KR20090074087A - Controlled foam aqueous quaternary ammonium and phosphonium compositions - Google Patents

Abstract

The foaming tendency of aqueous systems containing biocidal quaternary ammonium and/or phosphonium compounds is reduced by addition of anionic surfactants in a molar ratio of anionic surfactant(s) to quaternary compound(s) of from 0.001 to 0.2. A preferred application of the aqueous systems according to the invention is in swimming pool or spa waters as algaecides.

Description

Foam-controlled aqueous quaternary ammonium and phosphonium compositions {CONTROLLED FOAM AQUEOUS QUATERNARY AMMONIUM AND PHOSPHONIUM COMPOSITIONS}

The present invention is directed to a method of controlling foam formation in an aqueous system comprising bactericidal quaternary ammonium and / or phosphonium compounds ("quats"). The present invention also relates to low foamed aqueous formulations containing quaternary ammonium and / or phosphonium compounds and to the use of such formulation compounds in methods of killing or inhibiting the growth of microorganisms, algae and fungi.

Some quaternary ammonium and phosphonium compounds ("quats") exhibit significant bactericidal activity, and therefore, for many years, disinfectants, preservatives or other agents that kill or control the growth of algae and fungi as well as microorganisms such as bacteria or viruses. It has been used as an active ingredient in compositions. However, since many of these quarts also have surfactant properties, they cause severe foaming even at low quench concentrations in the ppm range (this is especially true for aqueous systems during exposure to the atmosphere, such as swimming pool or spa water or water in cooling towers). Disadvantageous in this stirred application), often impairing its usefulness in aqueous systems.

Accordingly, the problem to be solved by the present invention was to provide a method for suppressing foaming in an aqueous system containing one or more bactericidal quarts.

According to the invention, the problem has been solved by the method of claim 1. Applicant discloses that in an aqueous system comprising one or more bactericidal quaternary ammonium and / or phosphonium compounds, the molar ratio of the anionic surfactant to the quaternary ammonium and / or phosphonium compound is 0.001 to 0.2. (Ie 0.001: 1 to 0.2: 1), preferably in an amount corresponding to 0.001 to 0.09, has been found to substantially reduce the volume and life of the foam formed while the aqueous system is in use.

Since anionic surfactants are known to reduce the bactericidal efficacy of quaternary ammonium compounds, it is important from the standpoint of quart performance efficiency that the observed reduction in foaming is achieved by adding far less than molar equivalents of the anionic surfactant. Since only small amounts, for example 0.1 or 0.02 molar equivalents of anionic surfactant, are needed, the compositions have their active quart concentrations of about 90 or 98%, respectively.

In a more preferred embodiment, the molar ratio of the anionic surfactant to quaternary ammonium and / or phosphonium compounds is from 0.001 to 0.05.

Preferably, at least one quaternary ammonium and / or phosphonium compound is selected from:

의 화합물:(i) chemical formula

Compound of:

[In the meal,

Q is nitrogen or phosphorus;

R ¹ and R ² are independently unsubstituted or hydroxy-substituted linear or branched C _1-4 alkyl; -(CH ₂ CH ₂ O) _m CH ₂ CH ₂ OH or-(CH ₂ CH (CH ₃ ) O) _m CH ₂ CH (CH ₃ ) OH (wherein m in each molecule is independently 1 to Is an integer of 10);

R ³ is an optionally substituted benzyl, ethylbenzyl, naphthylmethyl, or a linear or branched C _6-22 alkyl group;

R ⁴ is optionally substituted benzyl, ethylbenzyl, methylnaphthyl, or linear or branched C _1-22 alkyl or -R ⁵ (O) _n (C ₆ H ₄ ) R ⁶ , wherein n is 0 or 1 Is);

R ⁵ is substituted or unsubstituted C _1-8 alkanediyl or — (CH ₂ ) _p —O— (CH ₂ ) _q −, wherein p and q are independently integers from 1 to 8;

R ⁶ is hydrogen or substituted or unsubstituted, linear or branched C _1-12 alkyl;

X ⁻ is a monovalent or 1 equivalent polyvalent anion;

의 화합물:(ii) chemical formula

Compound of:

[In the meal,

Q is nitrogen or phosphorus,

R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently saturated, unsaturated hydrocarbyl groups of linear, branched, cyclic or any combination thereof,

X ⁻ is a monovalent or one equivalent polyvalent anion,

The sum of the carbon atoms of R ¹⁹ , R ²⁰ , R ²¹ and R ²² is in the range of 10 to 50;

(iii) polymeric quaternary ammonium or phosphonium fungicides; And

(iv) a mixture of at least two quaternary compounds of any of (i)-(iii) above.

