Additive manufacturing using polyurea materials

Patent metadata

Field	Value
Publication number	US-2019054681-A1
Application number	US-201715680846-A
Country	US
Kind code	A1
Filing date	Aug 18, 2017
Priority date	Aug 18, 2017
Publication date	Feb 21, 2019
Grant date	—

Abstract

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

First claim

1 . A method of reactive additive manufacturing, comprising:
providing a first component comprising a first prepolymer into a first pump; providing a second component comprising a second prepolymer into a second pump, wherein the second prepolymer is reactive with the first prepolymer; pumping the first component from the first pump, and the second component from the second pump through a mixer to provide a reactive composition; and depositing the reactive composition through a nozzle connected to the mixer.

2 . The method of claim 1 , wherein the first component comprises a polyisocyanate prepolymer; and the second component comprises a polyamine prepolymer.

3 . The method of claim 1 , wherein each of the first pump and the second pump independently comprise a syringe pump, a peristaltic pump, or a progressive cavity pump.

4 . The method of claim 1 , wherein each of the first pump and the second pump comprises a progressive cavity pump.

5 . The method of claim 1 , wherein the mixer comprises a static mixer, a dynamic mixer, or a combination thereof.

6 . The method of claim 1 , wherein the mixer comprises a static mixer.

7 . 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.

8 . The composition of claim 7 , wherein the first viscosity is within ±10% of the second viscosity.

9 . The composition of claim 7 , 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.

10 . The composition of claim 9 , wherein the filler comprises an inorganic filler, an organic filler, or a combination thereof.

11 . The composition of claim 7 , wherein,
the polyisocyanate prepolymer comprises a difunctional polyisocyanate prepolymer; and the polyamine prepolymer comprises a difunctional polyamine prepolymer.

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

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

14 . The composition of claim 7 , wherein the polyamine prepolymer comprises a trifunctional polyetheramine.

15 . The composition of claim 7 , wherein the polyamine prepolymer comprising a difunctional polyamine, a trifunctional polyamine, or a combination thereof.

16 . The composition of claim 7 , wherein the second component comprises a monomeric diamine and a rheology modifier.

17 . The composition of claim 7 , wherein the second component comprises a secondary aliphatic diamine and a polyethylene/polypropylene copolymer.

18 . The composition of claim 7 , 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.

19 . The composition of claim 18 , wherein,
the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polytetramethylene prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.

20 . The composition of aspect 18, wherein, the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polyetheramine prepolymer, such as an isophorone diisocyanate-terminated polyoxypropylenediamine prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.

21 . The composition of aspect 18, wherein, the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polyoxypropylenediamine prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.

22 . The composition of claim 18 , wherein,
the monomeric amine comprises a secondary aliphatic diamine; and the rheology modifier comprises a propylene/ethylene copolymer.

23 . The composition of claim 18 , 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.

24 . The composition of claim 18 , 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.

25 . The composition of claim 7 , 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.

26 . The composition of claim 7 , 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.

27 . The composition of claim 7 , wherein the composition is characterized by a tack free time of greater than 3 minutes.

28 . An object formed using the composition of claim 7 .

29 . The object of claim 28 , wherein the object comprises a plurality of layers, wherein adjacent layers forming the object are covalently bonded.

30 . A method of additive manufacturing, comprising extruding the reactive additive manufacturing composition of claim 7 using a two component progressive cavity pump.

31 . The method of claim 30 , wherein the method comprises extruding each of the first component and the second component into a mixer.

32 . The method of claim 30 , 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.

33 . The method of claim 30 , 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.

Assignees

• Ppg Ind Ohio Inc

Inventors

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

Classifications

• B33Y10/00

  Processes of additive manufacturing · CPC title

• C08G75/14

  Polysulfides · CPC title

• C08K3/36

  Silica · CPC title

• C08G59/66 Primary

  Mercaptans · CPC title

• C08G18/4854

  Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group · CPC title