Fabrication of luminescent quantum dot thiol-yne nanocomposites with tailorable optical, thermal and mechanical properties

Patent metadata

Field	Value
Publication number	US-12247152-B2
Application number	US-202117363526-A
Country	US
Kind code	B2
Filing date	Jun 30, 2021
Priority date	Oct 11, 2017
Publication date	Mar 11, 2025
Grant date	Mar 11, 2025

Abstract

This disclosure concerns a method of making a ligand for Quantum Dot functionalization, a method of making a functionalized Quantum Dot (QD) with a ligand, and a method of making a transparent luminescent quantum dot thiol-yne nanocomposite with tailorable optical, thermal, and mechanical properties. The prepolymer solution and functionalized Quantum Dot can be used in additive manufacturing.

First claim

What we claim is:

1. A method of making a transparent luminescent quantum dot thiol-yne nanocomposite, comprising the steps of:
making a functionalized Quantum Dot (QD) with a ligand, comprising the steps of:
mixing QDs with a chloroform solution comprising synthesized ligands to functionalize the QDs forming functionalized QDs; and
suspending the functionalized QDs in 1.5 uM solution of chloroform forming a functionalized QD solution;

preparing a thiol-yne prepolymer by combining 1 mole equivalent of one selected from the group consisting of monovinyl, monoalkynyl, polyvinyl, polyalkynyl, and combinations thereof with 1 mole equivalent of one selected from the group consisting of monothiol, polythiol, and combinations thereof;
mixing the thiol-yne prepolymer and the functionalized QD solution;
agitating the thiol-yne prepolymer and the functionalized QD solution; and
polymerizing the thiol-yne prepolymer and the functionalized QD solution;
wherein the resulting nanocomposites are transparent and luminescent; and
wherein the thiol-yne prepolymer is prepared by combining 1 mole equivalent of tetrathiol pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) with 1 mole equivalent of dialkyne 1,7-octadiyne (ODY).

2. The method of making a transparent luminescent quantum dot thiol-yne nanocomposite of claim 1 , further comprising the steps of:
mixing a silica gel with the thiol-yne prepolymer and thereby
changing the viscosity of the thiol-yne prepolymer.

3. The method of making the luminescent quantum dot thiol-yne nanocomposite of claim 1 ,
wherein the step of polymerizing is by thermal curing.

4. The method of making the luminescent quantum dot thiol-yne nanocomposite of claim 3 ,
wherein the step of thermal curing is at 80° C. for about 30 minutes.

5. The method of making the luminescent quantum dot thiol-yne nanocomposite of claim 1 ,
wherein the step of polymerizing is by ultraviolet irradiation.

6. The method of making the luminescent quantum dot thiol-yne nanocomposite of claim 5 ,
further including the step of adding less than 1 mol % 2, 3-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator prior to the step of polymerizing by ultraviolet irradiation.

7. The method of making the luminescent quantum dot thiol-yne nanocomposite of claim 6 ,
wherein the step of polymerizing by ultraviolet irradiation is at about 365 nm for about 10 seconds.

8. The method of making the luminescent quantum dot thiol-yne nanocomposite of claim 1 , further comprising the steps of:
adding the quantum dot thiol-yne nanocomposite to a material in additive manufacturing techniques; and
forming a solid material comprising the quantum dot thiol-yne nanocomposite.

Assignees

• Us Gov Sec Navy

Inventors

• Boyd Darryl A
• Stewart Michael H
• Susumu Kimihiro
• Oh Eunkeu
• Wissman James P

Classifications

• C08F138/00

  Homopolymers of compounds having one or more carbon-to-carbon triple bonds · CPC title

• C07C323/60

  with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms · CPC title

• C07D339/04

  having the hetero atoms in positions 1 and 2, e.g. lipoic acid · CPC title

• C09K11/02

  Use of particular materials as binders, particle coatings or suspension media therefor · CPC title

• C08G75/23

  Polyethersulfones · CPC title