Free-standing non-fouling polymers, their compositions, and related monomers

Abstract

Free-standing non-fouling polymers and polymeric compositions, monomers and macromonomers for making the polymers and polymeric compositions, objects made from the polymers and polymeric compositions, and methods for making and using the polymers and polymeric compositions

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 
     
         1 . A monomer having a formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         and wherein 
         R 1  is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C 1 -C 20  alkyl, and C 6 -C 12  aryl groups, or CN; 
         R 4 , R 5 , R 6 , and R 7  are independently selected from the group consisting of hydrogen, C 1 -C 20  alkyl, and C 6 -C 12  aryl, cyclic alkyl, fluoroalkyl, and void; 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening; 
         L is C or Si or void; 
         L 1 , L 3 , and L 4  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         L 2  is independently selected from —(CH 2 ) x —, or —(CH(CN)) x —, where x is an integer from 1 to 20; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO 2   − ; 
         B 2  is C or SO; 
         C 1  is PO 4 ; and 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C 1 -C 20  alkyl), lactate, benzoate, and salicylate, or void. 
       
     
     
         2 . A monomer having a formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening; 
         L is C or Si or void; 
         L 1 , L 2 , L 3 , and L 4  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO 2   − ; 
         B 2  is C or SO; 
         C 1  is PO 4 ; and 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C 1 -C 20  alkyl), lactate, benzoate, and salicylate or void. 
       
     
     
         3 . A monomer having a formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 6  is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, C6-C12 aryl, CN, cyclic alkyl, fluoro alkyl, and void; 
         R 4 , R 5 , R 7 , and R 8  are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl group, fluoro alkyl, and void; 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening; 
         L 0  and L 4  are C or Si or void; 
         L 1 , L 2 , L 3 , L 5 , and L 6  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO2-; 
         B 2  is C or SO; 
         C 1  is PO 4 ; and 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C1-C20 alkyl), lactate, benzoate, salicylate, or void. 
       
     
     
         4 . A macromonomer having a formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         and wherein 
         R 1  is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C 1 -C 20  alkyl, C 6 -C 12  aryl, CN; 
         R 4 , R 5 , R 6 , and R 7 , are independently selected from the group consisting of hydrogen, C 1 -C 20  alkyl, C 6 -C 12  aryl, cyclic alkyl, fluoro alkyl, and void; 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization; 
         L is C or Si or void; 
         L 1 , L 3 , and L 4  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         L 2  is independently selected from —(CH 2 ) x —, or —(CH(CN)) x —, where x is an integer from 1 to 20; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO 2   − ; 
         B 2  is C or SO; 
         C 1  is PO 4 ; 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C 1 -C 20  alkyl), lactate, benzoate, salicylate, or void; and 
         j is an integer from 1 to about 1000. 
       
     
     
         5 . A macromonomer having a formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein 
         R 4 , R 5 , R 6 , and R 7  are independently selected from the group consisting of hydrogen, C 1 -C 20  alkyl, C 6 -C 12  aryl, cyclic alkyl, fluoro alkyl, and void; 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization; 
         L is C or Si or void; 
         L 1 , L 3 , and L 4  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         L 2  is independently selected from —(CH 2 ) x —, or —(CH(CN)) x —, where x is an integer from 1 to 20; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO 2   − ; 
         B 2  is C or SO; 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C 1 -C 20  alkyl), lactate, benzoate, salicylate, or void; and 
         j is an integer from 1 to about 1000. 
       
     
     
         6 . A macromonomer having a formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 6  are selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, C6-C12 aryl, CN, cyclic alkyl, fluoroalkyl, and void; 
         R 4 , R 5 , R 7 , and R 8  are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoroalkyl, and void; 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization; 
         L 0  and L 4  are C or Si or void; 
         L 1 , L 2 , L 3 , L 5 , and L 6  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO 2   − ; 
         B 2  is C or SO; 
         C 1  is PO 4 ; 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C1-C20 alkyl), lactate, benzoate, and salicylate or void; and 
         j and k are integers independently selected from 1 to about 1000. 
       
     
     
         7 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization; 
         X a  is selected from —(CH 2 ) n —, where n is 0 to 6; 
         X b  is —(CH 2 ) p —, where p is 1 to 6; 
         R a  is selected from hydrogen and C1-C6 alkyl; 
         X c  is —(CH 2 ) q —, where q is 1 to 6; and 
         Y is selected from CO 2   − , SO 3   − , or PO 4   2− . 
       
