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

A monomer having a formula selected from the group consisting of:

• wherein
• R2 and R3 are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening;
• L is C or Si or void;
• L1, L2, L3, and L4 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• A1 is N;
• B1 is C, S, SO, PO, or PO2−;
• B2 is C or SO;
• C1 is PO4;
• and
• M is selected from Cl, Br, I, SO4, NO3 ClO4, BF4, PF6, N(SO2CF3)2, SO3CF3, RCOO (R is C1-C20 alkyl), lactate, benzoate, and salicylate or void.

A monomer having a formula selected from the group consisting of:

• wherein
• R1 and R6 is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, C6-C12 aryl, CN, cyclic alkyl, fluoro alkyl, and void;
• R4, R5, R7, and R8 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl group, fluoro alkyl, and void;
• R2 and R3 are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening;
• L0 and L4 are C or Si or void;
• L1, L2, L3, L5, and L6 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• A1 is N;
• B1 is C, S, SO, PO, or PO2-;
• B2 is C or SO;
• C1 is PO4;
• and
• M is selected from Cl, Br, I, SO4, NO3 ClO4, BF4, PF6, N(SO2CF3)2, SO3CF3, RCOO (R is C1-C20 alkyl), lactate, benzoate, salicylate, or void.

A macromonomer having a formula selected from the group consisting of:

• and wherein
• R1 is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, C6-C12 aryl, CN;
• R4, R5, R6, and R7, are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoro alkyl, and void;
• R2 and R3 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;
• L1, L3, and L4 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• L2 is independently selected from —(CH2)x—, or —(CH(CN))x—, where x is an integer from 1 to 20;
• A1 is N;
• B1 is C, S, SO, PO, or PO2−;
• B2 is C or SO;
• C1 is PO4;
• M is selected from Cl, Br, I, SO4, NO3 ClO4, BF4, PF6, N(SO2CF3)2, SO3CF3, RCOO (R is C1-C20 alkyl), lactate, benzoate, salicylate, or void;
• and
• j is an integer from 1 to about 1000.

A macromonomer having a formula selected from the group consisting of:

• wherein
• R4, R5, R6, and R7 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoro alkyl, and void;
• R2 and R3 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;
• L1, L3, and L4 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• L2 is independently selected from —(CH2)x—, or —(CH(CN))x—, where x is an integer from 1 to 20;
• A1 is N;
• B1 is C, S, SO, PO, or PO2−;
• B2 is C or SO;
• M is selected from Cl, Br, I, SO4, NO3 ClO4, BF4, PF6, N(SO2CF3)2, SO3CF3, RCOO (R is C1-C20 alkyl), lactate, benzoate, salicylate, or void;
• and
• j is an integer from 1 to about 1000.

A macromonomer having a formula selected from the group consisting of:

• wherein
• R1 and R6 are selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, C6-C12 aryl, CN, cyclic alkyl, fluoroalkyl, and void;
• R4, R5, R7, and R8 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoroalkyl, and void;
• R2 and R3 are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization;
• L0 and L4 are C or Si or void;
• L1, L2, L3, L5, and L6 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• A1 is N;
• B1 is C, S, SO, PO, or PO2−;
• B2 is C or SO;
• C1 is PO4;
• M is selected from Cl, Br, I, SO4, NO3 ClO4, BF4, PF6, N(SO2CF3)2, SO3CF3, 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.

A monomer having the formula:

• or a salt thereof,
• wherein
• R2 and R3 are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization;
• Xa is selected from —(CH2)n—, where n is 0 to 6;
• Xb is —(CH2)p—, where p is 1 to 6;
• Ra is selected from hydrogen and C1-C6 alkyl;
• Xc is —(CH2)q—, where q is 1 to 6;
• and
• Y is selected from CO2−, SO3−, or PO42−.

A monomer having the formula:

• or a salt thereof,
• wherein
• R2 and R3 are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization;
• Xa is selected from —(CH2)n—, where n is 0 to 6;
• Xb is —(CH2)p—, where p is 1 to 6;
• Ra, Rb, and Rc are independently selected from hydrogen and C1-C6 alkyl;
• Xc is —(CH2)q—, where q is 1 to 6;
• Xd is —(CH2)r—, where r is 1 to 6;
• and
• Y is selected from CO2−, SO3−, or PO42−.

