CA2058688A1 - Biocide for aqueous based systems - Google Patents
Biocide for aqueous based systemsInfo
- Publication number
- CA2058688A1 CA2058688A1 CA002058688A CA2058688A CA2058688A1 CA 2058688 A1 CA2058688 A1 CA 2058688A1 CA 002058688 A CA002058688 A CA 002058688A CA 2058688 A CA2058688 A CA 2058688A CA 2058688 A1 CA2058688 A1 CA 2058688A1
- Authority
- CA
- Canada
- Prior art keywords
- dithiolan
- benzoazole
- composition according
- weight
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
Abstract
ABSTRACT
"BIOCIDE FOR AOUEOUS BASED SYSTEMS"
A method for treating an aqueous system is described which comprises incorporating therein a dithiolan having the general formula:
wherein each of X and Y, which may be the same or different, represents fluorine, chlorine or bromine, and a benzoazole having the general formula:
"BIOCIDE FOR AOUEOUS BASED SYSTEMS"
A method for treating an aqueous system is described which comprises incorporating therein a dithiolan having the general formula:
wherein each of X and Y, which may be the same or different, represents fluorine, chlorine or bromine, and a benzoazole having the general formula:
Description
- 1 - 2~8~'8~
BIOCIDE
The invention relates to the use of biocide~ in aqueous systems.
Biocides are commonly used in various aqueous systems in order to control the formation of slime and other microorganisms which can cause fouling of the systems and also harbour materials which can give rise to corrosion of the system. Fouling not only reduces water flow but it also reduces heat transfer. Thus it is common practice to add biocides to, in particular, cooling water systems such as those involving cooling towers and also to the aqueous systems used in pulp and paper mill systems.
A wide variety of materials has been employed to act as biocides in such systems. One material which has recently been found to be an effective biocide is 5-oxo-3,4-dichloro-1,2-dithiolan (commonly referred to as "2-dithiolan").
It has now surprisingly been found that if dithiolan is used in combination with 2-(thiocyanomethylthio)benzothiazole (TCMTB) broad spectrum activity can be obtained and, indeed, the combination is synergistic.
Accordingly, the present invention provides a composition suitable for addition to an aqueous system which comprises a dithiolan having the general formula given below and benzoazole having the general formula given below.
The dithiolans which can be used in the present invention have the general formula:
Y.~f/ S\
,JL ~\
O
BIOCIDE
The invention relates to the use of biocide~ in aqueous systems.
Biocides are commonly used in various aqueous systems in order to control the formation of slime and other microorganisms which can cause fouling of the systems and also harbour materials which can give rise to corrosion of the system. Fouling not only reduces water flow but it also reduces heat transfer. Thus it is common practice to add biocides to, in particular, cooling water systems such as those involving cooling towers and also to the aqueous systems used in pulp and paper mill systems.
A wide variety of materials has been employed to act as biocides in such systems. One material which has recently been found to be an effective biocide is 5-oxo-3,4-dichloro-1,2-dithiolan (commonly referred to as "2-dithiolan").
It has now surprisingly been found that if dithiolan is used in combination with 2-(thiocyanomethylthio)benzothiazole (TCMTB) broad spectrum activity can be obtained and, indeed, the combination is synergistic.
Accordingly, the present invention provides a composition suitable for addition to an aqueous system which comprises a dithiolan having the general formula given below and benzoazole having the general formula given below.
The dithiolans which can be used in the present invention have the general formula:
Y.~f/ S\
,JL ~\
O
2~8~
wherein each of X and Y, which may be the same or different, represents fluorine, chlorine or bromine, especially chlorine.
The benzoazoles which may be used in the present invention have the general formula:
(A)m ~ / N S(CH2)n-SCN
where Z represents oxygen or sulphur, A represents hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy, hydroxyl, sulphonate, carboxylate, cyano, halo, nitro or optionally substituted amino, n is from 1 to 4 and m is 1 or 2 such that when m is 2 each A may be the same or different. Preferably Z is sulphur, A is hydrogen and n is 1.
While the ratios of the dithiolan to the TCMTB can vary over a wide range it has been found that a weight ratio from 3:1 to 1:3 is generally particularly effective.
The compositions of the present invention typically comprise one or more solvents. Dithiolan is available commercially as a methyl carbitol solution. Other solvents which can be used include butyldiglycol as well as N-methyl pyrrolidone and tripropylene glycol n-butyl ether (TPnB~.
Typical solvents for the benzoazole include, dimethylformamide, diethylene glycol monoethylether and N-methyl pyrrolidone (NMP). While NMP is a good solvent for both products it is not in general, therefore, a mixture of solvents is employed to ensure a homogeneous and stable solution. Typical combinations of solvents include N-methyl pyrrolidone and either butyldiglycol or diethylene glycol.
