Network polymers and methods of making and using same

1. 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):

A 1 and A 2 are each independently selected from the group consisting of optionally substituted C 1 -C 15 alkylene, optionally substituted C 2 -C 15 alkenylene, optionally substituted C 2 -C 15 alkynylene, optionally substituted C 12 -C 15 heteroalkylene, optionally substituted C 2 -C 15 heteroalkenylene, and optionally substituted C 2 -C 15 heteroalkynylene;

E 1 and E 2 are each independently selected from the group consisting of:

wherein each instance of Y 1 is independently selected from the group consisting of O and NR 1 ; and each instance of R 1 being independently selected from the group consisting of H and C 1 -C 6 alkyl;

m1 is 0 or 1;

m2 is 0 or 1;

X 1 is

 wherein:

bond a is to A 1 ,

bond b is to E 1 ,

Q is CH 2 or

and

n is 0, 1, 2, 3, 4, 5 or 6;

X 2 is

 wherein:

bond a is to A 2 ,

bond b is to E 2 ,

Q is CH 2 or

 and

n is 0, 1, 2, 3, 4, 5 or 6;

each instance of Y 2 , and Y 3 is independently selected from the group consisting of CR 1 2 , O and NR 1 ; and

each instance of R 1 is independently selected from the group consisting of H and C 1 -C 6 alkyl.

2. The composition of claim 1 , wherein the base has a conjugate acid with a pKa from about 2 to about 15, or the nucleophile has a nucleophilicity value (N) greater than about 10.

3. The composition of claim 1 , wherein the CAN polymer is formed through one or more processes selected from the group consisting of thiol-ene polymerization, thiol-alkyne polymerization, thiol-acrylate polymerization, thiol-methacrylate, acrylate polymerization, methacrylate polymerization, styrene polymerization, alcohol-isocyanate polymerization, thiol-isocyanate polymerization, thiol-epoxide polymerization, thiol-isothiocyanate polymerization, thiol-halide polymerization, thiol-malemide, thiol-activated ester polymerization, copper-catalyzed azide alkyne polymerization, strain-promoted azide alkyne polymerization, and epoxide-carboxylic acid polymerization.

4. The composition of claim 1 , wherein at least one applies:

(a) the photo-activatable base is a compound selected from the group consisting of:

 1,2-Diisopropyl-3-[Bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, and (Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate;

(b) the base is a thermal-activatable base selected from the group consisting of:

(c) the photo-activatable acid is a compound selected from the group consisting of:

 Bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, Bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, Bis(4-tert-butylphenyl)iodonium, Boc-methoxyphenyldiphenylsulfonium triflate, (4-tert-Butylphenyl)diphenylsulfonium triflate, Diphenyliodonium hexafluorophosphate, Diphenyliodonium nitrate, Diphenyliodonium perfluoro-1-butanesulfonate, Diphenyliodonium p-toluenesulfonate, Diphenyliodonium triflate, (4-Fluorophenyl)diphenylsulfonium triflate, N-Hydroxynaphthalimide triflate, N-Hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, (4-Iodophenyl)diphenylsulfonium triflate, (4-Methoxyphenyl) diphenylsulfonium triflate, 2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, (4-Methylphenyl)diphenylsulfonium triflate, (4-Methylthiophenyl)methyl phenyl sulfonium triflate, (4-Phenoxyphenyl)diphenylsulfonium triflate, (4-Phenylthiophenyl)diphenylsulfonium triflate, Triarylsulfonium hexafluorophosphate salts, Triphenylsulfonium perfluoro-1-butanesufonate, Triphenylsulfonium triflate, Tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate, and Tris(4-tert-butylphenyl)sulfonium triflate; or

(d) the thermal-activatable acid is selected from the group consisting of:

5. The composition of claim 1 , wherein the CAN polymer does not exhibit significant bond exchange before activation of the base, and wherein the CAN polymer exhibits bond exchange after activation of the base.

6. The composition of claim 1 , wherein the CAN polymer exhibits bond exchange before activation of the acid and wherein the CAN polymer does not exhibit significant bond exchange after activation of the acid.

7. The composition of claim 1 , wherein the at least one polymerized multifunctional thioester containing monomer is a monomer of Formula (Ia):

8. The composition of claim 1 , wherein the at least one polymerized multifunctional thioester containing monomer is selected from the group consisting of:

wherein each occurrence of m is independently selected from the group consisting of 0, 1, 2, 3, 4, 5, and 6.