Method of forming a three-dimensional object comprised of a silicone polymer or co-polymer

1. A method of forming a three-dimensional object comprised of a silicone polymer or a copolymer thereof, said method comprising:

(a) providing a carrier, a fill level, and optionally an optically transparent member having a build surface, said carrier and said fill level defining a build region therebetween (and said build surface defining said fill level when present);

(b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising at least one of: (i) a blocked or reactive blocked siloxane-containing prepolymer, (ii) a blocked or reactive blocked siloxane-containing polyisocyanate, or (iii) a blocked or reactive blocked siloxane-containing polyisocyanate chain extender;

(c) irradiating said build region with light (through said optically transparent member when present) to form a solid blocked polymer scaffold and advancing said carrier away from said build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object, with said intermediate containing said (i) blocked or reactive blocked siloxane-containing prepolymer, (ii) blocked or reactive blocked siloxane-containing polyisocyanate, or (iii) blocked or reactive blocked siloxane-containing polyisocyanate chain extender; then

(d) optionally washing said three-dimensional intermediate; and then

(e) heating or microwave irradiating said three-dimensional intermediate sufficiently to form from said three-dimensional intermediate said three-dimensional object comprised of said silicone polymer or copolymer thereof.

2. The method of claim 1 , said polymerizable liquid comprising a mixture of (i) the blocked or reactive blocked siloxane-containing prepolymer, (ii) a chain extender, (iii) a photoinitiator, (iv) optionally a polyol and/or a polyamine, (v) optionally a reactive diluent, (vi) optionally a pigment or dye, and (vii) optionally a filler.

3. The method of claim 2 , 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 method of claim 1 , said polymerizable liquid comprising a mixture of (i) the blocked or reactive blocked siloxane-containing polyisocyanate, (ii) optionally a polyol and/or polyamine, (iii) a chain extender, (iv) a photoinitiator, (v) optionally a reactive diluent, (vi) optionally a pigment or dye, and (vii) optionally a filler.

5. The method of claim 4 , 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.

6. The method of claim 4 , 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.

7. The method of claim 4 , 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 method of claim 4 , wherein said chain extender is present and comprises at least one diol, diamine or dithiol chain extender.

9. The method of claim 1 , wherein said polymerizable liquid comprises a mixture of (i) a polyol and/or polyamine, (ii) the blocked or reactive blocked siloxane-containing polyisocyanate chain extender, (iii) optionally one or more additional chain extenders, (iv) a photoinitiator, (v) optionally a reactive diluent, (vi) optionally a pigment or dye, and (vii) optionally a filler.

10. The method of claim 9 , 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.

11. The method of claim 1 , wherein said polymerizable liquid is changed at least once during said method with a subsequent solidifiable or polymerizable liquid;

optionally wherein said subsequent solidifiable or polymerizable liquid is cross-reactive with each previous solidifiable or polymerizable liquid during said subsequent curing, to form an object having a plurality of structural segments covalently coupled to one another, each structural segment having different structural properties.