Tough, high temperature polymers produced by stereolithography

Abstract

The present invention concerns methods of forming a three-dimensional object, and polymerizable liquids such as dual cure resins useful for making a three-dimensional object by sterolithography, such as by continuous liquid interface production (CLIP).

What is claimed is: 
     
         1 . 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. 
     
     
         2 . The polymer blend of  claim 1 , wherein said polymer blend comprises a toughener. 
     
     
         3 . The polymer blend of  claim 1 , wherein said heat polymerized second component comprises an epoxy or cyanate ester polymer. 
     
     
         4 . The polymer blend of  claim 1  configured as a three-dimensional object, said object produced by the process of additive manufacturing. 
     
     
         5 . 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;   (b) heat-polymerizable monomers and/or prepolymers;   (c) a hardener; 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.   
     
     
         6 . The resin of  claim 5 , further comprising:
 (e) a toughener, optionally wherein the toughener has a phenol, amine, epoxide, or isocyante reactive end group reactive with epoxides.   
     
     
         7 . The resin of  claim 5 , wherein said hardener comprises a polyamine. 
     
     
         8 . The resin of  claim 5 , wherein said resin comprises a chain extender, and optionally further comprises a chain extender catalyst. 
     
     
         9 . The resin of  claim 5 , wherein said diluent comprises N,N′-dimethylacrylamide, n-vinyl-2-pyrrolidone, n-vinyl formamide, n-vinyl caprolactam, acryloylmorpholine, or a mixture of two or more thereof. 
     
     
         10 . The resin of  claim 5 , 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. 
     
     
         11 . The resin of  claim 5 , 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. 
     
     
         12 . The resin of  claim 5 , further comprising at least one photoinitiator, optionally at least one dye, and optionally at least one filler. 
     
     
         13 . The resin of  claim 5 , wherein said resin comprises a cyanate ester or epoxy resin. 
     
     
         14 . A method of making a three-dimensional object, comprising:
 (a) providing a resin of  claim 5 ;   (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 to produce said three-dimensional object.   
     
     
         15 . The method of  claim 14 , said irradiating carried out under conditions in which said organic diluent chemically reacts by an amount sufficient to increase the strength of said intermediate. 
     
     
         16 . The method of  claim 14 , 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. 
     
     
         17 . The method of  claim 14 , wherein said producing step (b) is carried out by stereolithography. 
     
     
         18 . The method of  claim 14 , wherein said producing step (b) is carried out by continuous liquid interface production.