Methods for reactive three-dimensional printing by extrusion
Methods of printing a three-dimensional object using co-reactive components are disclosed. Thermosetting compositions for three-dimensional printing are also enclosed.
1. A method of three-dimensional printing an object comprising:
extruding a first component comprising a first functional group and a second component comprising a second functional group, wherein,
the second functional group is reactive with the first functional group; and
at least one of the first functional group and the second functional group comprises a saturated functional group; and
building a three-dimensional printed object,
wherein extruding comprises extruding a coreactive composition comprising the first component and the second component; and
wherein the coreactive composition is characterized by a shear storage modulus G′ and a shear loss modulus G″, wherein,
the initial G″/G′ ratio is less than 2;
the initial G′ is greater than 1,500 Pa;
the G′ at 6 minutes is greater than 500,000 Pa; and
the G″ at 6 minutes is greater than 400,000 Pa; wherein,
the initial G″/G′ ratio and the initial G′ refer to values measured within 30 seconds after the first component and the second component are mixed;
the G′ and G″ after 6 minutes refers to the values measured 6 minutes after the first component and the second component are mixed; and
the shear storage modulus G′ and the shear loss modulus G″ are measured using a rheometer with a gap from 1 mil to 2 mils, with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C.
2. The method of claim 1 , wherein the coreactive composition comprises a thermosetting composition.
3. The method of claim 1 , wherein,
the first component comprises a polyol; and
the second component comprises a polyisocyanate.
4. The method of claim 1 , wherein,
the first component comprises a polyamine and the second component comprises a polyisocyanate;
the first component comprises a polyalkenyl compound and the second component comprises a polythiol;
the first component comprises a Michael addition acceptor and the second component comprises a Michael addition donor; or
a combination of any of the foregoing.
5. The method of claim 1 , wherein the coreactive composition is characterized by an initial mole equivalent ratio of the first functional group to the second functional group from 1.5:1 to 1:1.5.
6. The method of claim 1 , wherein the coreactive composition is characterized by a viscosity from 5,000 cP to 5,000,000 cP, measured using a rheometer with a gap from 1 mm to 2 mm and a shear rate of 0.1 s −1 at a temperature of 25° C.
7. The method of claim 1 , wherein the coreactive composition is substantially free of solvent.
8. The method of claim 1 , wherein the first functional group comprises a hydroxyl, a thiol, a primary amine, a secondary amine, an epoxy, or a combination of any of the foregoing.
9. The method of claim 1 , wherein each of the first functional group and the second functional group does not comprise an acrylate group or a methacrylate group.
10. The method of claim 1 , wherein
extruding comprises forming an extrusion comprising the coreactive composition;
the extrusion is characterized by a cross-sectional profile having a first portion and a second portion; and
a cross-sectional profile of the extrusion has an inhomogeneous composition.
11. The method of claim 10 , wherein,
the first portion comprises a molar ratio of the first component to the second component greater than 1; and
the second portion comprises a molar ratio of the first component to the second component less than 1.
12. The method of claim 10 , wherein the first portion and the second portion are on opposite sides of the cross-sectional profile.
13. The method of claim 10 , wherein,
the first portion comprises a mole equivalent ratio of the first functional group to the second functional group greater than 1; and
the second portion comprises a mole equivalent ratio of the first functional group to the second functional group less than 1.
14. The method of claim 10 , wherein a mole equivalents ratio of the first component to the second component is not homogeneous throughout the cross-sectional profile.
15. The method of claim 10 , wherein a mole equivalents ratio of the first component to the second component is homogeneous throughout the cross-sectional profile.
16. The method of claim 10 , wherein extruding comprises extruding the coreactive composition through a single nozzle.
17. The method of claim 1 , wherein extruding comprises;
extruding a first layer; and
extruding a second layer overlying the first layer.
18. The method of claim 1 , wherein,
the first component comprises an isocyanate-functional prepolymer; and
the second functional group comprises a primary amine, a secondary amine, a hydroxyl, or a combination of any of the foregoing.
19. The method of claim 18 , wherein the first component further comprises an isocyanate-functional monomer.
20. The method of claim 1 , wherein the coreactive composition is characterized by an extrusion temperature less than 30° C.
