Network polymers and methods of making and using same

A composition comprising a cross-linked CAN polymer comprising a plurality of thioester linkages and a plurality of free thiol groups, and further comprising at least one exchange catalyst selected from the group consisting of a base and a nucleophile,

• wherein the base is selected from the group consisting of a photo-activatable base and a thermal-activatable base,
• wherein the polymer network undergoes bond exchange through nucleophilic attack on at least one thioester linkage by at least one free thiol group,
• optionally wherein the at least one exchange catalyst is covalently bound to the CAN polymer;
• and
• optionally wherein the composition further comprises an acid selected from the group consisting of a photo-activatable acid and a thermal-activatable acid,
• wherein the CAN polymer comprises at least one polymerized multifunctional thioester containing monomer of Formula (I):
• wherein in (I):
• A1 and A2 are each independently selected from the group consisting of optionally substituted C1-C15 alkylene, optionally substituted C2-C15 alkenylene, optionally substituted C2-C15 alkynylene, optionally substituted C12-C15 heteroalkylene, optionally substituted C2-C15 heteroalkenylene, and optionally substituted C2-C15 heteroalkynylene;
• E1 and E2 are each independently selected from the group consisting of:
• wherein each instance of Y1 is independently selected from the group consisting of O and NR1;
• and each instance of R1 being independently selected from the group consisting of H and C1-C6 alkyl;
• m1 is 0 or 1;
• m2 is 0 or 1;
• X1 is
• wherein:
• bond a is to A1,
• bond b is to E1,
• Q is CH2 or
• and
• n is 0, 1, 2, 3, 4, 5 or 6;
• X2 is
• wherein:
• bond a is to A2,
• bond b is to E2,
• Q is CH2 or
• and
• n is 0, 1, 2, 3, 4, 5 or 6;
• each instance of Y2, and Y3 is independently selected from the group consisting of CR12, O and NR1;
• and
• each instance of R1 is independently selected from the group consisting of H and C1-C6 alkyl.