Flame resistant build materials and associated printed 3D articles
Polymerizable liquids for 3D printing applications are described herein which, in some embodiments, impart flame resistant and/or flame retardant properties to articles printed from the build materials. The polymerizable liquids may also impart desirable mechanical properties to the articles. In some embodiments, a polymerizable liquid comprises a curable isocyanurate component in an amount of at least 20 wt. %, based on total weight of the polymerizable liquid, and an organophosphate component comprises one or more organophosphate compounds. In some embodiments, the polymerizable liquid further comprises an acrylate component.
1. A method of printing a three-dimensional article comprising:
providing a polymerizable liquid comprising:
a curable isocyanurate component in an amount of at least 20 wt. %, based on total weight of the polymerizable liquid; and
an organophosphate component comprising one or more organophosphate compounds; and
printing and curing the polymerizable liquid with light to form the article,
wherein the article has a limiting oxygen index of 25-30% according to ISO 4589.
2. The polymerizable liquid of claim 1 , wherein the curable isocyanurate component is polymerizable via free radical polymerization.
3. The polymerizable liquid of claim 2 , wherein the curable isocyanurate component comprises isocyanurate polyacrylate, polyallyl isocyanurate, or a mixture thereof.
4. The polymerizable liquid of claim 1 , wherein the organophosphate component is present in an amount of 10-40 wt. %, based on total weight of the polymerizable liquid.
5. The polymerizable liquid of claim 1 , wherein the one or more organophosphate compounds comprise bis(organophosphate).
6. The polymerizable liquid of claim 1 , wherein the curable isocyanurate component is present in an amount of 30-80 wt. %, based on total weight of the polymerizable liquid.
7. The method of claim 1 , wherein the polymerizable liquid further comprising an acrylate component.
8. The method of claim 7 , wherein the acrylate component is present in an amount of 30-70 wt. %, based on total weight of the polymerizable liquid.
9. The method of claim 7 , wherein the acrylate component comprises a mixture of acrylate monomer and acrylate oligomer.
10. The method of claim 1 , wherein the polymerizable liquid further comprising a photoinitiator component.
11. The method of claim 10 , wherein the photoinitiator component is present in an amount of 0.1-5 wt. %, based on total weight of the polymerizable liquid.
12. The method of claim 1 , wherein the article has a limiting oxygen index of 28-30% according to ISO 4589.
13. The method of claim 1 , wherein the polymerizable liquid is provided in a layer-by-layer process.
14. The method of claim 1 , wherein the curable isocyanurate component comprises isocyanurate polyacrylate, polyallyl isocyanurate, or a mixture thereof and the isocyanurate polyacrylate is of Formula I:
wherein R 1 -R 3 are each independently selected from the group consisting of hydrogen and alkyl and m, n, and p are each integers independently ranging from 1 to 10; or
the polyallyl isocyanurate is of Formula II:
wherein m, n, and p are integers independently ranging from 1 to 10.
15. The method of claim 1 , wherein the one or more organophosphate compounds are of the formula:
wherein R 1 -R 3 are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heteroalkenyl, heterocyclyl, aryl, and heteroaryl.