     
     
         8 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization; 
         X a  is selected from —(CH 2 ) n —, where n is 0 to 6; 
         X b  is —(CH 2 ) p —, where p is 1 to 6; 
         R a , R b , and R c  are independently selected from hydrogen and C 1 -C 6  alkyl; 
         X c  is —(CH 2 ) q —, where q is 1 to 6; 
         X d  is —(CH 2 ) r —, where r is 1 to 6; and 
         Y is selected from CO 2   − , SO 3   − , or PO 4   2− . 
       
     
     
         9 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         R 2  and R 3  are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization; 
         X a  is selected from —(CH 2 ) n —, where n is 0 to 6; 
         X b  is —(CH 2 ) p —, where p is 1 to 6; 
         R a  and R b  are independently selected from hydrogen and C1-C6 alkyl; and 
         X c  is —(CH 2 ) q —, where q is 1 to 6. 
       
     
     
         10 . The monomer of any one of  claim 1 - 9 , wherein R 2  and R 3  are independently selected from the group consisting of F, Cl, Br, I, SH, protected thiols, NH 2 , —NH— (secondary amine), N═C═O, protected NCO, N═C═S, COOH, COSH, C(═S)SH, OCOOH, OCOSH, OC(═S)OH, SC(═O)SH, SC(═S)SH, N(C═O)NH 2 , N(C═NH)NH 2 , N(C═S)NH 2 , δ-valerolactone moiety, ε-caprolactone moiety, CH 2 ═CH—C(═O)—O—, CH 2 ═CH—C(═O)—NH—, CH 2 ═CH—C(═O)—S—, CN, CH 2 ═CH(CH 3 )—C(═O)—O—, CH 2 ═CH(CH 3 )—C(═O)—O—, OH, azides, alkynes, or void. 
     
     
         11 . The monomer of any one of  claim 1 - 9 , wherein R 2  and R 3  are selected from the group consisting of —N═C═O and —N═C═S. 
     
     
         12 . The monomer of any one of  claim 1 - 9 , wherein R 2  and R 3  are Michael acceptors selected from the group consisting of CH 2 ═CH—C(═O)—O—, CH 2 ═CH—C(═O)—NH—, CH 2 ═CH—C(═O)—S—, CH 2 ═CH(CH 3 )—C(═O)—O—, and CH 2 ═CH(CH 3 )—C(═O)—O—. 
     
     
         13 . The monomer of any one of  claim 1 - 9 , wherein R 2  and R 3  are selected from the group consisting of 
       
         
           
           
               
               
           
         
         wherein 
         m and n are independently selected from 1 to 3. 
         R 4  and R 5  are independently selected from the group consisting of hydrogen, C 1 -C 20  alkyl, and C 6 -C 12  aryl, cyclic alkyl, fluoroalkyl, and void; 
         L 1  is independently selected from —(CH 2 ) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         L 2  is —(CH 2 ) x  where x is an integer from 1 to 20; 
         A 1  is N; 
         B 2  is C or SO; and 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C 1 -C 20  alkyl), lactate, benzoate, and salicylate, or void. 
       
     
     
         14 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         X a  is selected from —O(C═O)(CH 2 ) n — where n is 1 to 6, —O(CH 2 ) m — where m is 1 to 6, or is absent; 
         R a  and R b  are independently selected from hydrogen and C1-C6 alkyl; and 
         X b  is —(CH 2 ) n — where n is 1 to 6. 
       
     
     
         15 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         X a  is selected from —O(C═O)(CH 2 ) n —, where n is 1 to 6, or —NH(C═O)(CH 2 ) m —, where m is 1 to 6; 
         R a  and R b  are independently selected from hydrogen and C1-C6 alkyl; and 
         X b  is —(CH 2 ) p —, where p is 1 to 6; and 
         X c  is —(CH 2 ) q —, where q is 1 to 6. 
       
     
     
         16 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         X a  is selected from —(CH 2 ) n —, where n is 0 to 6; 
         X b  is —(CH 2 ) p —, where p is 1 to 6; 
         R a  and R b  are independently selected from hydrogen and C1-C6 alkyl; and 
         X c  is —(CH 2 ) q —, where q is 1 to 6. 
       
     
     
         17 . A monomer having the formula: 
       
         
           
           
               
               
           
         
         or a salt thereof, 
         wherein 
         X a  is selected from —(CH 2 ) n —, where n is 0 to 6; 
         X b  is —(CH 2 ) p —, where p is 1 to 6; 
         R a  and R b  are independently selected from hydrogen and C1-C6 alkyl; and 
         X c  is —(CH 2 ) q —, where q is 1 to 6. 
       
