Biocide compositions

1. A method of controlling microbe proliferation in a system used in a coal-fired process, a waste-water process, a farm, a slaughter house, a land-fill, a municipality waste-water plant, a coking coal process, or a biofuel process, the method comprising contacting the system with an effective amount of a biocide composition, the biocide composition comprising

an imidazoline compound;

a quaternary amine; and

a phosphonium compound;

wherein the imidazoline compound has a structure of formula (I), (II), or (III),

wherein

R 1 , R 4 , and R 5 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,

said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle each independently, at each occurrence, unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, —COR 6 , —CO 2 R 7 , —SO 3 R 8 , —PO 3 H 2 ,)—CON(R 9 )(R 10 ), —OR 11 , and —N(R 12 )(R 13 );

R 2 is a radical derived from a fatty acid;

R 3 and R x are independently selected from a radical derived from an unsaturated acid;

R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;

R 12 and R 13 are each independently, at each occurrence, selected from hydrogen, alkyl, —COR 14 , —CO 2 R 15 , -alkyl-COR 16 , and -alkyl-CO 2 R 17 ; and

R 14 ,R 15 , R 16 , and R 17 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

2. The method of claim 1 , wherein the imidazoline compound has formula (I),

wherein

R 1 , R 4 , and R 5 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,

said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle each independently, at each occurrence, unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, -COR 6 , —CO 2 R 7 , —SO 3 R 8 , —PO 3 H 2 , —CON(R 9 )(R 10 ) —OR 11 , and —N(R 12 )(R 13 );

R 2 is a radical derived from a fatty acid;

R 3 is selected from a radical derived from an unsaturated acid;

R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;

R 12 and R 13 are each independently, at each occurrence, selected from hydrogen, alkyl, —COR 14 , —CO 2 R 15 , -alkyl-COR 16 , and -alkyl-CO 2 R 17 ; and

R 14 , R 15 , R 16 , and R 17 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

3. The method of claim 2 , wherein

R 1 is unsubstituted C 2 -C 6 -alkyl;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 3 is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R 4 is hydrogen; and

R 5 is hydrogen.

4. The method of claim 2 , wherein

R 1 is linear C 2 -alkyl, substituted with one substituent that is a terminal —N(R 12 )(R 13 ), wherein R 12 is hydrogen and R 13 is —COR 14 , wherein R 14 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 3 is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R 4 is hydrogen; and

R 5 is hydrogen.

5. The method of claim 2 , wherein

R 1 is linear C 2 -alkyl, substituted with one substituent that is a terminal —N(R 12 )(R 13 ), wherein R 12 and R 13 are each a —C 2 -alkyl-CO 2 R 17 , wherein R 17 is hydrogen or R 17 is absent;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 3 is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R 4 is hydrogen; and

R 5 is hydrogen.

6. The method of claim 1 , wherein the imidazoline compound has formula (II),

wherein

R 1 , R 4 , and R 5 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,

said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle each independently, at each occurrence, unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, —COR 6 , —CO 2 R 7 , —SO 3 R 8 , —PO 3 H 2 ,)—CON(R 9 )(R 10 ), —OR 11 , and —N(R 12 )(R 13 );

R 2 is a radical derived from a fatty acid;

R 3 and R x are each independently selected from a radical derived from an unsaturated acid;

R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;

R 12 and R 13 are each independently, at each occurrence, selected from hydrogen, alkyl, —COR 14 , —CO 2 R 15 , -alkyl-COR 16 , and -alkyl-CO 2 R 17 ; and

R 14 , R 15 , R 16 , and R 17 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

7. The method of claim 6 , wherein

R 1 is unsubstituted C 2 -C 6 -alkyl;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 3 is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R x is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R 4 is hydrogen; and

R 5 is hydrogen.

8. The method of claim 6 , wherein

R 1 is linear C 2 -alkyl, substituted with one substituent that is a terminal —N(R 12 )(R 13 ), wherein R 12 is hydrogen and R 13 is —COR 14 , wherein R 14 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 2 is —C i7 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 3 is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R x is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R 4 is hydrogen; and

R 5 is hydrogen.