TCMTB is available commercially as an 80% solution.
The compositions of the present invention will generally contain from 0.1 to 10~, especially from 0.25 to 3%, by weight of each of the dithiolan and the benzoazole.
Other ingredients conventiona:Lly employed in biocidal compositions for water treatment can be included if desired.
In particular biodispersants can be incorporated especially phenol ethoxylates of the formula:
~0 (CH2CH20) XH
where x is 2 to 40, especially 4. Typically biodispersants are present in an amount from 1 to 10, especially about 5, %
weight.
While it will generally be more convenient to add the two active ingredients together they can be added separately if desired. Accordingly, the present invention also provides a method for treating an aqueous system which comprises incorporating therein a dithiolan as defined above and a benzoazole as defined above.
Typically the active ingredients are present in an amount from 1 to 500, preferably 1 to 100, and especially 1 to 25, ppm (active).
The following Examples further illustrate the present invention:
Pseudomonas fluorescens previously isolated from an industrial cooling system water sample was grown on nutrient agar. Dilutions were prepared in Ringers solution, using standard microbiological techniques, to obtain bacterial counts of between 105 - 106 organisms per ml when incubated at 22C for 3 days on nutrient agar. This bacterial suspension was then exposed for l, 2 and 4 hours to various concentrations of 2-(thiocyanomethylthio)benzothiazole and 5-oxo-3,4-dichloro-1,2-dithiolan both alone and in combination at different ratios, namely:
Formula 1 TCMTB 2.5 (80% active) N - Methyl Pyrrolidone lO.0 Butyl Diglycol 87.5 Formula 2 TCMTB 1.75 (80~ active) N - Methyl Pyrrolidone 10.0 Dithiolan 5.0 (10% active) Butyl Diglycol 83.25 Formula 3 TCMTB 1.25 (80~ active) N - Methyl Pyrrolidone 2.0 Dithiolan lO.0 (10% active) Diethylene Glycol 86.75 Formula 4 TCMTB 0.625 (80% active) N - Methyl Pyrrolidone 2.0 Dithiolan 15.0 (10% active) Diethylene Glycol 82.375 Formula 5 Dithiolan 20.0 (10% active) N-Methyl Pyrrolidone lO.0 Butyl Diglycol 70Ø
At the various contact periods samples were taken and incubated at 22CC for 3 days on nutrient agar and surviving bacteria counted.
For each contact period and ration of biocides studied, graphs were constructed of per cent bacteria surviving as a function of biocide concentration.
The result obtained can be seen in Table l.
A Penicillium sp previously isolated from an industrial water system was grown on Rose Bengal Chloramphenicol agar base. Serial dilutions were prepared in Ringers solution using standard microbiological techniques to obtain fungal counts of between 104 - 105 colony forming units per ml when incubated at 30 C for 3 days on Rose Bengal Chloramphenicol agar base. This fungal suspension was then exposed for the same contact periods and to the same concentrations of 2-(thiocyanomethylthio)benzothiazole and 5-oxo-3,4-dichloro-1,2-dithiolan as for EXAMPLE 1.
At the stated contact periods, samples were taken and incubated at 30C for 3 days on Rose Bengal Chloramphenicol agar base and surviving fungi counted, for each contact period and ratio of biocide concentration.
The results obtained can be seen in Table 2.
Figures 1 and 2 clearly show that the combination tested displayed synergy because much less than the theoretical amounts were needed to achieve 100~ kill.
P~eudomon~s fl~ores~n~
CONTACT PERIOD CONCENTRATION ~ ~ILL
(HOURS) (ppm) RATIO OF TCMT8:DITHIOLE
2:0 1.5:0.5 1:1 1 0.5:1.5 1 0:2 ~lLA 1 ~o~ , En~vr~ ~ Fo~lLA 4 ¦~o~LLA S
., _ ~ ~
1.0 100 0 0 100 86.30 !
200 0 0 100 98.32 ' 97.3 400 0 0 100 100 1 97.31 600 0 0 100 100 , 100 _ 2.0 100 0 0 100 93.93 ' 96.9 200 0 0 100 99.92 , 99.8 ~00 0 0 100 100 99.98 600 0 0 10~ 100 100 .
