Antifouling polymeric agent for marine applications

1. A polymeric matrix composition 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 pK a less than about 9 and at least one cationic biocide selected from

(a) guanidinium cations of general formula

wherein R 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R 2 , R 3 , R 4 , R 5 and R 6 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 R 1 R 2 R 3 R 4 N + , where R 1 , R 2 , R 3 , and R 4 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.

2. The polymeric matrix composition of claim 1 comprising about 20-70 wt % ionic monomer.

3. The polymeric matrix composition of claim 2 comprising about 20-40 wt % ionic monomer.

4. The polymeric matrix composition of claim 3 comprising about 30 wt % ionic monomer.

5. The polymeric matrix composition of claim 2 comprising at least two structural monomers.

6. The polymeric matrix composition of claim 1 wherein said cationic biocide is selected from guanidinium cations of the general formula:

wherein R 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl.

7. The polymeric matrix composition of claim 6 comprising about 20-70 wt % ionic monomer.

8. The polymeric matrix composition of claim 7 comprising about 20-40 wt % ionic monomer.

9. The polymeric matrix composition of claim 8 comprising about 30 wt % ionic monomer.

10. The polymeric matrix composition of claim 7 wherein said ionic monomer comprises polysubstituted guanidinium methacrylate.

11. The polymeric matrix composition of claim 10 wherein said cationic biocide is N-butyl-N′decylguanidinium, N-butyl-N′decyl-N″-(3-hydroxypropyl)guanidinium, or N-hexyl-N′-(3-hydroxypropyl)-N″-octylguanidinium.

12. The polymeric matrix composition of claim 7 wherein said structural monomers are selected from

(a) substituted alkyl, branched alkyl, or aryl esters of acrylic acid, alkyl acrylic acids, polyalkyl acrylic acids, or substituted alkyl acrylic acids;

(b) esters of alkyl acrylic acids, polyalkyl acrylic acids, or alkyl acrylic acids substituted with diols, triols, or other polyols;

(c) alkyl, substituted alkyl, branched alkyl, or aryl amides of acrylic acid, alkyl acrylic acids, polyalkyl acrylic acids, or substituted alkyl acrylic acids;

(d) amides of alkyl acrylic acids, polyalkyl acrylic acids, oralkyl acrylic acids substituted with diamines, triamines or other polyamines; or

(e) vinyl esters of alkanoic, substituted alkanoic, benzoic, or substituted benzoic acids.

13. The polymeric matrix composition of claim 12 wherein said structural monomers comprise 2-ethylhexyl acrylate and methyl methacrylate.

14. The polymeric matrix composition of claim 13 comprising greater than 0% up to 30 wt % 2-ethylhexyl acrylate and greater than 0% up to 40 wt % methyl methacrylate.

15. 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 pK a less than about 9 and at least one cationic biocide selected from

(a) guanidinium cations of general formula

wherein R 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R 2 , R 3 , R 4 , R 5 and R 6 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 R i R 2 R 3 R 4 N + , where R 1 , R 2 , R 3 , and R 4 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.

16. The polymeric matrix composition of claim 15 synthesized from about 20-70 wt % ionic monomer.

17. The polymeric matrix composition of claim 16 synthesized from about 20-40 wt % ionic monomer.

18. The polymeric matrix of claim 17 synthesized from about 30 wt % ionic monomer.

19. The polymeric matrix composition of claim 16 synthesized from at least two structural monomers.

20. The polymeric matrix composition of claim 15 wherein said cationic biocide is selected from guanidinium cations of the general formula:

wherein R 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl and R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl.

21. The polymeric matrix composition of claim 20 synthesized from about 20-70 wt % ionic monomer.

22. The polymeric matrix composition of claim 21 synthesized from about 20-40 wt % ionic monomer.

23. The polymeric matrix composition of claim 22 synthesized from about 30 wt % ionic monomer.

24. The polymeric matrix composition of claim 21 wherein said ionic monomer comprises polysubstituted guanidinium methacrylate.

25. The polymeric matrix composition of claim 24 wherein said cationic biocide is N-butyl-N′decylguanidinium, N-butyl-N′decyl-N″-(3-hydroxylpropyl)guanidinium or N-hexyl-N′-(3-hydroxypropyl)-N″-oetylguanidinium.

