “On-Surface Azide-Alkyne Cycloaddition on Cu(111): Does It ‘Click’ in Ultrahigh Vacuum?” Journal of the American Chemical Society, 2013, pp. 2136-2139. [cited by applicant]
Campbell et al., U.S. Appl. No. 16/045,621, filed Jul. 25, 2018. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 15/253,640, dated Aug. 3, 2018. [cited by applicant]
Durmaz et al., “Surface Modification of UV-Cured Epoxy Resins by Click Chemistry,” Journal of Polymer Science, Part A, vol. 48, 2010, pp. 2862-2868. [cited by applicant]
Doran et al., “Tandem Photoiniduced Cationic Polymerization and CuAAC for Macromolecular Synthesis,” Macromolecules, vol. 48, 2015, pp. 7446-7452. [cited by applicant]
Hilf et al., “Propargyl-Functional Aliphatic Polycarbonate Obtained form Carbon Dioxide and Glycidyl Propargyl Ether,” Macromolecular Rapid Communications, vol. 34, 2013, pp. 1395-1400. [cited by applicant]
Final Office Action from U.S. Appl. No. 15/253,654, dated Nov. 14, 2018. [cited by applicant]
Lowe, A., “Thiol-ene “click” reactions and recent applications in polymer and materials synthesis: a first update,” Polymer Chemistry, 2014, pp. 4820-4870. [cited by applicant]
Final Office Action from U.S. Appl. No. 15/253,654, dated Jan. 17, 2019. [cited by applicant]
Final Office Action from U.S. Appl. No. 15/253,640, dated Feb. 4, 2019. [cited by applicant]
Mizuno et al., “Ring opening reaction of epoxides with diphenyl phosphorazidate,” Tetrahedron Letters, vol. 40, 1999, pp. 7105-7108. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 15/253,654, dated May 16, 2019. [cited by applicant]
Examiner's Answer to Appeal Brief from U.S. Appl. No. 15/253,640, dated Sep. 13, 2019. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 15/253,654, dated Oct. 29, 2019. [cited by applicant]
Notice of Allowance from U.S. Appl. No. 15/253,654, dated Apr. 20, 2020. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 16/045,621, dated Aug. 5, 2020. [cited by applicant]
Notice of Allowance from U.S. Appl. No. 16/045,621, dated Nov. 25, 2020. [cited by applicant]
Patent Board Decision on Appeal from U.S. Appl. No. 15/253,640, dated Dec. 15, 2020. [cited by applicant]
Notice of Allowance from U.S. Appl. No. 15/253,640, dated Apr. 28, 2021. [cited by applicant]