Antifouling polymeric agent for marine applications

A polymeric matrix composition synthesized from:

• at least one structural monomer selected from esters of acrylic acid or substituted acrylic acids, amides of acrylic acid or substituted acrylic acids, styrene, substituted styrenes, acrylonitrile, substituted acrylonitriles, vinyl esters, vinyl chloride, alkenes, dienes, polyvinylic compounds, or polyalkenyl compounds;
• and
• at least one ionic monomer comprising a salt, said salt comprising an anionic monomer that is a conjugate base of an acid having a pKa less than about 9 and at least one cationic biocide selected from
• (a) guanidinium cations of general formula
• wherein R1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R2, R3, R4, R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl;
• (b) quaternary ammonium cations of general formula RiR2R3R4N+, where R1, R2, R3, and R4 are independently selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl;
• and
• (c) pyridinium cations selected from N-substituted pyridinium where the N substituent is selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl;
• N,N′-disubstituted bipyridinium where the N and N′ substituents are independently selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl;
• N-alkyl-2, 3, 4, or 5- substituted pyridinium compounds where the N substituent is selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl and where the 2, 3, 4 or 5- substituents are independently selected from the group alkyl, branched alkyl, substituted alkyl, alkenyl, aryl, heteroaryl, hydroxyl, O-alkyl, O-aryl, cyano, nitro, chloro, bromo, formyl, or acetyl,
• wherein the at least one structural monomer and the anionic monomer are bonded to one another to form the polymeric matrix.

A method, comprising treating a surface with an agent comprising a polymeric matrix, the polymeric matrix comprising:

• at least one structural monomer selected from esters of acrylic acid or substituted acrylic acids, amides of acrylic acid or substituted acrylic acids, styrene, substituted styrenes, acrylonitrile, substituted acrylonitriles, vinyl esters, vinyl chloride, alkenes, dienes, polyvinylic compounds, or polyalkenyl compounds;
• and
• at least one ionic monomer comprising a salt, said salt comprising an anionic monomer that is a conjugate base of an acid having a pKa less than about 9 and at least one cationic biocide selected from
• (a) guanidinium cations of general formula
• wherein R1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R2, R3, R4, R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl;
• (b) quaternary ammonium cations of general formula R1R2R3R4N+, where R1, R2, R3, and R4 are independently selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl;
• and
• (c) pyridinium cations selected from N-substituted pyridinium where the N substituent is selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl;
• N,N′-disubstituted bipyridinium where the N and N′ substituents are independently selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl;
• N-alkyl-2, 3, 4, or 5- substituted pyridinium compounds where the N substituent is selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl and where the 2, 3, 4 or 5- substituents are independently selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl, heteroaryl, hydroxyl, O-alkyl, O-aryl, cyano, nitro, chloro, bromo, formyl, or acetyl,
• wherein the at least one structural monomer and the anionic monomer are bonded to one another to form the polymeric matrix.

A composition comprising a polymeric matrix, the polymeric matrix consisting of:

• at least one structural monomer selected from esters of acrylic acid or substituted acrylic acids, amides of acrylic acid or substituted acrylic acids, styrene, substituted styrenes, acrylonitrile, substituted acrylonitriles, vinyl esters, vinyl chloride, alkenes, dienes, polyvinylic compounds, or polyalkenyl compounds;
• and
• at least one ionic monomer consisting of an anionic monomer that is a conjugate base of an acid having a pKa less than about 9 and at least one cationic biocide selected from
• (a) guanidinium cations of general formula
• wherein R1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R2, R3, R4, R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl;
• (b) quaternary ammonium cations of general formula R1R2R3R4N+, where R1, R2, R3, and R4 are independently selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl;
• and
• (c) pyridinium cations selected from N-substituted pyridinium where the N substituent is selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl;
• N,N′-disubstituted bipyridinium where the N and N′ substituents are independently selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl;
• N-alkyl-2, 3, 4, or 5- substituted pyridinium compounds where the N substituent is selected from alkyl, branched alkyl, substituted alkyl, alkenyl, aryl or heteroaryl and where the 2, 3, 4 or 5- substituents are independently selected from the group alkyl, branched alkyl, substituted alkyl, alkenyl, aryl, heteroaryl, hydroxyl, O-alkyl, O-aryl, cyano, nitro, chloro, bromo, formyl, or acetyl,
• wherein the at least one structural monomer and the anionic monomer are bonded to one another to form the polymeric matrix.