Methods for Reactive Three-Dimensional Printing by Extrusion

Abstract

Methods of printing a three-dimensional object using co-reactive components are disclosed. Thermosetting compositions for three-dimensional printing are also enclosed.

1 .- 26 . (canceled) 
     
     
         27 . A method of three-dimensional printing an object comprising:
 (a) extruding a coreactive composition, wherein,
 the coreactive composition comprises a first component comprising at least two first functional groups and a second component comprising at least two second functional groups, 
 the second functional group is reactive with the first functional group; and 
 at least one of the first functional group and the second functional group comprises a saturated functional group; and 
   (b) building a three-dimensional printed object;   wherein extruding comprises forming an extrusion wherein the extrusion is characterized by a cross-sectional profile having an inhomogeneous material composition.   
     
     
         28 . The method of  claim 27 , wherein,
 the cross-sectional profile comprises a first proton and a second portion;   the first portion comprises a molar ratio of the first component to the second component greater than 1; and   the second portion comprises a molar ratio of the first component to the second component less than 1.   
     
     
         29 . The method of  claim 28 , wherein the first portion and the second portion are on opposite sides of the cross-sectional profile. 
     
     
         30 . The method of  claim 28 , wherein,
 the first portion comprises an equivalent ratio of the first functional group to the second functional group greater than 1; and   the second portion comprises an equivalent ratio of the first functional group to the second functional group less than 1.   
     
     
         31 . The method of  claim 27 , wherein an equivalents ratio of the first component to the second component is not homogeneous throughout the cross-sectional profile. 
     
     
         32 . The method of  claim 27 , wherein an equivalents ratio of the first component to the second component is homogeneous throughout the cross-sectional profile. 
     
     
         33 . The method of  claim 27 , wherein a surface of the extrudate has an excess of the first functional groups with respect to the second functional groups. 
     
     
         34 . The method of  claim 27 , wherein the cross-sectional profile is characterized by a variable ratio of the first coreactive component and the second coreactive component. 
     
     
         35 . The method of  claim 27 , wherein,
 the first functional group is a carboxylic acid; and the second functional group is an epoxy; or   the first functional group is an activated unsaturated group selected from a (meth)acrylate, a maleic acid, a fumaric acid, a Michael acceptor, a vinyl ether, an acetoacetate, an acyclic carbonate, and a malonate; and the second functional group is selected from a primary amine, a secondary amine, and a malonate; or   the first functional group is an isocyanate; and the second functional group is a hydroxyl; or   the first functional group is an isocyanate; and the second functional group is selected from a primary amine and a secondary amine; or   the first functional group is selected from a cyclic carbonate, an acetoacetate, and an epoxy; and the second functional group is selected from a primary amine and a secondary amine; or   the first functional group is a thiol; and the second functional group is selected from an alkenyl, a vinyl ether, a Michael acceptor group and a (meth)acrylate; or   at least one of the first functional group and the second functional group comprises a saturated functional group.   
     
     
         36 . The method of  claim 27 , wherein the first component comprises a polyisocyanate and the second component comprises a polyamine. 
     
     
         37 . The method of  claim 27 , wherein the first component comprises a polythiol; and the second component comprises a polyalkenyl. 
     
     
         38 . The method of  claim 27 , wherein the first component comprises a polyfunctional Michael acceptor and the second component comprises a polyfunctional Michael donor. 
     
     
         39 . The method of  claim 27 , wherein extruding comprises extruding the coreactive composition through a single nozzle. 
     
     
         40 . The method of  claim 27 , wherein the coreactive composition is a thermosetting composition. 
     
     
         41 . The method of  claim 27 , wherein the coreactive composition is reactive at a temperature less than 30° C.