21. The method of claim 1 , wherein building comprises depositing successive layers by extrusion.
22. The method of claim 1 , wherein extruding comprises extruding the coreactive composition through a single nozzle.
23. A method of three-dimensional printing an object comprising:
extruding a first component comprising a first functional group and a second component comprising a second functional group, wherein,
the second functional group is reactive with the first functional group; and
at least one of the first functional group and the second functional group comprises a saturated functional group; and
building a three-dimensional printed object,
wherein extruding comprises extruding a coreactive composition comprising the first component and the second component; and
wherein the coreactive composition is characterized by a shear storage modulus G′ and a shear loss modulus G″, wherein,
the initial G″/G′ ratio is less than 1.5;
the initial G′ is greater than 2,000 Pa;
the G′ at 6 minutes is greater than 1,000,000 Pa; and
the G″ at 6 minutes is greater than 600,000 Pa.; wherein,
the initial G″/G′ ratio and the initial G′ refer to values measured within 30 seconds after the first component and the second component are mixed;
the G′ and G″ after 6 minutes refers to the values measured 6 minutes after the first component and the second component are mixed; and
the shear storage modulus G′ and the shear loss modulus G″ are measured using a rheometer with a gap from 1 mil to 2 mils, with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C.
24. The method of claim 23 , wherein the coreactive composition comprises a thermosetting composition.
25. The method of claim 23 , wherein,
the first component comprises a polyol; and
the second component comprises a polyisocyanate.
26. The method of claim 23 , wherein,
the first component comprises a polyamine and the second component comprises a polyisocyanate;
the first component comprises a polyalkenyl compound and the second component comprises a polythiol;
the first component comprises a Michael addition acceptor and the second component comprises a Michael addition donor; or
a combination of any of the foregoing.
27. The method of claim 23 , wherein the coreactive composition is characterized by an initial mole equivalent ratio of the first functional group to the second functional group from 1.5:1 to 1:1.5.
28. The method of claim 23 , wherein the coreactive composition is characterized by a viscosity from 5,000 cP to 5,000,000 cP, measured using a rheometer with a gap from 1 mm to 2 mm and a shear rate of 0.1 s −1 at a temperature of 25° C.
29. The method of claim 23 , wherein the coreactive composition is substantially free of solvent.
30. The method of claim 23 , wherein the first functional group comprises a hydroxyl, a thiol, a primary amine, a secondary amine, an epoxy, or a combination of any of the foregoing.
31. The method of claim 23 , wherein each of the first functional group and the second functional group does not comprise an acrylate group or a methacrylate group.
32. The method of claim 23 , wherein,
extruding comprises forming an extrusion comprising the coreactive composition;
the extrusion is characterized by a cross-sectional profile having a first portion and a second portion; and
the cross-sectional profile of the extrusion has an inhomogeneous composition.
33. The method of claim 32 , wherein,
the first portion comprises a molar ratio of the first component to the second component greater than 1; and
the second portion comprises a molar ratio of the first component to the second component less than 1.
34. The method of claim 32 , wherein the first portion and the second portion are on opposite sides of the cross-sectional profile.
35. The method of claim 32 , wherein,
the first portion comprises a mole equivalent ratio of the first functional group to the second functional group greater than 1; and
the second portion comprises a mole equivalent ratio of the first functional group to the second functional group less than 1.
36. The method of claim 32 , wherein a mole equivalents ratio of the first component to the second component is not homogeneous throughout the cross-sectional profile.
37. The method of claim 32 , wherein a mole equivalents ratio of the first component to the second component is homogeneous throughout the cross-sectional profile.
38. The method of claim 32 , wherein extruding comprises extruding the coreactive composition through a single nozzle.
39. The method of claim 23 , wherein extruding comprises;
extruding a first layer; and
extruding a second layer overlying the first layer.
40. The method of claim 23 , wherein,
the first component comprises an isocyanate-functional prepolymer; and
the second functional group comprises a primary amine, a secondary amine, a hydroxyl, or a combination of any of the foregoing.
41. The method of claim 40 , wherein the first component further comprises an isocyanate-functional monomer.
42. The method of claim 23 , wherein the coreactive composition is characterized by an extrusion temperature less than 30° C.
43. The method of claim 23 , wherein building comprises depositing successive layers by extrusion.
44. The method of claim 23 , wherein extruding comprises extruding the coreactive composition through a single nozzle.