     
     
         18 . A polymer prepared by polymerizing a monomer of any one of  claim 1 - 17 . 
     
     
         19 . A polymer prepared by polymerizing a monomer of any one of  claim 1 - 17  with a second monomer. 
     
     
         20 . A polymer having the formula: 
       
         
           
           
               
               
           
         
         wherein 
         K 1 , K 2 , K 3 , and K 4  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         R 2  and R 3  are independently selected from H, F, Cl, Br, I, OH, SH, protected thiols, NH 2 , —NH— (secondary amine), N═C═O, N═C═S, COOH, COSH, C(═S)SH, OCOOH, OCOSH, OC(═S)OH, SC(═O)SH, SC(═S)SH, N(C═O)NH 2 , N(C═NH)NH 2 , N(C═S)NH 2 , δ-valerolactone moiety, ε-caprolactone moiety, CH 2 ═CH—C(═O)—O—, CH 2 ═CH—C(═O)—NH—, CH 2 ═CH—C(═O)—S—, CN, CH 2 ═CH(CH 3 )—C(═O)—O—, CH 2 ═CH(CH 3 )—C(═O)—NH—, or void; 
         n is an integer from 5 to about 10,000; 
         j is an integer from 1 to about 1000; 
         M 1  and M 2  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; and 
         Z and X are independently selected from zwitterionic groups. 
       
     
     
         21 . The polymer of  claim 20 , wherein the Z and X are independently selected from the group consisting of 
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 8  are selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, and C6-C12 aryl groups, CN; 
         R 4 , R 5 , R 6 , and R 7  are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoroalkyl, or void; 
         L is C or Si or void; 
         L 1 , L 3 , L 4 , and L 5  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         L 2  is independently selected from —(CH 2 ) x —, or —(CH(CN)) x —, where x is an integer from 1 to 20; 
         A 1  is N; 
         B 1  is C, S, SO, PO, or PO 2   − ; 
         B 2  is C or SO; 
         C 1  is PO 4 ; and 
         M is selected from Cl, Br, I, SO 4 , NO 3 , ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C1-C20 alkyl), lactate, benzoate, salicylate, or void. 
       
     
     
         22 . A polymer having the formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 5  is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C 1 -C 20  alkyl, and C 6 -C 12  aryl groups, CN; 
         R 2 , R 3 , R 4 , and R 6  are independently selected from the group consisting of hydrogen, C 1 -C 20  alkyl, C 6 -C 12  aryl, cyclic alkyl, fluoroalkyl, or void; 
         L 0  and L 5  are independently C or Si or void; 
         L 1 , L 2 , L 3 , L 4 , L 6 , and L 7  are independently selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         M 1  and M 2  are independently selected from the group consisting of —O—(CH 2 ) n —, —S—(CH 2 ) n —, —C(═O)—(CH 2 ) n —, —C(═S)—(CH 2 ) n —, —C(═NH)—(CH 2 ) n — and —NH—(CH 2 ) n —, wherein n is an integer from 1 to 20; —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, and —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void; 
         B 1  is C, S, SO, P, or PO; 
         B 2  is C or SO; 
         A 1  is N, S, or P; 
         M is selected from Cl, Br, I, SO 4 , NO 3  ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C 1 -C 20  alkyl), lactate, benzoate, salicylate, or void; 
         wherein the ratio between m and n is selected from 0.8 to 1.2; and 
         wherein m and n are independently integers from 1 to about 10,000. 
       
     
     
         23 . A polymer of any one of  claim 18 - 22  having a fibrinogen binding level of less than 30 ng/cm 2  in a fibrinogen binding assay (polymer surface is incubated at 37° C. for 90 minutes with a 1.0 mg/mL fibrinogen solution in 0.15 M phosphate buffered saline at pH 7.4). 
     
     
         24 . A polymer of any one of  claim 18 - 22  having a tensile or compressive strength greater than 0.5 MPa. 
     
     
         25 . A polymer of any one of  claim 18 - 22  having a fibrinogen binding level of less than 30 ng/cm 2  in a fibrinogen binding assay (polymer surface is incubated at 37° C. for 90 minutes with a 1.0 mg/mL fibrinogen solution in 0.15 M phosphate buffered saline at pH 7.4) and a tensile or compressive strengths greater than 0.5 MPa. 
     