을 갖고, 식 중, Q 는 앞서 정의된 바와 같고, R¹ 및 R² 의 둘 다는 C_1-4 알킬이고, R³ 은 선형 또는 분지형 C_6-22 알킬이고, R⁴ 는 벤질 또는 선형 또는 분지형 C_1-22 알킬이고, X^- 는 클로라이드이다.More preferably, the quaternary ammonium or phosphonium compound is of formula

Wherein Q is as defined above, both R ¹ and R ² are C _1-4 alkyl, R ³ is linear or branched C _6-22 alkyl, and R ⁴ is benzyl or linear or _Branched C _1-22 alkyl and X ⁻ is chloride.

을 갖고, 식 중, Q 는 앞서 정의된 바와 같고, R¹ 및 R² 의 둘 다는 메틸이고, R³ 은 선형 또는 분지형 C_6-22 알킬이고, R⁴ 는 벤질 또는 선형 또는 분지형 C_6-22 알킬이고, X^- 는 클로라이드이다.Even more preferably, the quaternary ammonium or phosphonium compound is

Wherein Q is as defined above, both R ¹ and R ² are methyl, R ³ is linear or branched C _6-22 alkyl, and R ⁴ is benzyl or linear or branched C _{6 -22} alkyl and X ^- is chloride.

Most preferably, Q is nitrogen.

Especially preferred are ammonium and phosphonium compounds such as alkyldimethylbenzylammonium chloride or tributyltetradecylphosphonium chloride.

In another preferred embodiment, X in the formula (I) and / or (II) ^- is ½CO ₃ ^2-, HCO ₃ ^- is selected from the group consisting of ^- and OH.

In another preferred embodiment, the at least one anionic surfactant is a sulfonate.

In another preferred embodiment, the at least one anionic surfactant is a diester.

In a particularly preferred embodiment, the at least one anionic surfactant is diamyl sulfosuccinate, dihexyl sulfosuccinate, dioctyl sulfosuccinate, ditridecyl sulfosuccinate, potassium, sodium of any of the above. And calcium salts, and any mixture of any of the foregoing sulfosuccinates and salts.

In one most preferred embodiment, the at least one anionic surfactant is selected from the group consisting of dihexyl sulfosuccinate and its potassium, sodium and calcium salts.

In another most preferred embodiment, the at least one anionic surfactant is selected from the group consisting of dioctyl sulfosuccinate and its potassium, sodium and calcium salts.

In another most preferred embodiment, the at least one anionic surfactant is selected from the group consisting of diamyl sulfosuccinate and its potassium, sodium and calcium salts.

Of the sulfosuccinate salts, sodium salts are particularly preferred.

The sulfonate has been observed to substantially reduce foaming while maintaining high levels of quart activity.

Preferably, the aqueous system comprises 0.1 to 100 ppm, more preferably 0.5 to 50 ppm of bactericidal quaternary ammonium and / or phosphonium compounds.

Another object of the present invention is a low foam formulation containing one or more bactericidal quaternary ammonium and / or phosphonium compounds and one or more anionic surfactants, anionic to the quaternary ammonium and / or phosphonium compound (s). Formulations having a molar ratio of surfactant (s) from 0.001 to 0.2, preferably from 0.001 to 0.09, more preferably from 0.001 to 0.05.

Preferably, the low foamed formulation contains 5 to 80% by weight, more preferably 10 to 50% by weight of one or more bactericidal quaternary ammonium and / or phosphonium compounds, based on 100% by weight total formulation.