26. The polymeric matrix composition of claim 21 wherein said structural monomers are selected from

(a) substituted alkyl, branched alkyl, or aryl esters of acrylic acid, alkyl acrylic acids, polyalkyl acrylic acids, or substituted alkyl acrylic acids;

(b) esters of alkyl acrylic acids, polyalkyl acrylic acids, or alkyl acrylic acids substituted with diols, triols, or other polyols;

(c) alkyl, substituted alkyl, branched alkyl, or aryl amides of acrylic acid, alkyl acrylic acids, polyalkyl acrylic acids, or substituted alkyl acrylic acids;

(d) amides of alkyl acrylic acids, polyalkyl acrylic acids, or alkyl acrylic acids substituted with diamines, triamines or other polyamines; or

(e) vinyl esters of alkanoic, substituted alkanoic, benzoic, or substituted benzoic acids.

27. The polymeric matrix composition of claim 26 wherein said structural monomers comprise 2-ethylhexyl acrylate and methyl methacrylate.

28. The polymeric matrix composition of claim 27 synthesized from N-hexyl-N′-(3-hydroxypropyl)-N″-octylguanidinium methacrylate, methyl methacrylate and 2-ethylhexylacrylate.

29. 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 pK a less than about 9 and at least one cationic biocide selected from

(a) guanidinium cations of general formula

wherein R 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R 2 , R 3 , R 4 , R 5 and R 6 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 R 1 R 2 R 3 R 4 N + , where R 1 , R 2 , R 3 , and R 4 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.

30. The method of claim 29 wherein the polymeric matrix comprises greater than 0% up to 30 wt % 2-ethylhexyl acrylate, greater than 0% up to 40 wt % methyl methacrylate, and about 20-70 wt % of at least one ionic monomer comprising a salt, said salt comprising an anion that is a conjugate base of an acid having a pK a less than about 9 and at least one cationic biocide selected from guanidinium cations of the general formula:

wherein R l is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl.

31. The method of claim 29 wherein the polymeric matrix is synthesized from 2-ethylhexyl acrylate, methyl methacrylate, and about 20-70 wt % of N-hexyl-N′-(3-hydroxypropyl)-N″-octylguanidinium methacrylate.

32. The method of claim 29 wherein treating comprises coating.

33. The method of claim 30 wherein treating comprises coating.

34. The method of claim 31 wherein treating comprises coating.

35. The polymeric matrix composition of claim 13 comprising from about 20 to about 30 wt % 2-ethylhexyl acrylate and from about 20 to about 40 wt % methyl methacrylate.

36. 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 pK a less than about 9 and at least one cationic biocide selected from

(a) guanidinium cations of general formula

wherein R 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl, substituted aryl, heteroaryl and substituted heteroaryl, and R 2 , R 3 , R 4 , R 5 and R 6 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 R 1 R 2 R 3 R 4 N + , where R 1 , R 2 , R 3 , and R 4 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.

37. The composition of claim 36 , where the cationic biocide is N-butyl-N′ decylguanidinium, N-butyl-N′decyl-N″-(3-hydroxylpropyl)guanidinium, or N-hexyl-N′ -(3-hydroxypropyl)-N″-octylguanidinium.

38. A polymeric matrix composition comprising:

at least one structural monomer selected from methyl methacrylate, 2-ethylhexylmethacrylate, 2-ethylhexylacrylate, or a combination thereof; and

at least one ionic monomer consisting of an anionic monomer and a cationic biocide, wherein the ionic monomer is selected from the methacrylate salt of N-butyl-N′-decylguanidinium, the methacrylate salt of N-butyl-N′-decyl-N″-(3-hydroxypropyl)guanidinium, or a combination thereof, wherein the at least one structural monomer and the anionic monomer are bonded to one another to form the polymeric matrix.

39. The polymeric matrix composition of claim 1 , wherein the composition is formulated for use as a biocidal agent.

40. The polymeric matrix composition of claim 1 , wherein the polymeric matrix is capable of releasing the cationic biocide via an ion-exchange reaction with another cation.