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Provided herein is a method of recycling additively manufactured articles or recovered coating material that comprises a crosslinked polymer formed from a single-cure resin comprising a reactive blocked prepolymer, into a regenerated resin useful for additive manufacturing. Recyclable light-polymeri

Provided herein is a method of recycling additively manufactured articles or recovered coating material that comprises a crosslinked polymer formed from a single-cure resin comprising a reactive blocked prepolymer, into a regenerated resin useful for additive manufacturing. Recyclable light-polymerizable resins, methods of making recyclable objects from such resins, and methods for sustainable manufacturing are also provided.

대표청구항 ▼

1. A light-polymerizable resin produced by the process of: (a) providing a preformed article, or recovered coating material, wherein said article or coating material is produced by the process of light polymerizing a single-cure resin in an additive manufacturing or coating process, said resin compr

1. A light-polymerizable resin produced by the process of: (a) providing a preformed article, or recovered coating material, wherein said article or coating material is produced by the process of light polymerizing a single-cure resin in an additive manufacturing or coating process, said resin comprising or consisting essentially of: (i) a reactive blocked prepolymer;(ii) optionally polymerized reactive blocking agents;(iii) optionally a reactive blocking agent;(iv) a photoinitiator;(v) optionally a reactive diluent;(vi) optionally a light absorber;(vii) optionally a solvent;(viii) optionally a radical polymerization inhibitor;(ix) optionally pigments and/or dyes; and(x) optionally at least one filler;said preformed article or recovered coating material comprised of at least 70, 80 or 90 percent by weight of a crosslinked polymer, said crosslinked polymer consisting essentially of said reactive blocked prepolymer, said reactive diluent when included, and said polymerized reactive blocking agents when included, in light polymerized, cross-linked, thermoset form; then(b) comminuting said preformed article or recovered coating material into a reactive particulate material; and(c) combining said reactive particulate material with additional unpolymerized light reactive, and optionally non-reactive, blocking agent, optionally additional unpolymerized UV-curable diluent or solvent, and optionally additional radical polymerization inhibitor, to form a mixture, and heating said mixture for a time sufficient to form a homogeneous solution or suspension comprising a regenerated light reactive, and non-reactive, when present, blocked prepolymer; optionally said additional light reactive and/or non-reactive blocking agent; optionally said additional solvent; optionally said additional radical polymerization inhibitor; and polymerized light reactive blocking agent, or a copolymer of light reactive blocking agent and UV-curable diluent. 2. The resin of claim 1, wherein said reactive particulate material is provided in an amount of from 1 percent by weight to 30 percent by weight of the mixture. 3. The resin of claim 1, wherein the resin comprises a copolymer of reactive blocking agent and reactive diluent. 4. The resin of claim 1, wherein said method further comprises: (d) mixing said homogeneous solution or suspension with additional photoinitiator, optionally but in some embodiments preferably additional light absorber, optionally but in some embodiments preferably additional reactive blocked prepolymer, optionally but in some embodiments preferably additional reactive diluent, optionally but in some embodiments preferably additional reactive and/or non-reactive blocking agent, and optionally but in some embodiments preferably additional polymerized reactive blocking agents and/or a copolymer of reactive blocking agent and reactive diluent. 5. A recyclable light-polymerizable resin useful for additive manufacturing, comprising or consisting essentially of: (i) a reactive blocked prepolymer, and optionally a non-reactive blocked prepolymer;(ii) polymerized reactive blocking agent, and optionally polymerized reactive diluent copolymerized therewith;(iii) optionally, but in some embodiments preferably, a reactive and/or non-reactive blocking agent;(iv) a photoinitiator;(v) optionally a reactive diluent;(vi) optionally a light absorber;(vii) optionally a solvent;(viii) optionally pigments and/or dyes;(ix) optionally a radical polymerization inhibitor; and(x) optionally at least one filler. 6. The resin of claim 5, wherein said polymerized reactive blocking agent comprises a polymer formed from the polymerization of vinyl group-containing monomers, such as: a poly(methacrylate), a poly(acrylate), a poly(styrene), a poly(acrylamide), or a copolymer thereof. 7. The resin of claim 5, wherein said reactive blocking agent comprises an amine (meth)acrylate monomer blocking agent. 8. The resin of claim 5, wherein said reactive blocked prepolymer comprises a reactive blocked polyurethane prepolymer, a reactive blocked polyurea prepolymer, a reactive blocked polyurethane-polyurea copolymer, or a combination thereof. 9. The resin of claim 5, wherein said reactive blocked prepolymer comprises reactive end groups selected from the group consisting of acrylates, methacrylates, alpha-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers. 10. The resin of claim 5, wherein said reactive blocked prepolymer comprises a (meth)acrylate-blocked prepolymer. 11. The resin of claim 5, 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. 12. The resin of claim 5, wherein said reactive diluent is present and comprises a monofunctional reactive diluent. 13. The resin of claim 5, wherein said resin further comprises a chain transfer agent. 14. The resin of claim 13, wherein said chain transfer agent comprises butyl 3-mercaptopropionate, dodecane thiol, 2,2′-(ethylenedioxy)diethanethiol, nonyl thiol, 4-methylthiophenol, isooctylmercapto propionate, or a mixture of two or more thereof. 15. A method of making a recyclable object by additive manufacturing, comprising: (a) providing a resin of claim 14; and(b) producing said object by light polymerizing said resin in an additive manufacturing process. 16. The method of claim 15, further comprising: (c) comminuting said object to form a reactive particulate material useful for the production of a light-polymerizable additive manufacturing resin. 17. A sustainable manufacturing method, comprising the steps of: (a) shipping the resin of claim 5 to at least one user;(b) collecting objects produced from said resin back from said at least one user; and(c) converting said objects back to a subsequent recyclable light-polymerizable resin. 18. The method of claim 17, further comprising: (d) shipping said subsequent recyclable light-polymerizable resin to said at least one user. 19. The method of claim 17, wherein said objects comprise dental models. 20. The method of claim 17, wherein said at least one user comprises a plurality of users.