Quaternary ammonium etidronates
The present invention provides a quaternary ammonium etidronate compound (QAE) comprising a quaternary ammonium cation and an etidronate anion, having the Formula I. A method for the preparation of such compounds is described by reacting a quaternary ammonium salt with an etidronic acid or salt thereof. Variable ratios of each reactant may also be used to form different QAE compounds. The quaternary ammonium etidronate compounds is useful in water treatment, cosmetic, hygiene, personal care, paint, coating, wood treatment, agrochemical, antimicrobial, disinfectant, or biocidal compositions; as the compound provides high anti-corrosive and biocidal properties; and low scaling properties. A water treatment composition is also described, having a QAE compound of Formula I and a water treating biocidal agent, useful in cooling towers and other recirculating water, or recreational water system.
1. A quaternary ammonium etidronate compound, comprising a quaternary ammonium cation and an etidronate anion, having the Formula I,
wherein in the quaternary ammonium cation in the Formula I,
R1 or R2, is a H or a substituted or unsubstituted straight chain or branched C 1 -C 8 alkyl, aryl, alkylaryl/arylalkyl, cycloalkyl, (aromatic or non-aromatic) heterocyclyl, or alkoxy;
R3 or R4 is a substituted or unsubstituted straight chain or branched C 6 -C 30 alkyl, aryl, alkylaryl/arylalkyl, cycloalkyl, (aromatic or non-aromatic) heterocyclyl, alkenyl, phenyl, alkyl-substituted phenyl, benzyl, naphthylmethyl, or ethylbenzyl group;
wherein two or more of R1, R2, R3 and R4 may together with a nitrogen atom form a substituted or unsubstituted heterocyclic ring; and wherein the total number of carbon atoms in the groups R1, R2, R3 and R4 must be at least 12;
wherein the quaternary ammonium cation, comprises a C 8 -C 30 dialkyldimethyl ammonium, C 8 -C 30 dialkylmethylpoly(oxyethyl) ammonium, C 8 -C 30 alkylbenzyldimethyl ammonium, C 8 -C 30 alkyltrimethylammonium, C 8 -C 30 dialkyldihydroxyethyl ammonium, C 8 -C 30 dialkylmethylhydroxyethyl ammonium, or C 8 -C 30 alkylmethyldihydroxyethyl ammonium;
wherein the etidronate anion, having the Formula I, is an etidronic salt wherein R5 and R6 is PO 3 2− or PO 3 X y ; wherein each X is a H, M, H − , HM, M − or M + ; wherein y is 0-2; and M is lithium, sodium, potassium or any combinations thereof, and wherein R7 group is a H or a substituted or unsubstituted straight chain or branched C 1 -C 8 alkyl;
wherein m is 1-4 and n is 1; and
wherein the quaternary ammonium etidronate compound does not comprise a chloride ion.
2. The compound of claim 1 , wherein R1, R2, R3 or R4 when substituted comprises substituent groups selected from one or more of a F, Br, I, Cl, —OR′, —NR′R″, —CF 3 , —CN, —NO 2 , —C 2 R′, —SR′, —N 3 , —C(═O)NR′R″, —NR′C(O)R″, —O(CR′R″)rC(═O)R′, O(CR′R″)rNR′C(O)R′, —(CR′R″)rNR″SO 2 R′, —OC(O)NR′R″, —NR′C(O)OR″, —SO 2 R′, —SO 2 NR′R″, —NR′SO 2 R″; or combinations thereof, wherein R′ and R″ are individually hydrogen, C 1 -C 8 alkyl, cycloalkyl, heterocyclyl, aryl, or arylalkyl, and is an integer from 1 to 6, or R′ and R″ together form a cyclic functionality.
3. The compound of claim 1 , wherein the etidronate anion, having the group R5 is a PO32-, PO3H2, PO3M2, PO3HM, PO3H— or PO3M- and the group R6 is a PO32-, PO3H2, PO3M2, PO3HM, PO3H— or PO3M-.
4. The compound of claim 1 , wherein the quaternary ammonium etidronate is one having the Formula II, III, IV, V or combinations thereof, and wherein R1-R4 are as defined according to claim 1 .
