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

Patent metadata

Field	Value
Publication number	US-10787583-B2
Application number	US-201616061205-A
Country	US
Kind code	B2
Filing date	Dec 21, 2016
Priority date	Dec 22, 2015
Publication date	Sep 29, 2020
Grant date	Sep 29, 2020

Abstract

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.

First claim

We claim:

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.

Assignees

• Carbon Inc

Inventors

• Drazba Jessica D
• Chen Kai
• Rolland Jason P

Classifications

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C09D4/00

  Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} · CPC title

• G03F7/037

  the binders being polyamides or polyimides · CPC title

• G03F7/0755

  Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence) · CPC title