The low foam formulations of the present invention are stable single phase clear solutions.

Preferably the low foam formulations contain one or more functional additives such as dyes or perfumes.

Another object of the present invention is a method of killing or inhibiting the growth of microorganisms, zooplankton, algae and / or fungi, the method comprising applying the formulation to an aqueous system or to a porous or hard surface.

In a preferred embodiment, the porous or hard surface is wood, metal or plastic.

In another preferred embodiment, the formulation is used as wood preservative.

In another preferred embodiment, the formulation is used as a disinfectant or hygiene for hard surfaces.

In another preferred embodiment, the aqueous system comprises cooling water; Wastewater; Water used for infusion, testing or recovery in oil fields; Recreational pool or spa water, ballast water, and pulp or paper slurry.

Most preferably, the aqueous system is cooling water, ballast water or recreational pool or spa water.

Particular preference is given to application as algae in pool or spa water.

Preferably, the aqueous system comprises 0.1 to 100 ppm, preferably 0.5 to 50 ppm of bactericidal quaternary ammonium and / or phosphonium compounds.

The invention is further illustrated by the following non-limiting examples.

Way:

In 20 ° C. tap water (pH = 7-8, total hardness = 160-300 ppm (as CaCO ₃ ) and total alkalinity = 150-250 ppm (as CaCO ₃ ) from selected quaternary ammonium compounds and selected anionic surfactants Test solution was prepared. 150 mL of each test solution is added to a 250 mL stopper graduated mixing cylinder, the solution is shaken by inverting the cylinder 10 times, the foaming volume is measured immediately after shaking, and after the standing time for 30 seconds, the foaming volume is again Was measured. In addition, the time taken for all foaming to collapse was measured ("time to foam member"). All quart concentrations in ppm or% are by weight unless otherwise indicated and represent the actual content of the active ingredient.

Example 1 (Reference example)

Representative quaternary ammonium compounds for evaluating foaming are alkyl (67% C ₁₂ , 25% C ₁₄ , 7% C ₁₆ , 1% C _{8, 10, 18} ) Dimethylbenzylammonium chloride (ADBAC; Barquat® 50-65B, Lonza Inc., Allendale, NJ). As shown in Table 1 below, ADBAC produced a substantial amount of foaming, which resulted in an initial foaming volume of 25 mL and after 30 seconds, maintained 10 mL of foaming. For comparison, the foaming behavior of polymeric quart poly [oxyethylene (dimethylimminio) ethylene (dimethylimminio) ethylene dichloride] (WSCP; Buckman Laboratories International, Inc., Memphis, TN) was also tested.

Example 2

The effect of the anionic surfactant sodium dioctyl sulfosuccinate (NaDOSS) on ADBAC foaming was measured as described above. The results are shown in Table 1 below. Adding only 0.1 molar equivalents of NaDOSS to the active quarts reduced the initial foaming volume by 85% from 25 mL to 4 mL. Even application of only 0.02 molar equivalents of NaDOSS yielded an initial foam volume of only 6 mL and the extinction of the foam was completed within 10 seconds.

Example 3

The ability of NaDOSS to control foaming at low concentrations of quaternary ammonium compounds (because they are frequently used in water treatments such as swimming pool algae) was tested at a quart concentration of 2 ppm using the method of Example 2 did. For comparison purposes, the test was performed once without adding NaDOSS. The results are shown in Table 1 below. The low concentration of 0.05 ppm NaDOSS was found to control foam formation at 2 ppm quart concentration.

Example 4

Using the method of Example 2, alternative anionic surfactants sodium dihexyl sulfosuccinate (NaDHSS) and sodium ditridecyl sulfosuccinate (NaDTSS) as foam reducers were also tested. The results are shown in Table 1 below. NaDHSS at a low concentration of 1.1 ppm regulated the foaming of 10 ppm quarts (corresponding to a molar ratio of anionic surfactant to quart of 0.10), and also found that low concentrations of 0.2 ppm still have some effect. Similar results were obtained for NaDTSS at concentrations of 1.7 ppm (the molar ratio of anionic surfactant to quart corresponds to 0.10) and 0.4 ppm, respectively. NaDHSS produced a clear solution at all test concentrations and was therefore desirable.

