Additives for build materials and associated printed 3D articles
Additives for three-dimensional build materials or inks are described herein which, in some embodiments, can impart flame retardant properties and/or structural enhancements to articles printed from the build materials. In some embodiments, such an additive comprises a compound of Formula I herein, 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.
1. A polymerizable liquid comprising:
at least one additive of Formula I:
wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate or L and Z each comprise a cyclopolymerizable functionality;
wherein R 1 and R 2 are alkylene moieties;
wherein 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;
wherein n is 2 or 3; and
wherein the additive is present in an amount of 5-40 wt. % based on total weight of the polymerizable liquid.
2. The polymerizable liquid of claim 1 , wherein L and Z each comprise a cyclopolymerizable functionality.
3. The polymerizable liquid of claim 2 , wherein the cyclopolymerizable functionality is of the formula:
where is an attachment point of the cyclopolymerizable moiety or functionality to the compound of Formula I.
4. The polymerizable liquid of claim 1 , wherein L and Z each comprise an acrylate moiety or a methacrylate moiety.
5. The polymerizable liquid of claim 1 , wherein the additive is present in an amount of 10-30 wt. % based on total weight of the polymerizable liquid.
6. The polymerizable liquid of claim 1 further comprising an acrylate component.
7. The polymerizable liquid of claim 6 , wherein the additive is present in an amount of 10-30 wt. % and the acrylate component is present in an amount of 30-70 wt. % based on total weight of the polymerizable liquid.
8. The polymerizable liquid of claim 6 , wherein the acrylate component is an acrylate monomer, acrylate oligomer, or mixtures thereof.
9. The polymerizable liquid of claim 6 , wherein the acrylate component is present in an amount of 30-70 wt. % based on total weight of the polymerizable liquid.
10. The polymerizable liquid of claim 1 further comprising a photoinitiator component.
11. The polymerizable liquid of claim 10 , wherein the photoinitiator component is present in an amount of 0.1 wt. % to 5 wt. % based on total weight of the polymerizable liquid.
12. The polymerizable liquid of claim 1 further comprising a sensitizer.
13. The polymerizable liquid of claim 12 , wherein the sensitizer is present in an amount of 0.1 wt. % to 2 wt. % based on total weight of the polymerizable liquid.
14. A method of printing a three-dimensional article comprising:
providing a polymerizable liquid comprising:
an acrylate component; and
at least one additive of Formula I:
wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate or L and Z each comprise a cyclopolymerizable functionality,
wherein R 1 and R 2 are alkylene moieties,
wherein 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,
wherein n is 2 or 3, and
wherein the additive is present in an amount of 5-40 wt. % based on total weight of the polymerizable liquid; and
printing and curing the polymerizable liquid with light to form the article.
15. The method of claim 14 , wherein the acrylate component is present in an amount of 30-70 wt. %, based on total weight of the polymerizable liquid.
16. The method of claim 14 , wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.
17. The method of claim 14 , wherein L and Z each comprise an acrylate moiety or a methacrylate moiety.
18. The method of claim 14 , wherein the additive is present in an amount of 10-30 wt. % and the acrylate component is present in an amount of 30-70 wt. % based on total weight of the polymerizable liquid.
19. The method of claim 14 , wherein L and Z each comprise a cyclopolymerizable functionality.
20. The method of claim 19 , wherein the cyclopolymerizable functionality is of the formula:
where is an attachment point of the cyclopolymerizable moiety or functionality to the compound of Formula I.