Non-isocyanate polyurethane inks for 3D printing
In one aspect, inks for use with a 3D printer are described herein. In some embodiments, an ink described herein comprises a cyclic carbonate monomer and an amine monomer. Further, in some instances, an ink described herein also comprises an ethylenically unsaturated monomer such as a (meth)acrylate. Additionally, an ink described herein, in some cases, further comprises a colorant, such as a molecular dye, a particulate inorganic pigment, or a particulate organic colorant. An ink described herein may also comprise one or more additives selected from the group consisting of inhibitors, stabilizing agents, photoinitiators, and photosensitizers.
1. A method of printing a three-dimensional article comprising:
selectively depositing layers of an ink in a fluid state onto a substrate, wherein the ink comprises
a cyclic carbonate monomer; and
an amine monomer.
2. The method of claim 1 , wherein the cyclic carbonate monomer comprises two cyclic carbonate moieties.
3. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A1), Formula (A2), Formula (A3), or Formula (A4):
wherein R 1 , R 2 , R 3 , and R 4 are each independently a linear or branched C1 -C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.
4. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A6):
5. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A9):
wherein m is an integer from 1 to 36.
6. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A10), Formula (A11), Formula (A12), or Formula (A13):
wherein R 1 , R 2 , and R 3 are each independently a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, and R 5 is a linear or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.
7. The method of claim 1 , wherein the cyclic carbonate monomer comprises one or more (meth)acrylate moieties.
8. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A14) or Formula (A15):
wherein R 1 and R 2 are each independently a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and
R 6 is H or CH 3 .
9. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A17) or Formula (A18):
wherein m is an integer from 1 to 36;
R 1 is a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and
R 6 is H or CH 3 .
10. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A20):
wherein R 2 is a linear or branched C1-C20 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety;
R 6 is H or CH 3 ;
R 7 is a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH 2 CH(R 8 )O) n ;
R 8 is H or CH 3 ; and
n is an integer from 1 to 100.
11. The method of claim 1 , wherein the cyclic carbonate monomer has the structure of Formula (A21):
wherein R 2 and R 9 are each independently a linear or branched C1-C36alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and
R 6 is H or CH 3 ;
R 7 is a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH 2 CH(R 8 )O)n;
R 8 is H or CH 3 ; and
n is an integer from 1 to 100.
12. The method of claim 1 , wherein the amine monomer comprises two amine moieties.
13. The method of claim 1 , wherein the amine monomer has the structure of Formula (B1):
H 2 N—R 10 —NH 2 (B1),
wherein R 10 is a linear or branched C 1 -C 36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.
14. The method of claim 1 , wherein the amine monomer comprises at least one secondary or tertiary amine moiety.
15. The method of claim 1 , wherein the ink further comprises one or more (meth)acrylates.
16. The method of claim 15 , wherein the method further comprises curing the (meth)acrylates with UV light and thermally curing the cyclic carbonate monomer and the amine monomer.
17. The method of claim 1 , wherein the ink, when non-cured, has a dynamic viscosity of 200 to 2000 cP at 30° C., when measured according to ASTM D2983.
18. The method of claim 1 , wherein the layers of the ink in a fluid state are selectively deposited on the substrate according to an image of the three-dimensional article in a computer readable format.
19. The method of claim 1 , wherein one or more layers of the ink has a thickness of 10 μm to 100 μm.