Example 5

As shown in the preceding examples, NaDOSS can be applied separately to quart-containing solutions to achieve the desired foam reduction. However, for practical reasons, in particular for ease of application, it is desirable to provide a single formulation (concentrate) containing quarts and anionic surfactants in an optimal molar ratio. Therefore, the phase stability of both formulations containing Barquat® 50-65B and NaDOSS was tested. The results are shown in Table 2 below.

NaDOSS / Quart Mole Ratio Quart Content [%] NaDOSS content [%] Exterior 0.02 49.2 1.2 Single phase, sunny 0.10 46.1 5.8 Single phase, sunny

It was found that clear phase-stable formulations containing NaDOSS and ADBAC in molar ratios of 0.02 and 0.10 can be prepared. Test solutions with 10 ppm quarts were prepared from the formulations, which showed essentially the same foaming behavior as that in Example 2.

Example 6

Sodium dioctyl sulfosuccinate (NaDOSS) and sodium dihexyl sulfosuccinate (NaDHSS) were tested in a dynamic recirculation foam test designed to simulate cooling applications. The dynamic foaming test consisted of recycling the 1.5 liter water sample through a large graduated cylinder at a flow rate of 5.7 liters / minute (1.5 GPM). Water conditions were as follows: total hardness (as CaCO ₃ ) 280 ppm, total alkalinity (as CaCO ₃ ) 164 ppm, temperature 22 ° C., and pH = 7.3. If necessary, a master solution of the test formulation was added to obtain the recorded concentration. The results are shown in Table 3 below.

Sample Stabilized foam height after 5 minutes (cm) LF 7.25-8.0 LF + 0.02 mol NaDOSS 4.0 LF + 0.02 mol NaDHSS 6.0

Both of the compounds tested significantly reduced the foaming properties of 90 ppm active dioctyldimethylammonium chloride (Bardac® LF 18, Lonza Inc.). As shown in Table 3, addition of NaDOSS at a molar ratio of 0.02 (sulfosuccinate / Bardac® LF 18) provided a 50% foaming reduction from 8 cm to 4 cm, but addition of NaDHSS at the same molar ratio was 25 Provided a% foaming reduction.

Example 7

The phase stability of both formulations containing Bardac® LF 18 and NaDOSS was tested. As shown in Table 4 below, formulations containing NaDOSS in molar ratios of 0.02 and 0.05 provided compatible, clear, single phase solutions.

NaDOSS / Quart Mole Ratio Quart Content [%] NaDOSS content [%] Exterior 0.02 51.0 1.5 Single phase, sunny 0.05 50.0 3.6 Single phase, sunny

Claims (21)

A method of controlling foam formation in an aqueous system comprising at least one bactericidal quaternary ammonium and / or phosphonium compound, wherein the aqueous system contains at least one anionic surfactant for an anion to the quaternary ammonium and / or phosphonium compound. Adding in an amount such that the molar ratio of the surfactant is from 0.001 to 0.2, preferably from 0.001 to 0.09. The method of claim 1 wherein the molar ratio of the anionic surfactant to the quaternary ammonium and / or phosphonium compound is from 0.001 to 0.05. The method of claim 1 or 2, wherein the at least one quaternary ammonium and / or phosphonium compound is selected from: (i) chemical formula

Compound of: [In the meal, Q is nitrogen or phosphorus, preferably nitrogen; R ¹ and R ² are independently unsubstituted or hydroxy-substituted linear or branched C _1-4 alkyl; -(CH ₂ CH ₂ O) _m CH ₂ CH ₂ OH or-(CH ₂ CH (CH ₃ ) O) _m CH ₂ CH (CH ₃ ) OH (wherein m in each molecule is independently 1 to Is an integer of 10); R ³ is optionally substituted benzyl, ethylbenzyl, naphthylmethyl, or linear or branched C _6-22 alkyl; R ⁴ is optionally substituted benzyl, ethylbenzyl, methylnaphthyl, or linear or branched C _1-22 alkyl or -R ⁵ (O) _n (C ₆ H ₄ ) R ⁶ , wherein n is 0 or 1 Is); R ⁵ is substituted or unsubstituted C _1-8 alkanediyl or — (CH ₂ ) _p —O— (CH ₂ ) _q −, wherein p and q are independently integers from 1 to 8; R ⁶ is hydrogen or substituted or unsubstituted, linear or branched C _1-12 alkyl; X ⁻ is a monovalent or 1 equivalent polyvalent anion; (ii) chemical formula

