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1. (WO2018165090) TOUGH, HIGH TEMPERATURE POLYMERS PRODUCED BY STEREOLITHOGRAPHY
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What is claimed is:

1. A method of forming a three-dimensional object, comprising:

(a) providing a polymerizable liquid comprising a mixture of (i) a light polymerizable first component, (ii) a second solidifiable component that is different from said first component, and (in) an organic diluent {e.g., a reactive organic diluent) in an amount sufficient to reduce the viscosity of said polymerizable liquid;

(b) producing a three-dimensional intermediate from said polymerizable liquid by an additive manufacturing process including irradiating said polymerizable liquid with light to form a solid polymer scaffold from said first component and containing said second solidifiable component carried in said scaffold in unsolidified and/or uncured form, said intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object;

said irradiating under conditions in which said organic diluent chemically reacts {e.g., degrades, isomerizes, cross-reacts, or polymerizes {e.g., with a light polymerizable component), etc.) by an amount sufficient to increase the strength of said intermediate;

(c) optionally washing said intermediate, and

(d) concurrently with or subsequent to said producing step (b), further curing said second solidifiable component in said three-dimensional intermediate to form said three-dimensional object.

2. The method of claim 1, wherein said polymerizable liquid comprises a toughener {e.g., a core-shell rubber, a thermoplastic toughener, etc., including combinations thereof), preferably in an amount of from about 5 or 10 to 20, 25 or 30 percent by weight, and optionally wherein the toughener has a phenol, amine, epoxide, or isocyante reactive end group reactive with epoxides.

3. The method of claim 1 or claim 2, wherein said producing step (b) is carried out by stereolithography {e.g., bottom-up stereolithography such as continuous liquid interface production).

4. The method of any preceding claim, wherein said producing step (b) is carried out by: (i) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween; (ii) filling said build region with said polymerizable liquid, and (Hi) irradiating said build region with light through said optically transparent member to form said solid polymer scaffold from said first component and also advancing said carrier and said build surface away from one another to form said three-dimensional intermediate.

5. The method of any preceding claim, wherein said further curing step (d) is carried out subsequent to said producing step (b), and optionally but preferably subsequent to said washing step (c).

6. The method of any preceding claim, wherein said further curing step (d) is carried out by heating, microwave irradiating, or both heating and microwave irradiating.

7. The method of any preceding claim, wherein said polymerizable liquid comprises: (a) light-polymerizable monomers and/or prepolymers that can participate in forming an intermediate object by stereolithography (preferably included in an amount of from 5, 10, or 20 percent by weight, to 50, 60, or 80 percent by weight); and (b) heat-polymerizable monomers and/or prepolymers (preferably included in an amount of from 5, 10 or 20 percent by weight, to 40, 50 or 60 percent by weight);

optionally but in some embodiments preferably wherein the light polymerizable monomers and/or prepolymers comprise reactive end groups selected from the group consisting of acrylates, methacrylates, oc-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers; and/or

optionally but in some embodiments preferably wherein the heat polymerizable monomers and/or prepolymers comprise reactive end groups selected from the group consisting of: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate/hydroxyl, isocyanate/amine, isocyanate/carboxylic acid, cyanate ester, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si-H, Si-Cl/hydroxyl, Si-Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide, click chemistry reactive groups, alkene/sulfur, alkene/thiol, alkyne/thiol, hydroxyl/halide, isocyanate/water, Si-OH/hydroxyl, Si-OH/water, Si-OH/Si-H,

Si-OH/Si-OH, perfluorovinyl, diene/dienophiles, olefin metathesis polymerization groups, olefin polymerization groups for Ziegler-Natta catalysis, and ring-opening polymerization groups and mixtures thereof.

8. The method of any preceding claim, wherein said polymerizable liquid further comprises a hardener (e.g., included in an amount of at least 1, 5, or 10 percent by weight, up to 40 or 50 percent by weight) (e.g., the hardener comprising a compound having amine, thiol, vinyl ether, maleimide, or allyl reactive end groups).

9. The method of any preceding claim, said polymerizable liquid further comprising at least one photoinitiator (e.g., in an amount of from 0.1 to 1 or 5 percent by weight), optionally at least one dye (e.g., in an amount of 0.001 or 0.01 to 1 or 5 percent by weight), and optionally at least one filler (e.g., in an amount of 0.01 or 0.1 to 20 or 50 percent by weight).

10. The method of any preceding claim, wherein said second solidifiable component comprises an epoxy or cyanate ester resin, preferably in an amount from 20 or 30 percent by weight to 50, 60 or 70 percent by weight.

11. The method of any preceding claim, wherein said organic diluent comprises Ν,Ν'-dimethylacrylamide, n-vinyl-2-pyrrolidone, n-vinyl formamide, n-vinyl caprolactam, acryloylmorpholine, or a combination of two or more thereof.

12. The method of any preceding claim, wherein said polymerizable liquid comprises a hardener (e.g., an amine hardener such as a diaminodiphenyl sulfone hardener), optionally but preferably with said organic diluent included in an amount sufficient to dissolve said hardener in said polymerizable liquid.

13. The method of any preceding claim, wherein said polymerizable liquid comprises a chain extender (e.g., a dihydric phenolic compound) (e.g., in an amount of from 5 or 10 to 20, 25 or 30 percent by weight), and optionally further comprises a chain extender catalyst (e.g., an onium salt such as a phosphonium salt) (e.g., in an amount of from 0.01, 0.05 or 0.1 to 2, 5 or 10 percent by weight).

