Blocked silicone dual cure resins for additive manufacturing
A polymerizable liquid useful for the production of a three-dimensional object comprised of silicone, or a copolymer thereof, which includes at least one constituent selected from the group consisting of (i) a blocked or reactive blocked siloxane-containing prepolymer, (ii) a blocked or reactive blocked siloxane-containing polyisocyanate, and (iii) a blocked or reactive blocked siloxane-containing polyisocyanate chain extender. Methods of using the same in additive manufacturing processes such as continuous liquid interface production are also described.
1. A polymerizable liquid useful for the production of a three-dimensional object comprised of a silicone polymer or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) from 5 to 90 percent by weight of a blocked or reactive blocked siloxane-containing prepolymer,
(b) from 5 to 90 percent by weight of a chain extender,
(c) from 0.01 to 4 percent by weight of a photoinitiator,
(d) optionally a polyol and/or a polyamine,
(e) optionally a reactive diluent,
(f) optionally, a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight, and
(g) optionally a filler.
2. The polymerizable liquid of claim 1 , wherein said pigment or dye is present and is:
(i) titanium dioxide,
(ii) carbon black, and/or
(iii) an organic ultraviolet light absorber.
3. The polymerizable liquid of claim 1 , wherein said blocked or reactive blocked siloxane-containing prepolymer is a compound of the formula A-X-A, where X is a siloxane group, or a mixed hydrocarbyl and siloxane group, and each A is an independently selected substituent of Formula (X):
wherein R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group optionally having a reactive terminal group.
4. The polymerizable liquid of claim 1 , wherein said blocked or reactive blocked siloxane-containing prepolymer comprises a polyisocyanate;
and/or said reactive blocked prepolymer comprises two or more ethylenically unsaturated end groups.
5. The polymerizable liquid of claim 1 , wherein said blocked or reactive blocked siloxane-containing prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one polyol or polyamine.
6. The polymerizable liquid of claim 1 , wherein said siloxane-containing prepolymer is a reactive blocked siloxane-containing prepolymer blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.
7. The polymerizable liquid of claim 1 , wherein said reactive diluent is present and 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, or a combination of two or more of the foregoing.
8. The polymerizable liquid of claim 1 , wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.
9. The polymerizable liquid of claim 1 , wherein said polymerizable liquid comprises:
from 20 to 60 percent by weight of said blocked or reactive blocked siloxane-containing prepolymer;
from 10 to 50 percent by weight of said chain extender; and
from 1 to 40 percent by weight of said reactive diluent.
10. A polymerizable liquid useful for the production of a three-dimensional object comprised of a silicone polymer or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) a blocked or reactive blocked siloxane-containing polyisocyanate,
(b) optionally a polyol and/or polyamine,
(c) a chain extender,
(d) a photoinitiator,
(e) optionally a reactive diluent,
(f) optionally a pigment or dye, and
(g) optionally a filler.
11. The polymerizable liquid of claim 10 , further comprising:
(h) a blocked or reactive blocked, optionally siloxane-containing, diisocyanate prepolymer.
12. The polymerizable liquid of claim 10 , 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.
13. The polymerizable liquid of claim 12 , wherein said pigment or dye is:
(i) titanium dioxide,
(ii) carbon black, and/or
(iii) an organic ultraviolet light absorber.
14. The polymerizable liquid of claim 10 , wherein said blocked or reactive blocked siloxane-containing polyisocyanate is a compound of the formula A′-X′-A′, where X′ is a siloxane group, or a mixed hydrocarbyl and siloxane group, and each A′ is an independently selected substituent of Formula (X′):
wherein Z is a blocking group, said blocking group optionally having a reactive terminal group.
15. The polymerizable liquid of claim 14 , wherein each A′ is a substituent of Formula (XI′):
16. The polymerizable liquid of claim 10 , wherein said blocked or reactive blocked siloxane-containing polyisocyanate is blocked by reaction of a polyisocyanate with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.
17. The polymerizable liquid of claim 10 , wherein said reactive diluent is present and 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, or a combination of two or more of the foregoing.
18. The polymerizable liquid of claim 10 , wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.
19. The polymerizable liquid of claim 10 , wherein said polymerizable liquid comprises:
from 5 to 90 percent by weight of said blocked or reactive blocked siloxane-containing polyisocyanate,
optionally, 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,
from 0.1 to 4 percent by weight of said photoinitiator,
from 0.1 to 2 percent by weight of said pigment or dye when present, and
from 1 to 50 percent by weight of said filler when present.
20. A polymerizable liquid useful for the production of a three-dimensional object comprised of a silicone polymer or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) a polyol and/or polyamine,
(b) a blocked or reactive blocked siloxane-containing polyisocyanate chain extender,
(c) optionally one or more additional chain extenders,
(d) a photoinitiator,
(e) optionally a reactive diluent,
(f) optionally a pigment or dye, and
(g) optionally a filler.
21. The polymerizable liquid of claim 20 , further comprising:
(h) a blocked or reactive blocked diisocyanate prepolymer, and/or a blocked or reactive blocked polyisocyanate.
22. The polymerizable liquid of claim 20 , 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.
23. The polymerizable liquid of claim 22 , wherein said pigment or dye is:
(i) titanium dioxide,
(ii) carbon black, and/or
(iii) an organic ultraviolet light absorber.
24. The polymerizable liquid of claim 20 , wherein said blocked or reactive blocked siloxane-containing polyisocyanate chain extender is a compound of the formula A″-X″-A″, where X″ is a siloxane group, or a mixed hydrocarbyl and siloxane group, and each A″ is an independently selected substituent of Formula (X″):
wherein R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group optionally having a reactive terminal group.
25. The polymerizable liquid of claim 20 , wherein said blocked or reactive blocked siloxane-containing polyisocyanate chain extender comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one chain extender.
26. The polymerizable liquid of claim 20 , wherein said reactive blocked siloxane-containing chain extender is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide or n-vinylformamide monomer blocking agent.
27. The polymerizable liquid of claim 20 , wherein said reactive diluent is present and 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, or a combination of two or more of the foregoing.
28. The polymerizable liquid of claim 20 , wherein said polymerizable liquid comprises:
from 5 to 90 percent by weight of said polyol or polyamine,
from 5 to 90 percent by weight of said blocked or reactive blocked siloxane-containing polyisocyanate chain extender,
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,
from 0.01 to 2 percent by weight of said pigment or dye when present, and
from 1 to 50 percent by weight of said filler when present.
29. The polymerizable liquid of claim 3 , wherein each A is an independently selected substituent of Formula (XI):
wherein R and R′ are as provided in claim 3 .