FR composite composition for light-based additive manufacturing

Patent metadata

Field	Value
Publication number	US-11286327-B2
Application number	US-201916704704-A
Country	US
Kind code	B2
Filing date	Dec 5, 2019
Priority date	Dec 5, 2019
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

A fire retardant (FR) composite composition, including a liquid polymer, wherein the liquid polymer includes a photopolymer including at least two of a first molecule, a second molecule, and a third molecule, a FR thermoset, and a photoinitiator.

First claim

What is claimed, is:

1. A fire retardant (FR) composite composition, comprising:
from about 15.0 weight % to about 99.9 weight % of a liquid polymer, based on a total weight of the FR composite composition,
wherein the liquid polymer comprises:
from about 10.0 weight % to about 90.0 weight % of a photopolymer comprising at least two of a first molecule, a second molecule, and a third molecule, based on a total weight of the liquid polymer,
from about 15.0 weight % to about 80.0 weight % of a FR thermoset, based on the total weight of the liquid polymer, and
from about 0.001 weight % to about 10 weight % of a photoinitiator, based on the total weight of the liquid polymer, and

wherein the first molecule comprises one or more unsaturated carbon-carbon double bonds or triple bonds,
wherein the second molecule comprises a terminal thiol group, and
wherein the third molecule comprises one or more functional groups selected from the group consisting of an aliphatic ether, a cyclic ether, a vinyl ether, an epoxy, a cyclo aliphatic epoxy, an oxetane, an isocyanate, and a diisocyanate group.

2. The FR composite composition of claim 1 , wherein the FR thermoset comprises at least one of resole phenolics, novolac phenolics, cyanate esters, melamines, polycyanurates, and mixtures and combinations thereof.

3. The FR composite composition of claim 1 , wherein the photoinitiator comprises at least one of 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, camphorquinone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, benzophenone, benzoyl peroxide, thioxanones, and mixtures and combinations thereof.

4. The FR composite composition of claim 1 , wherein the FR composite composition has an UL-94 Rating of V-2 or better.

5. The FR composite composition of claim 1 , wherein the FR composite composition has a total heat release (THR) of about 12 KJ/g or less.

6. The FR composite composition of claim 1 , wherein the FR composite composition has an UL-94 Rating of V-2 or better and wherein the FR composite composition has a total heat release (THR) of about 12 KJ/g or less.

7. The FR composite composition of claim 1 , wherein the photopolymer comprises from about 5.0 weight % to about 90 weight % of the first molecule, based on a total weight of the photopolymer.

8. The FR composite composition of claim 7 , wherein the first molecule comprises at least one of tris (2-hydroxyethyl) isocyanurate triacrylate, 1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7-tetravinyl-1,3,5,7 tetra methylcyclo tetrasiloxane, vinylmethylsiloxane-dimethylsiloxane copolymer, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis[2-(methacryloyloxy)ethyl] phosphate, bisphenol A epoxy diacrylate, (acryloxypropyl)methylsiloxane, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethylene, substituted olefins, halogenated olefins, 1,3-dienes, styrene, x-methyl styrene, vinyl esters, acrylonitriles, acrylamides, N-vinyl carbazole, N-vinyl pyrolidone, monoacrylates, diacrylates, triacrylates, tetraacrylates, pentaacrylates, monomethacrylates, dimethacrylates, trimethacrylates, tetramethacrylates, pentamethacrylates, pentabromobenzyl acrylate, pentabromobenzyl methacrylate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and mixtures and combinations thereof.

9. The FR composite composition of claim 1 , wherein the photopolymer comprises from about 1.0 weight % to about 90 weight % of the second molecule, based on a total weight of the photopolymer.

10. The FR composite composition of claim 9 , wherein the second molecule comprises at least one of 1,4-butanedithiol, benzene-1,4-dithiol, biphenyl-4,4-dithiol, 4,4′-thiobisbenzenethiol, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropanetris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), tetrakis(dimethyl-2-mercaptoacetate siloxy)silane, (mercaptopropyl)methylsiloxane-dimethylsiloxane copolymer, (mercaptopropyl)methylsiloxane homopolymer, and pentaerythritol tetrakis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(thioglycolate), 2-[2,4-bis(2-mercaptoethyl) cyclohexyl]ethanethiol, 2-[3,5-bis(2-mercaptoethyl)cyclohexyl]ethanethiol and mixtures and combinations thereof.

11. The FR composite composition of claim 1 , wherein the photopolymer comprises from about 1.0 weight % to about 80.0 weight % of the third molecule, based on a total weight of the photopolymer.

12. The FR composite composition of claim 11 , wherein the third molecule comprises at least one of epoxy functional dimethylpolysiloxane, (epoxycyclohexylethyl)methylsiloxane-dimethylsiloxane copolymer, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 3-ethyl-3-hydroxymethyl oxetane, and mixtures and combinations thereof.

13. The FR composite composition of claim 1 , further comprising:
from about 15.0 weight % to about 80.0 weight % of a solid filler,
wherein the solid filler comprises at least one of an inert, a nonflammable, and a flame retarding material.

14. The FR composite composition of claim 13 , wherein the solid filler has an average particle size from about 5 nm to about 100 micrometers.

15. The FR composite composition of claim 13 , wherein the solid filler comprises at least one of silica, alumina trihydrate, ammonium polyphosphate, red phosphorous, organic phosphinate, melamine polyphosphate, borates, expandable graphite, and mixtures and combinations thereof.

16. The FR composite composition of claim 1 , wherein the FR composite composition is configured to create an FR composite by a light-based additive process.

17. The FR composite composition of claim 16 , wherein the light-based additive process comprises a self-propagating waveguide (SPPW) process, and
wherein the FR composite composition is configured to form a plurality of self-propagating polymer optical waveguides.

18. The FR composite composition of claim 16 , wherein the light-based additive process comprises a light based stereo lithography 3D printing process, and
wherein the FR composite composition is polymerized when exposed to light in layers of patterns that render a 3D structure upon completion.

19. An FR composite created from an FR composite composition according to claim 1 .

Assignees

• Boeing Co

Inventors

• Eckel Zak
• Bui Phuong
• O'Masta Mark
• Hundley Jacob
• Koung Tony

Classifications

• C08K5/5397

  Phosphine oxides · CPC title

• C08K5/14

  Peroxides · CPC title

• B33Y70/00 Primary

  Materials specially adapted for additive manufacturing · CPC title

• C08G8/10 Primary

  with phenol · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title