A monomer having the formula:

• or a salt thereof,
• wherein
• R2 and R3 are independently selected from a functional group suitable for polymerization by addition, condensation, or ring opening, or free radical polymerization;
• Xa is selected from —(CH2)n—, where n is 0 to 6;
• Xb is —(CH2)p—, where p is 1 to 6;
• Ra and Rb are independently selected from hydrogen and C1-C6 alkyl;
• and
• Xc is —(CH2)q—, where q is 1 to 6.

A monomer having the formula:

• or a salt thereof,
• wherein
• Xa is selected from —O(C═O)(CH2)n— where n is 1 to 6, —O(CH2)m— where m is 1 to 6, or is absent;
• Ra and Rb are independently selected from hydrogen and C1-C6 alkyl;
• and
• Xb is —(CH2)n— where n is 1 to 6.

A monomer having the formula:

• or a salt thereof,
• wherein
• Xa is selected from —O(C═O)(CH2)n—, where n is 1 to 6, or —NH(C═O)(CH2)m—, where m is 1 to 6;
• Ra and Rb are independently selected from hydrogen and C1-C6 alkyl;
• and
• Xb is —(CH2)p—, where p is 1 to 6;
• and
• Xc is —(CH2)q—, where q is 1 to 6.

A monomer having the formula:

• or a salt thereof,
• wherein
• Xa is selected from —(CH2)n—, where n is 0 to 6;
• Xb is —(CH2)p—, where p is 1 to 6;
• Ra and Rb are independently selected from hydrogen and C1-C6 alkyl;
• and
• Xc is —(CH2)q—, where q is 1 to 6.

A monomer having the formula:

• or a salt thereof,
• wherein
• Xa is selected from —(CH2)n—, where n is 0 to 6;
• Xb is —(CH2)p—, where p is 1 to 6;
• Ra and Rb are independently selected from hydrogen and C1-C6 alkyl;
• and
• Xc is —(CH2)q—, where q is 1 to 6.

A polymer having the formula:

• wherein
• K1, K2, K3, and K4 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• R2 and R3 are independently selected from H, F, Cl, Br, I, OH, SH, protected thiols, NH2, —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)NH2, N(C═NH)NH2, N(C═S)NH2, δ-valerolactone moiety, ε-caprolactone moiety, CH2═CH—C(═O)—O—, CH2═CH—C(═O)—NH—, CH2═CH—C(═O)—S—, CN, CH2═CH(CH3)—C(═O)—O—, CH2═CH(CH3)—C(═O)—NH—, or void;
• n is an integer from 5 to about 10,000;
• j is an integer from 1 to about 1000;
• M1 and M2 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)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.

A polymer having the formula selected from the group consisting of:

• wherein
• R1 and R5 is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, and C6-C12 aryl groups, CN;
• R2, R3, R4, and R6 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoroalkyl, or void;
• L0 and L5 are independently C or Si or void;
• L1, L2, L3, L4, L6, and L7 are independently selected from —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• M1 and M2 are independently selected from the group consisting of —O—(CH2)n—, —S—(CH2)n—, —C(═O)—(CH2)n—, —C(═S)—(CH2)n—, —C(═NH)—(CH2)n— and —NH—(CH2)n—, wherein n is an integer from 1 to 20;
• —(CH2)x—, —(CH(CN))x—, —C(═O)NH(CH2)x—, —C(═O)O(CH2)x—, —C(═O)OC(═O)O(CH2)x—, —(CH2)x—O—(CH2)x—, and —(CH2)x—S—S—(CH2)x—, where x at each occurrence is an integer independently selected from 0 to 20, combinations thereof, or void;
• B1 is C, S, SO, P, or PO;
• B2 is C or SO;
• A1 is N, S, or P;
• M is selected from Cl, Br, I, SO4, NO3 ClO4, BF4, PF6, N(SO2CF3)2, SO3CF3, RCOO (R is C1-C20 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.