.0 100 0 0 100 99.98 l 99~98 200 0 98.7 100 100 100 400 0 100 100 100 ~ 100 600 `90.55 100 100 100 100 290~
TABLE 2 ~ 5~
Penicilliu~ ~p ._ CONTACT PERIOD CONCENTRATION ~ KILL
(HOURS) (ppm) RATIO OF TCMTB:DITHIOLE
2:0 1 1.5:0.5 ~ 0~5 1-51 0:2 E3~LP 1 ~rLLA 2 Eo~fLA 3 'Eo~l~A 4 ~lMlA 5 . . __ . . _. . - A~-- _ _ 1.0 1 100 3.27 1 82.65 1 100 1 100 100 1 200 , 33.14 1 100 ; 100 ; 100 100 400 j 42.96 ~ 100 , 100 1 100 100 600 1 44.38 100 ' 100 , 100 100 800 , 5S.48 100 ~ 100 ' 100 100 ; , ~ , 2.0 , 100 41.68 100 ' 100 ~ 100 1 100 200 53.06 ' 100 ' 100 100 100 400 56.19 100 100 100 100 1 600 ; 93.53 ; 100 ' 100 , 100 100 800 93.83 100 1 100 1 100 100 . I ... _.
wherein each of X and Y, which may be the same or different, represents fluorine, chlorine or bromine, especially chlorine.
The benzoazoles which may be used in the present invention have the general formula:
(A)m ~ / N S(CH2)n-SCN
where Z represents oxygen or sulphur, A represents hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy, hydroxyl, sulphonate, carboxylate, cyano, halo, nitro or optionally substituted amino, n is from 1 to 4 and m is 1 or 2 such that when m is 2 each A may be the same or different. Preferably Z is sulphur, A is hydrogen and n is 1.
While the ratios of the dithiolan to the TCMTB can vary over a wide range it has been found that a weight ratio from 3:1 to 1:3 is generally particularly effective.
The compositions of the present invention typically comprise one or more solvents. Dithiolan is available commercially as a methyl carbitol solution. Other solvents which can be used include butyldiglycol as well as N-methyl pyrrolidone and tripropylene glycol n-butyl ether (TPnB~.
Typical solvents for the benzoazole include, dimethylformamide, diethylene glycol monoethylether and N-methyl pyrrolidone (NMP). While NMP is a good solvent for both products it is not in general, therefore, a mixture of solvents is employed to ensure a homogeneous and stable solution. Typical combinations of solvents include N-methyl pyrrolidone and either butyldiglycol or diethylene glycol.
TCMTB is available commercially as an 80% solution.
The compositions of the present invention will generally contain from 0.1 to 10~, especially from 0.25 to 3%, by weight of each of the dithiolan and the benzoazole.
Other ingredients conventiona:Lly employed in biocidal compositions for water treatment can be included if desired.
In particular biodispersants can be incorporated especially phenol ethoxylates of the formula:
~0 (CH2CH20) XH
where x is 2 to 40, especially 4. Typically biodispersants are present in an amount from 1 to 10, especially about 5, %
weight.
While it will generally be more convenient to add the two active ingredients together they can be added separately if desired. Accordingly, the present invention also provides a method for treating an aqueous system which comprises incorporating therein a dithiolan as defined above and a benzoazole as defined above.
Typically the active ingredients are present in an amount from 1 to 500, preferably 1 to 100, and especially 1 to 25, ppm (active).
The following Examples further illustrate the present invention:
Pseudomonas fluorescens previously isolated from an industrial cooling system water sample was grown on nutrient agar. Dilutions were prepared in Ringers solution, using standard microbiological techniques, to obtain bacterial counts of between 105 - 106 organisms per ml when incubated at 22C for 3 days on nutrient agar. This bacterial suspension was then exposed for l, 2 and 4 hours to various concentrations of 2-(thiocyanomethylthio)benzothiazole and 5-oxo-3,4-dichloro-1,2-dithiolan both alone and in combination at different ratios, namely:
Formula 1 TCMTB 2.5 (80% active) N - Methyl Pyrrolidone lO.0 Butyl Diglycol 87.5 Formula 2 TCMTB 1.75 (80~ active) N - Methyl Pyrrolidone 10.0 Dithiolan 5.0 (10% active) Butyl Diglycol 83.25 Formula 3 TCMTB 1.25 (80~ active) N - Methyl Pyrrolidone 2.0 Dithiolan lO.0 (10% active) Diethylene Glycol 86.75 Formula 4 TCMTB 0.625 (80% active) N - Methyl Pyrrolidone 2.0 Dithiolan 15.0 (10% active) Diethylene Glycol 82.375 Formula 5 Dithiolan 20.0 (10% active) N-Methyl Pyrrolidone lO.0 Butyl Diglycol 70Ø
At the various contact periods samples were taken and incubated at 22CC for 3 days on nutrient agar and surviving bacteria counted.
For each contact period and ration of biocides studied, graphs were constructed of per cent bacteria surviving as a function of biocide concentration.
The result obtained can be seen in Table l.
