Sustainable chemistry systems for recyclable dental models and other additively manufactured products

Patent metadata

Field	Value
Publication number	US-11299576-B2
Application number	US-201917053959-A
Country	US
Kind code	B2
Filing date	May 9, 2019
Priority date	May 11, 2018
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

Abstract

Provided herein are methods of recycling additively manufactured objects, which may include making a reactive particulate material by recycling preformed articles or recovered coating material. Methods of use of the reactive particulate material and material sets including the same are also provided.

First claim

We claim:

1. A method of making a reactive particulate material by recycling a preformed article or recovered coating material, comprising:
(a) providing a preformed article, or recovered coating material, produced by a process of light polymerizing a single-cure resin in an additive manufacturing or coating process, wherein said resin is solely polymerized by light polymerization in said process, the resin comprising more than 90% by weight of: (i) a reactive blocked polyurethane prepolymer, a reactive blocked polyurea prepolymer, a reactive blocked polyurethane-polyurea copolymer, or a combination thereof, and (ii) optionally a monofunctional reactive diluent; wherein said resin further comprises: (iii) a photo-initiator,
wherein said reactive blocked polyurethane prepolymer, reactive blocked polyurea prepolymer, reactive blocked polyurethane-polyurea copolymer, or combination thereof is blocked with a tertiary amine-containing (meth)acrylate selected from t-butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), acrylate analogs thereof, and mixtures thereof, and
wherein said resin does not include a chain extender for heat and/or microwave polymerization of a thermally reactive component of the reactive blocked polyurethane prepolymer, reactive blocked polyurea prepolymer, or reactive blocked polyurethane-polyurea copolymer; and then
(b) comminuting said preformed article or coating material into a reactive particulate material.

2. The method of claim 1 , wherein said preformed article or recovered coating material is comprised of a polymer, said polymer consisting essentially of said resin in light polymerized, cross-linked, thermoset form;
optionally, pigments and/or dyes; and
optionally, at least one filler.

3. The method of claim 1 , wherein said single-cure resin further comprises a nonreactive blocked polyurethane prepolymer.

4. The method of claim 1 , wherein said tertiary amine-containing (meth)acrylate is t-butylaminoethyl methacrylate (TBAEMA).

5. The method of claim 1 , wherein said tertiary amine-containing (meth)acrylate is selected from t-butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), and mixtures thereof.

6. The method of claim 1 , wherein said monofunctional 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.

7. The method of claim 1 , wherein said monofunctional reactive diluent is present and comprises isobornyl methacrylate.

8. The method of claim 1 , wherein said comminuting step is carried out by grinding, shredding, chopping, or pelletizing.

9. The method of claim 1 , wherein the additive manufacturing process comprises top-down or bottom-up stereolithography.

10. A reactive particulate material produced by a process comprising:
(a) providing a preformed article, or recovered coating material, produced by a process of light polymerizing a single-cure resin in an additive manufacturing or coating process, wherein said resin is solely polymerized by light polymerization in said process, the resin comprising more than 90% by weight of: (i) a reactive blocked polyurethane prepolymer, a reactive blocked polyurea prepolymer, a reactive blocked polyurethane-polyurea copolymer, or a combination thereof, and (ii) optionally a monofunctional reactive diluent; wherein said resin further comprises: (iii) a photo-initiator,
wherein said reactive blocked polyurethane prepolymer, reactive blocked polyurea prepolymer, reactive blocked polyurethane-polyurea copolymer, or combination thereof is blocked with a tertiary amine-containing (meth)acrylate selected from t-butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), acrylate analogs thereof, and mixtures thereof, and
wherein said resin does not include a chain extender for heat and/or microwave polymerization of a thermally reactive component of the reactive blocked polyurethane prepolymer, reactive blocked polyurea prepolymer, or reactive blocked polyurethane-polyurea copolymer; and then
(b) comminuting said preformed article or coating material into a particulate material,
to thereby produce the reactive particulate material.

11. A material set comprising:
(a) a reactive particulate material of claim 10 as a powder bed material; and
(b) a fusing agent, said fusing agent comprising a polyol and/or polyamine chain extender.

12. The material set of claim 11 , wherein the fusing agent comprises a sprayable composition, optionally further comprising a crosslinker selected from the group consisting of a diisocyanate, alkyl dihalide, dicarboxylic acid, diacyl halide, diepoxide, and a mixture thereof.

13. A method of making a three-dimensional object, comprising:
applying a fusing agent to a bed of a particulate material in sequential patterned repetitions thereof; and
employing a reactive particulate material of claim 10 as the particulate material in combination with the fusing agent, said fusing agent comprising a polyol and/or polyamine chain extender, optionally while heating said particulate before and/or after said fusing agent is applied.

14. A method of coating an object, comprising:
applying a particulate to the object with a reactive resin; and
employing a reactive particulate material of claim 10 as the particulate in combination with a polyol and/or polyamine chain extender as the reactive resin, optionally while heating the object before and/or after applying said particulate and resin thereto.

15. A method of making a staple thermoplastic material, comprising:
reacting a reactive particulate material of claim 10 with a polyol and/or polyamine chain extender, wherein said reacting is carried out by heating the reactive particulate material with the polyol and/or polyamine chain extender, whereby a homogeneous thermoplastic material is produced; and then
forming said homogeneous thermoplastic material into either a new object, or a staple article for subsequent use.

16. The method of claim 15 , wherein said reacting step is carried out by co-extrusion of said reactive particulate material with said chain extender.

17. The method of claim 15 , wherein said reacting step is carried out at a temperature of 30° C. to 350° C.

18. The method of claim 15 , wherein said reactive particulate material comprises light polymerized reactive blocked polyurethane prepolymer, reactive blocked polyurea prepolymer, reactive blocked polyurethane-polyurea copolymer, or combination thereof blocked with tert-butylaminoethyl methacrylate, copolymerized with isobornyl methacrylate, and wherein said thermoplastic material comprises a blend of linear or branched chain extended polyurethane or polyurethane-urea polymers and poly(isobornyl methacrylate-co-tert-butylaminoethyl methacrylate).

19. A method of making a recyclable preformed article, comprising:
(a) providing a single-cure resin comprising more than 90% by weight of: (i) a reactive blocked polyurethane prepolymer, a reactive blocked polyurea prepolymer, a reactive blocked polyurethane-polyurea copolymer, or a combination thereof, and (

Assignees

• Carbon Inc

Inventors

• Poelma Justin
• Zhang Mu San
• Gu Xinyu
• Rolland Jason P
• Desimone Joseph M

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

• C08G18/808

  Monoamines · CPC title

• B29C64/165

  using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber · CPC title

• C08L55/005

  Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond · CPC title