Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects
A polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object of polyurethane, polyurea, or a copolymer thereof, is described. The resin includes at least one of (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate, or (iii) a blocked or reactive blocked diisocyanate chain extender.
1. A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurethane, polyurea, or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) a reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:
where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group,
(b) a chain extender,
(c) a photoinitiator,
(d) optionally a polyol and/or a polyamine,
(e) optionally a reactive diluent,
(f) a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight, and
(g) optionally a filler, and
(h) a reactive blocked diisocyanate.
2. The polymerizable liquid of claim 1 , wherein said pigment or dye is:
(i) titanium dioxide,
(ii) carbon black, and/or
(iii) an organic ultraviolet light absorber.
3. The liquid of claim 1 , wherein said reactive blocked prepolymer comprises a polyisocyanate;
and/or said reactive blocked prepolymer comprises two or more ethylenically unsaturated end groups.
4. The liquid of claim 1 , wherein said reactive blocked prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one polyol or polyamine.
5. The liquid of claim 1 , wherein said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.
6. The liquid of claim 1 , wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
7. The liquid of claim 1 , wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.
8. The liquid of claim 1 , wherein said polymerizable liquid comprises:
from 5 to 90 percent by weight of said reactive blocked prepolymer;
optionally, from 1 to 40 percent by weight of said reactive diluent;
from 5 to 30 percent by weight of said chain extender;
from 0.1 to 4 percent by weight of said photoinitiator, and
from 1 to 50 percent filler when present.
9. A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurethane, polyurea, or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) a reactive blocked diisocyanate comprising a compound of the formula A′-X′-A′, where X′ is a hydrocarbyl group and each A′ is an independently selected substituent of Formula (X′):
where Z is a blocking group, said blocking group having — a reactive epoxy, alkene, alkyne, or thiol terminal group,
(b) a polyol and/or polyamine,
(c) a chain extender,
(d) a photoinitiator, and
(e) optionally a reactive diluents,
(f) optionally a pigment or dye, and
(g) optionally a filler.
10. The liquid of claim 9 , further comprising:
(h) a reactive blocked diisocyanate prepolymer.
11. The liquid of claim 9 , wherein said pigment or dye is present and is a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight.
12. The liquid of claim 11 , wherein said pigment or dye is:
(i) titanium dioxide,
(ii) carbon black, and/or
(iii) an organic ultraviolet light absorber.
13. The liquid of claim 9 , wherein each A′ is an independently selected substituent of Formula XI′:
14. The liquid of claim 9 , wherein said reactive blocked diisocyanate is blocked by reaction of a polyisocyanate with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.
15. The liquid of claim 9 , wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
16. The liquid of claim 9 , wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.
17. The liquid of claim 9 , wherein said polymerizable liquid comprises:
from 5 to 90 percent by weight of said reactive blocked diisocyanate;
from 5 to 90 percent by weight of said polyol or polyamine;
optionally, from 1 to 40 percent by weight of said reactive diluent;
from 5 to 30 percent by weight of said chain extender; and
from 0.1 to 4 percent by weight of said photoinitiator;
from 0.1 to 2 percent pigment when present, and
from 1 to 50 percent filler when present.
18. A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurethane, polyurea, or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) a polyol and/or polyamine,
(b) a reactive blocked diisocyanate chain extender comprising a compound of the formula A″-X″-A″, where X″ is a hydrocarbyl group, and each A″ is an independently selected substituent of Formula (X″):
where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkene, or thiol terminal group,
(c) optionally one or more additional chain extenders,
(d) a photoinitiator,
(e) optionally a reactive diluent;
(f) optionally a pigment or dye,
(g) optionally a filler, and
(h) a reactive blocked diisocyanate prepolymer, and/or a reactive blocked diisocyanate.
19. The liquid of claim 18 , comprising:
(h) both a reactive blocked diisocyanate prepolymer and a reactive blocked diisocyanate.
20. The liquid of claim 18 , wherein said pigment or dye is present and is a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight.
21. The liquid of claim 20 , wherein said pigment or dye is:
(i) titanium dioxide,
(ii) carbon black, and/or
(iii) an organic ultraviolet light absorber.
22. The liquid of claim 18 , wherein said reactive blocked diisocyanate chain extender comprises a diisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one chain extender.
23. The liquid of claim 18 , wherein said reactive blocked diisocyanate chain extender is blocked by reaction of a diisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide or n-vinylformamide monomer blocking agent.
24. The liquid of claim 18 , wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
25. The liquid of claim 1 , said reactive blocked diisocyanate comprising a compound of the formula A′-X′-A′, where X′ is a hydrocarbyl group and each A′ is an independently selected substituent of Formula (X′):
where Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group.
26. The liquid of claim 10 , said reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:
where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group.
27. The liquid of claim 18 , said reactive blocked diisocyanate comprising a compound of the formula A′-X′-A′, where X′ is a hydrocarbyl group and each A′ is an independently selected substituent of Formula (X′):
where Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group; and
said reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:
where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group.
28. The liquid of claim 19 , said reactive blocked diisocyanate comprising a compound of the formula A′-X′-A′, where X′ is a hydrocarbyl group and each A′ is an independently selected substituent of Formula (X′):
where Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group; and
said reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:
where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group.
29. The liquid of claim 1 , wherein said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.
30. The liquid of claim 9 , wherein said reactive blocked diisocyanate is blocked by reaction of a polyisocyanate with an alcohol (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.