Biofouling resistant coatings and methods of making and using the same

1. A copolymer comprising:

a) a repeating unit of Formula (VII):

wherein

each R 1a and R 1b is independently selected from hydrogen and halogen;

each R 2a and R 2b is independently selected from halogen, —CN, and optionally substituted C 1 -C 6 fluoroalkyl;

each A 1 and A 2 is independently selected from —C(═O)—, —S(═O)—, —S(═O) 2 —, and —S(═O)(═NR 3c )—;

each B 1 and B 2 is independently selected from —O— and —NR 3c —;

Z 1 is —(CR 6c R 6d ) s —;

each R 4c , R 4d , R 5d , R 5e , R 6c , and R 6d is independently selected from hydrogen, halogen, —CN, —OR 9a , optionally substituted C 1 -C 4 alkyl, optionally substituted C 1 -C 4 fluoroalkyl, optionally substituted C 2 -C 6 alkenyl, —NR 3c R 3d , —S(═O) 2 O − , —S(═O) 2 OR 9a , —C(═O)O − , and —C(═O)OR 9a ;

each R 3c and R 3d is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, —X-optionally substituted C 1 -C 4 alkyl, optionally substituted C 2 -C 6 alkenyl, and optionally substituted aryl;

X is —C(═O)—, —S(═O)—, or —S(═O) 2 —;

each R 9a , R 11a , R 11b , and R 11c is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, and optionally substituted aryl;

n is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, and 8; and

s is an integer selected from 1, 2, 3, 4, and 5;

b) a repeating unit of Formula (VIII):

wherein,

A 3 is —C(═O)—, —S(═O)—, —S(═O) 2 —, or —S(═O)(═NR 3c )—;

B 3 is —O— or —NR 3c —;

D is —S(═O) 2 O − , —S(═O) 2 OR 9a , —C(═O)O − , or —C(═O)OR 9a ;

Z 2 is —(CR 6c R 6d ) t —;

Z 3 is —(CR 6c R 6d ) p —;

each R 3a and R 3b is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, and optionally substituted benzyl;

each R 6c and R 6d is independently selected from hydrogen, halogen, —CN, —OR 9a , optionally substituted C 1 -C 4 alkyl, optionally substituted C 1 -C 4 fluoroalkyl, optionally substituted C 2 -C 6 alkenyl, —NR 3c R 3d , —S(═O) 2 O − , —S(═O) 2 OR 9a , —C(═O)O − , and —C(═O)OR 9a ;

each R 3c and R 3d is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, —X-optionally substituted C 1 -C 4 alkyl, optionally substituted C 2 -C 6 alkenyl, and optionally substituted aryl;

X is —C(═O)—, —S(═O)—, or —S(═O) 2 —;

each R 9a , R 12a , R 12b , and R 12c is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, and optionally substituted aryl;

t is an integer selected from 1, 2, 3, 4, or 5;

p is an integer selected from 1, 2, 3, 4, or 5; and

wherein the repeating unit of Formula (VIII) is charged or zwitterionic; and

c) a repeating unit of Formula (IX):

A 4 is —C(═O)—, —S(═O)—, —S(═O) 2 —, or —S(═O)(═NR 3c )—;

B 4 is —O— or —NR 3c —;

Z 4 is —(CR 6c R 6d ) k —;

E is —CN, —OR 9a , —NR 9a R 9b , —NR 9a R 9b R 9c+ , optionally substituted C 1 -C 4 alkyl, optionally substituted C 1 -C 6 fluoroalkyl, —S(═O) 2 O − , —S(═O) 2 OR 9a , —C(═O)O − , or —C(═O)OR 9a ;

each R 6c , and R 6d is independently selected from hydrogen, halogen, —CN, —OR 9a , optionally substituted C 1 -C 4 alkyl, optionally substituted C 1 -C 4 fluoroalkyl, optionally substituted C 2 -C 6 alkenyl, —NR 3c R 3d , —S(═O) 2 O − , —S(═O) 2 OR 9a , —C(═O)O − , and —C(═O)OR 9a ;

each R 3c and R 3d is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, —X-optionally substituted C 1 -C 4 alkyl, optionally substituted C 2 -C 6 alkenyl, and optionally substituted aryl;

X is —C(═O)—, —S(═O)—, or —S(═O) 2 —;

each R 9a , R 9b , R 9c , R 13a , R 13b , and R 13c is independently selected from hydrogen, optionally substituted C 1 -C 4 alkyl, and optionally substituted aryl; and

k is an integer selected from 1, 2, 3, 4, or 5.

2. The copolymer of claim 1 , wherein each R 1a , R 1b , R 2a , and R 2b is F.

3. The copolymer of claim 1 , wherein A 1 is —S(═O) 2 — and each A 2 , A 3 , and A 4 is —C(═O)—.

4. The copolymer of claim 1 , wherein each B 1 , B 2 , and B 3 is independently —O— or —NR 3c —.

5. The copolymer of claim 4 , wherein each R 3c is hydrogen or —CH 3 .

6. The copolymer of claim 1 , wherein D is —S(═O) 2 O − or —C(═O)O − .

7. The copolymer of claim 1 , wherein E is —NR 9a R 9b R 9c+ or —S(═O) 2 OR 9a .

8. The copolymer of claim 7 , wherein each R 9a , R 9b , and R 9c is independently hydrogen or C 1 -C 4 alkyl.

9. The copolymer of claim 1 , wherein each R 3a and R 3b is —CH 3 .

10. The copolymer of claim 1 , wherein each R 3c , R 3d , R 4c , R 4d , R 5d , R 5e , R 6c , and R 6d is hydrogen.

11. The copolymer of claim 1 , wherein each R 11a , R 12a , and R 13a is hydrogen or —CH 3 .

12. The copolymer of claim 1 , wherein each R 11b , R 11c , R 12b , R 12c , R 13b , and R 13c is hydrogen.

13. The copolymer of claim 1 , wherein n is 0, 1, or 2.

14. The copolymer of claim 1 , wherein each s, t, p, and k is independently 1, 2 or 3.