5. A method for the preparation of a quaternary ammonium etidronate compound, said method comprising reacting a quaternary ammonium compound with an etidronate anion, as shown in Schematic A,
wherein in the quaternary ammonium compound R1 or R2, is a H or a substituted or unsubstituted straight chain or branched C 1 -C 8 alkyl, aryl, alkylaryl/arylalkyl, cycloalkyl, (aromatic or non-aromatic) heterocyclyl, or alkoxy;
R3 or R4 is a substituted or unsubstituted straight chain or branched C 6 -C 30 alkyl, aryl, alkylaryl/arylalkyl, cycloalkyl, (aromatic or non-aromatic) heterocyclyl, alkenyl, phenyl, alkyl-substituted phenyl, benzyl, naphthylmethyl, or ethylbenzyl group;
wherein two or more of R1, R2, R3 or R4 may together with a nitrogen atom form a substituted or unsubstituted heterocyclic ring; and wherein the total number of carbon atoms in the groups R1, R2, R3 or R4 must be at least 12;
wherein the etidronate anion, having the Formula I, is an etidronic salt wherein R5 and R6 is PO 3 2− or PO 3 X y ; wherein each X is a H, M, H − , HM, M − or M + ; wherein y is 0-2; and M is lithium, sodium, potassium or any combinations thereof, and wherein R7 group is a H or a substituted or unsubstituted straight chain or branched C 1 -C 8 alkyl;
wherein the etidronate anion comprises an ion of 1-hydroxyethane 1,1-diphosphonic acid (HEDP or etidronic acid), sodium etidronate, disodium etidronate (1-Hydroxyethanediphosphonic acid, sodium salt), dilithium etidronate, dipotassium etidronate, trisodium etidronate, tetrasodium etidronate, tetrapotassium etidronate or combinations thereof;
wherein Y − is an anion, and
wherein said quaternary ammonium compound reactant or etidronate anion is present at variable ratios.
6. The method as defined in claim 5 , wherein the weight ratio of the quaternary ammonium cation to the etidronate anion is from about 1:1 to about 4:1.
7. The method as defined in claim 5 , wherein the quaternary ammonium compound reactant is a quaternary salt; wherein a Y − anion comprises carbonates, bicarbonates, halides, phosphates, sulfates, bisulfates, acetates, nitrates, hydroxides, salicylates, bentonites, molybdates, formates, borates, sulfonates, phosphites, hypophosphite, or combinations thereof.
8. The method as defined in claim 5 , wherein the quaternary ammonium etidronate is formed by reacting a quaternary ammonium carbonate, bicarbonate or hydroxide with etidronic acid, as shown in Schematic B,
wherein said quaternary ammonium compound reactant to etidronic acid is present at variable ratios of about 1:1 to about 4:1.
9. The method as defined in claim 8 , wherein the reaction takes places in the presence of an aqueous solvent comprising of water, aqueous alcohols, ammonia water, acid solutions, salt solutions, water-miscible organic solvents, glycols, or combinations thereof.
10. The method as defined in claim 8 , wherein the reaction takes places in the presence of an optional antifoaming agent; wherein the antifoaming agent comprises polydimethylsiloxaneanti-foam.
11. The method as defined in claim 8 , wherein the reaction takes places in the presence of an optional base; wherein the base comprises a strong or weak base.
12. A method of treating recirculating water using one or more compounds as defined according to claim 1 , wherein the compound is contacted for an amount of time sufficient to kill microbes present in the water.
13. A water treatment composition comprising one or more of a quaternary ammonium etidronate compound or derivative thereof, as defined according to claim 1 , and a water treating biocidal agent.
14. The water treatment composition according to claim 13 , wherein the quaternary ammonium compound or derivative thereof is present from about 5 w/w % to about 35 w/w % of the total composition; and the water treating biocidal agent is present from about 0.1 w/w % to 25 w/w % of the total composition.
15. The water treatment composition as defined in claim 13 , wherein the water treating biocidal agent comprises a halogen releasing agent; a peroxy compound; a hydrogen peroxide source; an isothiazolone, derivatives or a mixture of isothiazolones; an amine, or combinations thereof.
16. The water treatment composition as defined in claim 15 , wherein the halogen releasing agent comprises a chlorinated isocyanuric acids or salts thereof, halogenated hydantoins, hypochlorous acid, hypochlorite salts or salts thereof, chlorine gas, chlorine dioxide, hypobromite salts, hypobromous acid or combinations thereof.
17. The water treatment composition, as defined in claim 13 , further comprising an acid, a carboxylic acid or mineral acid, wherein the total concentration of the acid is from about 0.1 w/w % to 10 w/w % of the total composition.
18. The water treatment composition, as defined in claim 13 , further comprising a stabilizer selected from an organic and inorganic sequestering agent, wherein the stabilizer is present from about 0.01 w/w % to about 5 w/w % of the total composition.
19. The water treatment composition, according to claim 13 , further comprising a second biocidal agent, wherein the second biocidal agent is present from about 0.1 w/w % to about 25 w/w % of the total composition.
20. A water treatment composition comprising (a) an effective amount of one or more of a quaternary ammonium etidronate compound or derivative thereof, as defined according to claim 1 , (b) a water treating biocidal agent, (c) a hydrogen peroxide source and (d) water.
21. A method of treating a body of water, wherein the water is a swimming pool, pond, lake, stream, canal; said method comprises adding the composition according to claim 20 to the water.
22. A water treatment, cosmetic, hygiene, personal care, paint, coating, wood treatment, agrochemical, antimicrobial, biocidal or disinfectant composition comprising one or more compounds according to claim 1 .
23. The compound of claim 1 , wherein m is 4.
24. The compound of claim 5 , wherein Y− is a carbonate anion or a bicarbonate anion.