Polymerization photoinhibitor

Patent metadata

Field	Value
Publication number	US-12173095-B2
Application number	US-202318389039-A
Country	US
Kind code	B2
Filing date	Nov 13, 2023
Priority date	Feb 20, 2018
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

Provided herein is technology relating to polymerization and producing polymers and particularly, but not exclusively, to methods, systems, and compositions for producing articles using three-dimensional printing and for improving control of polymerization using a polymerization photoinhibitor having fast back reaction kinetics such as hexaarylbiimidazole compounds and bridged hexaarylbiimidazole compounds.

First claim

We claim:

1. A system comprising:
a composition comprising a polymerizable monomer, a photoinitiator, and a photoinhibitor; and
a first electromagnetic radiation source providing an intensity-patterned image comprising a plurality of pixels, wherein said plurality of pixels comprises pixels providing a first wavelength of electromagnetic radiation at more than two intensities.

2. The system of claim 1 , wherein said composition further comprises a filler.

3. The system of claim 2 , wherein said filler comprises a polymeric particle, a metallic particle, an organic particle, an inorganic particle, a nonconductive particle, a semi-conductive particle, a conductive particle, a magnetic particle, a ferromagnetic magnetic particle, a paramagnetic particle, a nonmagnetic particle, a spherical particle, an elliptical particle, a cylindrical particle, a pigment, a dye, a pharmaceutical compound, a detectable compound, a protein, a peptide, a nucleic acid, a sugar, or a small organic compound.

4. The system of claim 1 , further comprising a microcontroller configured to control a pixel of the electromagnetic radiation source to provide a time-varying intensity of electromagnetic radiation produced by the pixel.

5. The system of claim 1 , further comprising a second electromagnetic radiation source.

6. The system of claim 1 , further comprising a reaction vessel comprising the polymerizable monomer, the photoinitiator, and the photoinhibitor.

7. The system of claim 1 , wherein the composition is a viscous composition.

8. The system of claim 7 , wherein the viscous composition has a viscosity greater than 1000 centipoise or greater than 10,000 centipoise.

9. The system of claim 1 , wherein the first electromagnetic radiation source is arranged at approximately 0° to 180° relative to the second electromagnetic radiation source.

10. The system of claim 1 , further comprising a vertically movable build plate.

11. The system of claim 1 , wherein said first wavelength of electromagnetic radiation produces an initiating species from said photoinitiator.

12. The system of claim 1 , wherein said first wavelength of electromagnetic radiation produces an inhibiting species from the photoinhibitor.

13. The system of claim 1 , wherein the composition further comprises a coinitiator, a solvent, a colorant, or a photon absorbing component.

14. The system of claim 1 , wherein the composition comprises a polymerized region.

15. The system of claim 14 , wherein the polymerized region comprises a volume of approximately 0.5 μm to 100 cm×0.5 μm to 100 cm×0.5 μm to 100 cm.

16. The system of claim 1 , wherein the first wavelength of electromagnetic radiation is an infrared, a visible, a near-ultraviolet, or an ultraviolet wavelength of electromagnetic radiation.

17. The system of claim 1 , wherein the first electromagnetic radiation source is a liquid crystal display (LCD), a light emitting diode (LED), a digital light projector (DLP), digital micromirror device (DMD), a spatial modulator (SLM), or a microelectromechanical system (MEMS) mirror array.

18. The system of claim 1 , wherein the first electromagnetic radiation source comprises an actinic source, an incandescent source, a fluorescent source, a phosphorescent source, a luminescent source, a laser, light-emitting diode, a collimated beam, a planar waveguide, or an array of any of the foregoing.

19. The system of claim 5 , wherein the second electromagnetic radiation source produces electromagnetic radiation having an emission peak that is at least 5 nm from the emission peak of the electromagnetic radiation produced by the first electromagnetic radiation source.

20. The system of claim 1 , wherein the first electromagnetic radiation source comprises an array of at least one million pixels.

21. The system of claim 1 , wherein the first wavelength of electromagnetic radiation is provided at an intensity of from 0.001 to 1000 mW/cm 2 .

22. The system of claim 1 , wherein the intensity patterned image has an area of 0.5 μm 2 to 10,000 mm 2 .

Assignees

• Univ Michigan Regents

Inventors

• Scott Timothy F
• Van Der Laan Harry
• Cole Megan A
• Burns Mark A
• De Beer Martin P
• Pritchard Zachary D
• Bregman Avi

Classifications

• C08F222/40

  Imides, e.g. cyclic imides · CPC title

• C08F4/40

  Redox systems · CPC title

• C08F4/04

  Azo-compounds · CPC title

• C08F222/10

  Esters · CPC title

• C08F222/12

  of phenols or saturated alcohols {(C08F222/1006 takes precedence)} · CPC title