14. The method of any preceding claim, wherein said three-dimensional object is rigid.

15. A polymer blend comprising a light polymerized first component and a heat polymerized second component, said polymer blend having a notched Izod Impact Strength of at least 50 J/m when measured in accordance with ASTM D256, and a heat deflection temperature of at least 100 degrees Centigrade when measured in accordance with ASTM D648.

16. The polymer blend of claim 15, wherein said polymer blend comprises a toughener (e.g., a core-shell rubber, a thermoplastic toughener, etc.), preferably in an amount of from about 5 or 10 percent by weight to 20, 25 or 30 percent by weight.

17. The polymer blend of claim 15 or claim 16, wherein said heat polymerized second component comprises an epoxy or cyanate ester polymer, preferably in an amount from 20 or 30 percent by weight to 50, 60 or 70 percent by weight.

18. The polymer blend of claim 15, claim 16 or claim 17 configured as a three-dimensional object, said object produced by the process of additive manufacturing (e.g., stereolithography, such as continuous liquid interface production).

19. A dual cure resin useful for making a three-dimensional object by stereolithography, comprising:

(a) light-polymerizable monomers and/or prepolymers that can participate in forming an intermediate object by stereolithography such as CLIP (e.g., included in an amount of from 1, 5, or 10 percent by weight, to 50, 60, or 80 percent by weight);

(b) heat-polymerizable monomers and/or prepolymers (e.g., included in an amount of from 5 or 10 percent by weight, to 50 or 60 percent by weight);

(c) a hardener (e.g., a compound having amine, thiol, vinyl ether, maleimide, or allyl reactive end groups) (e.g., included in an amount of at least 1, 5, or 10 percent by weight, up to 40 or 50 percent by weight); and

(d) an organic diluent in a viscosity-reducing effective amount, optionally but preferably wherein said diluent solubilizes or dissolves said hardener in said resin.

20. The resin of claim 19, further comprising:

(e) a toughener (e.g., a core-shell rubber, a thermoplastic toughener, etc., including combinations thereof), preferably in an amount of from about 5 or 10 to 20, 25 or 30 percent by weight, optionally wherein the toughener has a phenol, amine, epoxide, or isocyante reactive end group reactive with epoxides.

21. The resin of claim 19 or claim 20, wherein said hardener comprises a polyamine {e.g., a diamine hardener such as a diaminodiphenyl sulfone hardener), optionally but prerferably with said organic diluent included in an amount sufficient to dissolve said hardener in said resin.

22. The resin of any one of claims 19-21, wherein said resin comprises a chain extender (e.g., a dihydric phenolic compound) {e.g., in an amount of from 5 or 10 to 20, 25 or 30 percent by weight), and optionally further comprises a chain extender catalyst {e.g., an onium salt such as a phosphonium salt) {e.g., in an amount of from 0.01, 0.05 or 0.1 to 2, 5 or 10 percent by weight).

23. The resin of any one of claims 19-22, wherein said diluent comprises Ν,Ν'-dimethylacrylamide, n-vinyl-2-pyrrolidone, n-vinyl formamide, n-vinyl caprolactam, acryloylmorpholine, or a mixture of two or more thereof.

24. The resin of any one of claims 19-23, wherein the light polymerizable monomers and/or prepolymers comprise reactive end groups selected from the group consisting of acrylates, methacrylates, -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.

25. The resin of any one of claims 19-24, wherein the heat polymerizable monomers and/or prepolymers comprise reactive end groups selected from the group consisting of: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate/hydroxyl,

isocyanate/amine, isocyanate/carboxylic acid, cyanate ester, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si-H, Si-Cl/hydroxyl, Si-Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide, click chemistry reactive groups, alkene/sulfur, alkene/thiol, alkyne/thiol, hydroxyl/halide, isocyanate/water, Si-OH/hydroxyl, Si-OH/water, Si-OH/Si-H, Si-OH/Si-OH, perfluorovinyl, diene/dienophiles, olefin metathesis polymerization groups, olefin polymerization groups for Ziegler-Natta catalysis, and ring-opening polymerization groups and mixtures thereof.

26. The resin of any one of claims 19-25, further comprising at least one photoinitiator (e.g., in an amount of from 0.1 to 1 or 5 percent by weight), optionally at least one dye (e.g., in an amount of 0.001 or 0.01 to 1 or 5 percent by weight), and optionally at least one filler (e.g., in an amount of 0.01 or 0.1 to 20 or 50 percent by weight).

27. The resin of any one of claims 19-26, wherein said resin comprises a cyanate ester or epoxy resin.

28. A method of making a three-dimensional object, comprising:

(a) providing a resin of any one of claims 19 to 27;

(b) producing by additive manufacturing a three-dimensional intermediate from said dual cure resin, said intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object, said additive manufacturing including irradiating the resin with light;

(c) optionally washing said intermediate; and then

(d) heating said intermediate (i.e., to a temperature at which said heat-polymerizable monomers and/or prepolymers polymerize) to produce said three-dimensional object.

29. The method of claim 28, said irradiating carried out under conditions in which said organic diluent chemically reacts (e.g., degrades, isomerizes, cross-reacts, or polymerizes (e.g., with a light polymerizable component), etc.) by an amount sufficient to increase the strength of said intermediate.

30. The method of claim 28 or claim 29, wherein said light polymerizable monomers and/or prepolymers form a solid polymer scaffold during said stereolithography step (b), which scaffold degrades during said heating step (d) and forms a constituent necessary for the polymerization of said heat polymerizable monomers and/or prepolymers.

31. The method of any one of claims 28-30, wherein said producing step (b) is carried out by stereolithography {e.g., bottom-up stereolithography).

32. The method of any one of claims 28-31, wherein said producing step (b) is carried out by continuous liquid interface production.