Additive manufacturing using polyurea materials

Patent metadata

Field	Value
Publication number	US-10434704-B2
Application number	US-201715680846-A
Country	US
Kind code	B2
Filing date	Aug 18, 2017
Priority date	Aug 18, 2017
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

Abstract

Methods of additive manufacture using coreactive components are disclosed. Thermosetting compositions for additive manufacturing are also disclosed.

First claim

What is claimed is:

1. A reactive additive manufacturing composition, comprising:
a first component comprising a polyisocyanate prepolymer and a first viscosity; and
a second component comprising a polyamine prepolymer and a second viscosity,
wherein the first viscosity is within ±20% of the second viscosity,
wherein viscosity is measured using an Anton Paar MCR 301 or 302 rheometer 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.; and
wherein the composition is characterized by a tack free time of greater than 3 minutes.

2. The composition of claim 1 , wherein the first viscosity is within ±10% of the second viscosity.

3. The composition of claim 1 , wherein the first component, the second component, or both the first component and the second component comprise from 0.1 wt % to 30 wt % of a filler, wherein wt % is based on the total weight of the first component, the second component, or both the first and second components, respectively.

4. The composition of claim 3 , wherein the filler comprises an inorganic filler, an organic filler, or a combination thereof.

5. The composition of claim 1 , wherein,
the polyisocyanate prepolymer comprises a difunctional polyisocyanate prepolymer; and
the polyamine prepolymer comprises a difunctional polyamine prepolymer.

6. The composition of claim 1 , wherein the polyisocyanate prepolymer comprises an isocyanate-terminated polytetramethylene prepolymer.

7. The composition of claim 1 , wherein the polyisocyanate prepolymer comprises an isophorone-terminated polytetramethylene prepolymer.

8. The composition of claim 1 , wherein the polyamine prepolymer comprises a trifunctional polyetheramine.

9. The composition of claim 1 , wherein the polyamine prepolymer comprises a difunctional polyamine, a trifunctional polyamine, or a combination thereof.

10. The composition of claim 1 , wherein the second component comprises a monomeric diamine and a rheology modifier.

11. The composition of claim 1 , wherein the second component comprises a secondary aliphatic diamine and a polyethylene/polypropylene copolymer.

12. The composition of claim 1 , wherein,
the first component comprises from 80 wt % to 100 wt % of the polyisocyanate prepolymer, wherein wt % is based on the total weight of the first component; and
the second component comprises:
from 10 wt % to 30 wt % of a monomeric polyamine having a molecular weight within a range from 200 Daltons to 500 Daltons;
from 40 wt % to 90 wt % of a polyamine prepolymer having a molecular weight within a range from 3,000 Daltons to 7,000 Daltons; and
from 1 wt % to 20 wt % of a rheology modifier,
wherein wt % is based on the total weight of the second component.

13. The composition of claim 12 , wherein,
the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polytetramethylene prepolymer; and
the polyamine prepolymer comprises a polyetheramine prepolymer.

14. The composition of claim 12 , wherein, the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polyetheramine prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.

15. The composition of claim 12 , wherein, the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polyoxypropylenediamine prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.

16. The composition of claim 12 , wherein,
the monomeric amine comprises a secondary aliphatic diamine; and
the rheology modifier comprises a propylene/ethylene copolymer.

17. The composition of claim 12 , wherein the second component comprises from 0.1 wt % to 20 wt % of a filler, wherein wt % is based on the total weight of the second component.

18. The composition of claim 12 , wherein the second component comprises from 0.1 wt % to 20 wt % of hydrophilic fumed silica wherein wt % is based on the total weight of the second component.

19. The composition of claim 1 , wherein the composition has an initial G″/G′ ratio, immediately after mixing the first and second component, of greater than 2, wherein the shear storage modulus G′ and the shear loss modulus G″ are measured using a rheometer with a gap from 1 mm to 2 mm, 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.

20. The composition of claim 1 , wherein the composition has a G″/G′ ratio at 7 minutes after mixing the first and second component of greater than 1, wherein the shear storage modulus G′ and the shear loss modulus G″ are measured using a rheometer with a gap from 1 mm to 2 mm, 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.

21. An object formed using the composition of claim 1 .

22. The object of claim 21 , wherein the object comprises a plurality of layers, wherein adjacent layers forming the object are covalently bonded.

23. A method of additive manufacturing, comprising extruding the reactive additive manufacturing composition of claim 1 using a two component progressive cavity pump.

24. The method of claim 23 , wherein the method comprises extruding each of the first component and the second component into a mixer.

25. The method of claim 23 , wherein the method comprises extruding each of the first component and the second component into a mixer having an exit orifice diameter from 0.6 mm to 2.5 mm, and a length from 30 mm to 150 mm.

26. The method of claim 23 , wherein the method comprises extruding each of the first component and the second component into a mixer, wherein the composition has a residence time in the mixer within a range from 0.25 seconds to 5 seconds.

27. The composition of claim 1 , wherein the composition comprises a rheology modifier.

28. The composition of claim 27 , wherein the rheology modifier comprises a filler, a polymer, or a combination thereof.

29. The composition of claim 27 , wherein the rheology modifier comprises a reactive rheology modifier.

30. The composition of claim 27 , wherein the rheology modifier comprises polyethylene, a polyethylene/ethylene copolymer, a polypropylene/ethylene copolymer, or a combination of any of the foregoing.

31. The composition of claim 1 , wherein the composition comprises low-density filler, electrically conductive filler, magnetic filler, opaque filler, an inorganic filler, an organic filler, or a combination of any of the foregoing.

32. The composition of claim 1 , wherein the composition comprises from 1 wt % to 40 wt % of a filler, wherein wt % is based on the total weight of the composition.

33. The composition of claim 1 , wherein the polyisocyanate prepolymer and the polyamine prepolymer independently have a molecular weight from 400 Daltons to 8,000 Daltons.

34. The composition of claim 1 , wherein the first component comprises a polyisocyanate monomer and/or the second component comprises a polyamine monomer.

35. A method of additive manufacturing comprising extruding the reactive additive manufacturing composition of claim 1 .

36. A method of reactive ad

Assignees

• Ppg Ind Ohio Inc

Inventors

• Fenn David Robert
• Olson Kurt G
• Rock Reza M
• Kutchko Cynthia
• Donaldson Susan
• Fogl Anthony J

Classifications

• C08K3/046

  Carbon nanorods, nanowires, nanoplatelets or nanofibres · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G59/66 Primary

  Mercaptans · CPC title