9. The method of claim 6 , wherein

R 1 is linear C 2 -alkyl, substituted with one substituent that is a terminal —N(R 12 )(R 13 ), wherein R 12 and R 13 are each a —C 2 -alkyl-CO 2 R 17 , wherein R 17 is hydrogen or R 17 is absent;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 3 is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R x is —CH 2 CH 2 CO 2 R e , wherein R e is hydrogen, C 1 -C 6 -alkyl, or R e is absent;

R 4 is hydrogen; and

R 5 is hydrogen.

10. The method of claim 1 , wherein the imidazoline compound has formula (III),

wherein

R 1 , R 4 , and R 5 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,

said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle each independently, at each occurrence, unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, —COR 6 , —CO 2 R 7 , —SO 3 R 8 , —PO 3 H 2 , —CON(R 9 )(R 10 ), and —N(R 12 )(R 13 );

R 2 is a radical derived from a fatty acid;

R 6 , R 7 , R 8 , R 9 , and R 10 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;

R 12 and R 13 are each independently, at each occurrence, selected from hydrogen, alkyl, —COR 14 , —CO 2 R 15 , -alkyl-COR 16 , and -alkyl-CO 2 R 17 ; and

R 14 , R 15 , R 16 and R 17 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

11. The method of claim 10 , wherein

R 1 is unsubstituted C 2 -C 6 -alkyl;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 4 is hydrogen; and

R 5 is hydrogen.

12. The method of claim 10 , wherein

R 1 is linear C 2 -alkyl, substituted with one substituent that is a terminal —N(R 12 )(R 13 ), wherein R 12 is hydrogen and R 13 is —COR 14 , wherein R 14 is —C 17 H 35 , —C 17 H 33 , —C 17 H 31 ;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 4 is hydrogen; and

R 5 is hydrogen.

13. The method of claim 10 , wherein

R 1 is linear C 2 -alkyl, substituted with one substituent that is a terminal —N(R 12 )(R 13 ), wherein R 12 and R 13 are each a —C 2 -alkyl-CO 2 R 17 , wherein R 17 is hydrogen or R 17 is absent;

R 2 is —C 17 H 35 , —C 17 H 33 , or —C 17 H 31 ;

R 4 is hydrogen; and

R 5 is hydrogen.

14. The method of claim 1 , wherein the quaternary amine has the formula

[N + R 5a R 6a R 7a R 8a ][X]

wherein

R 5a , R 6a , R 7a , and R 8a are each independently selected from substituted or unsubstituted C 1 -C 18 -alkyl; and

X is Cl, Br or I.

15. The method of claim 14 , wherein

R 5a , R 6a , R 7a , and R 8a are each independently selected from the group consisting of unsubstituted C 1 -C 18 -alkyl, C 1 -C 18 -hydroxyalkyl, and benzyl.

16. The method of claim 1 , wherein the quaternary amine is selected from the group consisting of tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammonium chloride, tetraoctyl ammonium chloride, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammonium chloride, phenyltriethyl ammonium chloride, cetyl benzyldimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dimethyl C 12 - 16 -alkyl benzyl ammonium chloride, monomethyl di-C 12 - 16 -alkyl benzyl quaternary ammonium chloride, benzyl triethanolamine quaternary ammonium chloride, benzyl dimethylaminoethanolamine quaternary ammonium chloride, cocoalkyl dimethyl benzyl ammonium chloride, and combinations thereof.

17. The method of claim 1 , wherein the phosphonium compound is selected from the group consisting of alkyltris(hydroxyorgano)phosphonium salts, alkenyltri s(hydroxyorgano)phosphonium salts, tetrakis(hydroxyorgano)phosphonium salts, and combinations thereof.

18. The method of claim 17 , wherein the phosphonium compound is selected from the group consisting of C 1 -C 3 -alkyltris(hydroxymethyl)phosphonium salts, C 2 -C 3 -alkenyltris(hydroxymethyl)phosphonium salts, tetrakis(hydroxymethyl)phosphonium salts, and combinations thereof.

19. The method of claim 18 , wherein the phosphonium compound is selected from the group consisting of tetrakis(hydroxymethyl)phosphonium sulphate (THPS), tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis(hydroxymethyl)phosphonium formate, tetrakis(hydroxymethyl)phosphonium acetate, tetrakis(hydroxymethyl)phosphonium oxalate, and combinations thereof.

20. The method of claim 1 , further comprising a demulsifier, and the demulsifier is selected from the group consisting of dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic cationic and nonionic surfactants, and resins, phenolic and epoxide resins, and combinations thereof.