Network toughening of additively manufactured, high glass transition temperature materials via sequentially cured, interpenetrating polymers

A method of preparing an interpenetrating polymer network (IPN), the method comprising:

• applying vat photopolymerization (VPP) to a mixture of:
• a crosslinker comprising at least one amine functionality, and a monomer, oligomer, or polymer bearing at least one vinyl ester functionality and at least one epoxy functionality, under conditions whereby the vinyl ester functionality is photopolymerized;
• and
• exposing the resulting mixture to thermal conditions whereby epoxy-amine polymerization takes place to form the IPN,
• wherein the IPN further comprises
• or a crosslinked product thereof.

A composition comprising at least one monomer selected from the group consisting of:

• wherein:
• R1 is
• L is selected from the group consisting of a bond, C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl;
• R2 is selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl, wherein the substituents are selected from the group consisting of optionally substituted aryl and optionally substituted heteroaryl;
• each instance of R3 is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl;
• R4 is
• each instance of X is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl;
• n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20;
• m is 0, 2, 4, 6, or 8.

A monomer comprising of Formula II, Formula III, Formula III-A, or Formula IV:

• wherein:
• R1
• L is selected from the group consisting of a bond, C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl;
• R2 is selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, wherein the substituents are selected from the group consisting of optionally substituted aryl and optionally substituted heteroaryl;
• each instance of R3 is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl;
• R4 is
• each instance of Y is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl;
• n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20;
• m is 0, 2, 4, 6, or 8.