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 liquids. 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 5 wt. %, based on total weight of the polymerizable liquid, and a brominated acrylate ester component. Additionally, methods of printing three-dimensional articles using said polymerizable liquids are described herein.
1. A polymerizable liquid comprising:
a curable isocyanurate component in an amount of at least 5 wt. %, based on total weight of the polymerizable liquid;
a brominated acrylate ester component; and
an additive of formula I:
wherein L and Z are ring substituents comprising at least one polymerizable point of unsaturation, and wherein R 1 and R 2 are independently selected from the group consisting of alkylene and alkenylene, and R 3 -R 6 each represent one to four optional ring substituents, each one of the one to four ring substituents independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, amine, amide, and ether, and wherein n is an integer from 1 to 7.
2. The polymerizable liquid of claim 1 , wherein R 1 and R 2 are alkylene.
3. The polymerizable liquid of claim 1 , wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.
4. The polymerizable liquid of claim 1 , wherein L and Z each comprise a cyclopolymerizable functionality.
5. The polymerizable liquid of claim 4 , wherein the cyclopolymerizable functionality is of the formula:
where is an attachment point of the cyclopolymerizable functionality to the compound of formula I.
6. The polymerizable liquid of claim 1 , wherein n is 2 or 3.
7. The polymerizable liquid of claim 1 , wherein L and Z each comprise an acrylate moiety.
8. The polymerizable liquid of claim 1 , wherein and L and Z each comprise a methacrylate moiety.
9. A method of printing a three-dimensional article comprising:
providing a polymerizable liquid of claim 1 ; and
printing and curing the polymerizable liquid with light to form the article.
10. The method of claim 9 , wherein the polymerizable liquid is provided in a layer-by-layer process.
11. The method of claim 9 , wherein curing the polymerizable liquid proceeds via free radical polymerization.
12. The method of claim 9 , wherein the article has a v0 rating according to UL 94 V.
13. A polymerizable liquid comprising:
a curable isocyanurate component in an amount of at least 5 wt. %, based on total weight of the polymerizable liquid;
a brominated acrylate ester component; and
at least one of an organophosphate component, acrylate component, and an additive of formula I:
wherein L and Z are ring substituents comprising at least one polymerizable point of unsaturation, and wherein R 1 and R 2 are independently selected from the group consisting of alkylene and alkenylene, and R 3 -R 6 each represent one to four optional ring substituents, each one of the one to four ring substituents independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, amine, amide, and ether, and wherein n is an integer from 1 to 7.