Ternary orthogonal photopolymers

A method of generating a modulus gradient in a polymeric material, the method comprising:

• subjecting an initial precursor resin mixture to a polymerization or crosslinking stimulus, wherein the initial precursor resin mixture comprises one or more monofunctional, bifunctional, trifunctional, and tetrafunctional monomers, the one or more monomers comprising at least three different polymerizable or crosslinkable moieties selected from an alkene group, a thiol group, and an epoxy group, wherein the one or more monomers comprise at least a bifunctional thiol and a tetrafunctional thiol,
• generating one or more intermediate resin mixtures, and
• subjecting the one or more intermediate resin mixtures to one or more polymerization and/or crosslinking stimuli selected from at least two different raised temperatures, wherein a first raised temperature is between about 50° C. and about 100° C.,
• wherein the method is a 3D printing method.