Stress-responsive compositions and uses thereof

Patent metadata

Field	Value
Publication number	US-10968301-B2
Application number	US-201716326036-A
Country	US
Kind code	B2
Filing date	Aug 17, 2017
Priority date	Aug 17, 2016
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

The present disclosure is directed to stress-responsive compositions comprising (1) at least one (co)polymer comprising at least one mechanophore comprising at least one thiocarbonylthio functional group or derivative thereof and (2) at least one compound comprising at least one functional group capable of reacting with a free radical, The present disclosure is also directed to articles, coatings, and 3D printing binders comprising such stress-responsive compositions, as well as to processes of imparting the abilities of forming and maintaining protective barriers and mechanical self-healing to such articles, coatings, and 3D printing binders by incorporating such stress-responsive compositions therein.

First claim

The invention claimed is:

1. A stress-responsive composition comprising (1) at least one (co)polymer comprising at least one mechanophore and (2) at least one compound comprising at least one functional group capable of reacting with a free radical, wherein the at least one mechanophore comprises at least one functional group selected from the group consisting of thiocarbonylthio, trithiocarbonate, dithiocarbamate, xanthate, dithiobenzoate, and any combination thereof.

2. The stress-responsive composition of claim 1 , wherein the at least one compound comprising at least one functional group capable of reacting with a free radical comprises at least one crosslinker.

3. The stress-responsive composition of claim 1 , wherein the at least one compound comprising at least one functional group capable of reacting with a free radical comprises at least one free radical indicator.

4. The stress-responsive composition of claim 1 , wherein the at least one (co)polymer is selected from the group consisting of polystyrenes, polyacrylates, polymethacrylates, polytetrafluoroethylenes, polyvinylchlorides, polyacrylonitriles, polyvinylalcohols, polyvinyl acetates, polyacrylamides, copolymers thereof, and combinations thereof.

5. The stress-responsive composition of claim 1 , wherein the at least one (co)polymer is a poly[meth]acrylate.

6. The stress-responsive composition of claim 1 , wherein the at least one (co)polymer is derived from n-butyl acrylate.

7. The stress-responsive composition of claim 1 , wherein the at least one mechanophore comprises a trithiocarbonate functional group.

8. The stress-responsive composition of claim 2 , wherein the at least one crosslinker is selected from the group consisting of polyfunctional acrylates, polyfunctional methacrylates, mixtures of polythiols and polyfunctional vinyl compounds, and any combination thereof.

9. The stress-responsive composition of claim 2 , wherein the at least one crosslinker is a polyfunctional acrylate.

10. The stress-responsive composition of claim 2 , wherein the at least one crosslinker is tetraethylene glycol diacrylate.

11. The stress-responsive composition of claim 3 , wherein the at least one radical indicator is capable of a colorimetric response upon reaction with a free radical.

12. The stress-responsive composition of claim 3 , wherein the at least one radical indicator is a fluorogenic radical trap or a radical trap capable of eliciting a light absorbance or color shift.

13. The stress-responsive composition of claim 3 , wherein the at least one radical indicator is selected from the group consisting of 4-((9-acridinecarbonyl)amino)-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 2,2-diphenyl-1-picrylhydrazyl, and combinations thereof.

14. The stress-responsive composition of claim 1 , wherein the at least one mechanophore is a monomer unit in the backbone of the at least one (co)polymer.

15. The stress-responsive composition of claim 1 , wherein the at least one mechanophore is a monomer unit located at the midpoint of the backbone of the at least one (co)polymer.

16. The stress-responsive composition of claim 1 , wherein the at least one mechanophore is or is part of a pendant group on the backbone of the at least one (co)polymer.

17. The stress-responsive composition of claim 1 , wherein the at least one (co)polymer is crosslinked.

18. The stress-responsive composition of claim 17 , wherein the at least one mechanophore is and/or is part of crosslink(s) present in the at least one (co)polymer which is crosslinked.

19. The stress-responsive composition of claim 1 , wherein the at least one (co)polymer comprising at least one mechanophore is covalently or non-covalently bonded to the exterior of a particle.

20. The stress-responsive composition of claim 19 , wherein the particle is selected from the group consisting of colloidal particles, nanoparticles, fibers, nanocrystalline celluloses, graphene, graphene oxide, carbon black, metal organic frameworks, metal organic polyhedrons, polyhedral oligomeric sisesquioxanes, and any combination thereof.

21. An article comprising the stress-responsive composition of claim 1 .

22. The article of claim 21 , wherein the article is selected from the group consisting of protective materials for military, protective materials for space, and protective materials for law enforcement applications.

23. The article of claim 21 , wherein the article is selected from the group consisting of helmets, visors, goggles, body armor, space suits, gloves, face masks, boots, and clothing.

24. The article of claim 21 , wherein the article is selected from the group consisting of automobile components, contact lenses, clothing, and helmets.

25. The article of claim 21 , wherein the article is selected from the group consisting of bladder cloths, bladder textiles, bladder layers, bladder tanks, and bladder devices capable of maintaining a seal or pneumatic pressure difference.

26. A coating comprising the stress-responsive composition of claim 1 .

27. A 3D printing binder comprising the stress-responsive composition of claim 1 .

28. A process for imparting the ability of forming and maintaining a protective barrier to an article, coating, or 3D printing binder, comprising adding to the article, coating, or 3D printing binder the stress-responsive composition of claim 1 .

29. A process for imparting the ability of mechanical self-healing to an article, coating, or 3D printing binder, comprising adding to the article, coating, or 3D printing binder the stress-responsive composition of claim 1 .

30. A process for imparting the ability of detection of material fatigue and/or failure to an article, coating, or 3D printing binder, comprising adding to the article, coating, or 3D printing binder the stress-responsive composition of claim 1 .

Assignees

• Gordon Melissa B
• Kloxin Christopher J
• Wagner Norman J
• Epps Iii Thomas H
• Knappe Grant Alexander
• Wang Shu
• Univ Delaware

Inventors

• Gordon Melissa B
• Kloxin Christopher J
• Wagner Norman J
• Epps Iii Thomas H
• Knappe Grant Alexander
• Wang Shu

Classifications

• B33Y70/00 Primary

  Materials specially adapted for additive manufacturing · CPC title

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C08K5/3437

  condensed with carbocyclic rings · CPC title

• C08F2810/20

  leading to a crosslinking, either explicitly or inherently · CPC title