     
         26 . A polymer of any one of  claim 18 - 22 , wherein the polymer is crosslinked. 
     
     
         27 . A composite, comprising a polymer of any one of  claim 18 - 22  and a second polymer. 
     
     
         28 . The composite of  claim 27 , wherein the second polymer is selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyureas, polysulfides, polysulfones, polyimides, polyepoxies, aromatic polyesters, cellulosics, fluoropolymers, polyacrylics, polyamides, polyanhydrides, polyethers, vinyl polymers, phenolics, elastomers, and other addition polymers. 
     
     
         29 . The composite of  claim 27  further comprising a strength additive. 
     
     
         30 . The composite of  claim 27  further comprising a strength additive selected from the groups consisting of fiber, clays, nanotubes, and other inorganic objects. 
     
     
         31 . A polymer of any one of  claim 18 - 22  formed into an object by a method selected from the group consisting of injection molding, blow molding, extrusion molding, calendaring molding, flow casting, compression molding, prevarication molding, and 3D printing. 
     
     
         32 . A surface coating for a substrate, comprising a polymer of any one of  claim 18 - 22 . 
     
     
         33 . The surface coating of  claim 32 , wherein the substrate is a consumer product. 
     
     
         34 . The surface coating of  claim 32 , wherein the substrate is a marine product. 
     
     
         35 . The surface coating of  claim 32 , wherein the substrate is a marine product selected from the group consisting of marine vessel hulls, marine structures, bridges, propellers, heat exchangers, periscopes, sensors, fish nets, cables, tubes/pipes, containers, membranes, and oil booms. 
     
     
         36 . The surface coating of  claim 32 , wherein the substrate is a biomedical product. 
     
     
         37 . The surface coating of  claim 32 , wherein the substrate is a biomedical product selected from the group consisting of catheters, ear drainage tubes, feeding tubes, glaucoma drainage tubes, hydrocephalous shunts, keratoprosthesis, nerve guidance tubes, tissue adhesives, x-ray guides, artificial joints, artificial heart valves, artificial blood vessels, pacemakers, left ventricular assist devices (LVAD), artery grafts, vascular grafts, stents, intravascular stents, cardiac valves, joint replacements, blood vessel prostheses, skin repair devices, cochlear replacements, contact lenses, artificial ligaments and tendons, dental implants, and tissue scaffolds for regenerative tissue engineering. 
     
     
         38 . The surface coating of  claim 32 , wherein the substrate is a delivery vehicle selected from the group consisting of a drug delivery vehicle, a gene delivery vehicle, an RNA delivery vehicle, a protein delivery vehicle. 
     
     
         39 . A polymer of any one of  claim 18 - 22  coupled to a biomolecule. 
     
     
         40 . The polymer of  claim 39 , wherein the biomolecule is a therapeutic agent, a nucleic acid (e.g., a gene or DNA or RNA), a protein (e.g., antibody or functional fragment thereof), a lipid, a peptide, or a small molecule having a molecular weight less than about 800. 
     
     
         41 . A polymer of any one of  claim 18 - 22  coupled to a cell or microorganism. 
     
     
         42 . A polymer of any one of  claim 18 - 22  coupled to a nanoparticle. 
     
     
         43 . The polymer of  claim 42 , wherein the nanoparticle is a liposome or a micelle. 
     
     
         44 . The polymer of  claim 42 , wherein the nanoparticle is a quantum dot. 
     
     
         45 . The polymer of  claim 42 , wherein the nanoparticle is an iron oxide, silica, or gold nanoparticle. 
     
     
         46 . A bulk material comprising a polymer of any one of  claim 18 - 22 , wherein the bulk material is formed into an object by a method selected from the group consisting of injection molding, blow molding, extrusion molding, calendaring molding, flow casting, compression molding, prevarication molding, and 3D printing. 
     
     
         47 . A surface coating for a substrate, comprising a bulk material comprising a polymer of any one of  claim 18 - 22 . 
     
     
         48 . The surface coating of  claim 47 , wherein the substrate is a consumer product. 
     
     
         49 . The surface coating of  claim 47 , wherein the substrate is a marine product. 
     
     
         50 . The surface coating of  claim 47 , wherein the substrate is a marine product selected from the group consisting of marine vessel hulls, marine structures, bridges, propellers, heat exchangers, periscopes, sensors, fish nets, cables, tubes/pipes, containers, membranes, and oil booms.