Compound of: [In the meal, Q is as defined above, R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently saturated, unsaturated hydrocarbyl groups of linear, branched, cyclic or any combination thereof, X ⁻ is a monovalent or one equivalent polyvalent anion, The sum of the carbon atoms of R ¹⁹ , R ²⁰ , R ²¹ and R ²² is in the range of 10 to 50; (iii) polymeric quaternary ammonium or phosphonium fungicides; And (iv) a mixture of at least two quaternary compounds of any of (i)-(iii) above. 4. The quaternary compound of claim 3, wherein the quaternary compound is of formula

Q is as defined in claim ³ , wherein both R ¹ and R ² are C _1-4 alkyl, R ³ is linear or branched C _6-22 alkyl, and R ⁴ is benzyl or linear or _Branched C _1-22 alkyl and X ⁻ is chloride. 5. The method of claim 3 or 4, wherein X ⁻ is selected from the group consisting of ½ CO ₃ ²⁻ , HCO ₃ ^−, and OH ⁻ . The method of claim 1, wherein the at least one anionic surfactant is a sulfonate. The method of any one of claims 1 to 6, wherein the at least one anionic surfactant is a diester. 8. The method of claim 6 or 7, wherein the at least one anionic surfactant is diamyl sulfosuccinate, dihexyl sulfosuccinate, dioctyl sulfosuccinate, ditridecyl sulfosuccinate, any of the above. Potassium, sodium and calcium salts of one, and any mixture of any of the foregoing sulfosuccinates and salts. The method of claim 8, wherein the at least one anionic surfactant is selected from the group consisting of dihexyl sulfosuccinate and its potassium, sodium and calcium salts. The method of claim 8, wherein the at least one anionic surfactant is selected from the group consisting of dioctyl sulfosuccinate and its potassium, sodium and calcium salts. The process according to claim 1, wherein the aqueous system comprises 0.1-100 ppm, preferably 0.5-50 ppm of bactericidal quaternary ammonium and / or phosphonium compounds. A single phase liquid low foaming formulation containing at least one bactericidal quaternary ammonium compound and at least one anionic surfactant, wherein the molar ratio of anionic surfactant (s) to quaternary ammonium compound (s) is from 0.001 to 0.2, preferably Is 0.001 to 0.09, more preferably 0.001 to 0.05. 13. The formulation according to claim 12, containing from 5 to 80% by weight, preferably from 10 to 50% by weight of at least one bactericidal quaternary ammonium and / or phosphonium compound, based on 100% by weight total formulation. The formulation according to claim 12 or 13, which contains dyes or flavorings or other functional additives. A method of killing or inhibiting the growth of microorganisms, algae and / or fungi, the method comprising applying the formulation of claim 12 to an aqueous system or to a porous or hard surface. The method of claim 15, wherein the porous or hard surface is wood, metal or plastic. The method of claim 16, wherein the formulation is used as wood preservative. The method of claim 15 wherein the formulation is used as a disinfectant or sanitizer for hard surfaces. 16. The system of claim 15, wherein the aqueous system comprises cooling water; Wastewater; Water used for infusion, testing or recovery in oil fields; Recreational pool or spa water, ballast water, and pulp or paper slurry. 20. The method of claim 19, wherein the aqueous system is cooling water, ballast water or recreational pool or spa water. The process according to claim 19 or 20, wherein the aqueous system comprises 0.1 to 100 ppm, preferably 0.5 to 50 ppm of bactericidal quaternary ammonium and / or phosphonium compounds.