A Penicillium sp previously isolated from an industrial water system was grown on Rose Bengal Chloramphenicol agar base. Serial dilutions were prepared in Ringers solution using standard microbiological techniques to obtain fungal counts of between 104 - 105 colony forming units per ml when incubated at 30 C for 3 days on Rose Bengal Chloramphenicol agar base. This fungal suspension was then exposed for the same contact periods and to the same concentrations of 2-(thiocyanomethylthio)benzothiazole and 5-oxo-3,4-dichloro-1,2-dithiolan as for EXAMPLE 1.
At the stated contact periods, samples were taken and incubated at 30C for 3 days on Rose Bengal Chloramphenicol agar base and surviving fungi counted, for each contact period and ratio of biocide concentration.
The results obtained can be seen in Table 2.
Figures 1 and 2 clearly show that the combination tested displayed synergy because much less than the theoretical amounts were needed to achieve 100~ kill.
P~eudomon~s fl~ores~n~
CONTACT PERIOD CONCENTRATION ~ ~ILL
(HOURS) (ppm) RATIO OF TCMT8:DITHIOLE
2:0 1.5:0.5 1:1 1 0.5:1.5 1 0:2 ~lLA 1 ~o~ , En~vr~ ~ Fo~lLA 4 ¦~o~LLA S
., _ ~ ~
1.0 100 0 0 100 86.30 !
200 0 0 100 98.32 ' 97.3 400 0 0 100 100 1 97.31 600 0 0 100 100 , 100 _ 2.0 100 0 0 100 93.93 ' 96.9 200 0 0 100 99.92 , 99.8 ~00 0 0 100 100 99.98 600 0 0 10~ 100 100 .
.0 100 0 0 100 99.98 l 99~98 200 0 98.7 100 100 100 400 0 100 100 100 ~ 100 600 `90.55 100 100 100 100 290~
TABLE 2 ~ 5~
Penicilliu~ ~p ._ CONTACT PERIOD CONCENTRATION ~ KILL
(HOURS) (ppm) RATIO OF TCMTB:DITHIOLE
2:0 1 1.5:0.5 ~ 0~5 1-51 0:2 E3~LP 1 ~rLLA 2 Eo~fLA 3 'Eo~l~A 4 ~lMlA 5 . . __ . . _. . - A~-- _ _ 1.0 1 100 3.27 1 82.65 1 100 1 100 100 1 200 , 33.14 1 100 ; 100 ; 100 100 400 j 42.96 ~ 100 , 100 1 100 100 600 1 44.38 100 ' 100 , 100 100 800 , 5S.48 100 ~ 100 ' 100 100 ; , ~ , 2.0 , 100 41.68 100 ' 100 ~ 100 1 100 200 53.06 ' 100 ' 100 100 100 400 56.19 100 100 100 100 1 600 ; 93.53 ; 100 ' 100 , 100 100 800 93.83 100 1 100 1 100 100 . I ... _.
4.0 1 100 47.79 100 1 100 100 100 200 64.72 , 100 100 100 100 400 1 90.26 1 100 1 100 , 100 100 600 96.17 100 1 100 ' 100 100 800 100 100 1 100 i 100 100 _ 290~
Claims (15)
1. A method for treating an aqueous system which comprises incorporating therein a dithiolan having the general formula:
wherein each of X and Y, which may be the same or different, represents fluorine, chlorine or bromine, and a benzoazole having the general formula:
where Z represents oxygen or sulphur, A represents hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy, hydroxyl, sulphonate, carboxylate, cyano, halo, nitro or optionally substituted amino, n is from 1 to 4 and m is 1 or 2 such that when m is 2 each A may be the same or different.
wherein each of X and Y, which may be the same or different, represents fluorine, chlorine or bromine, and a benzoazole having the general formula:
where Z represents oxygen or sulphur, A represents hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy, hydroxyl, sulphonate, carboxylate, cyano, halo, nitro or optionally substituted amino, n is from 1 to 4 and m is 1 or 2 such that when m is 2 each A may be the same or different.
2. A method according to claim 1 in which X and Y
both represent chlorine.
both represent chlorine.
3. A method according to claim 1 in which Z
represents sulphur, A represents hydrogen and n is 1.
represents sulphur, A represents hydrogen and n is 1.
4. A method according to claim 1 in which the weight ratio of dithiolan to benzoazole is from 3:1 to 1:3.
5. A method according to any one of the preceding claims in which the dithiolan and benzoazole are each present in an amount from 1 to 500 ppm.
6. A method according to claim 5 in which the dithiolan and benzoazole are each present in an amount from 1 to 25 ppm.
7. A composition suitable for addition to an aqueous system which comprises at least one dithiolan as defined in claim 1 and at least one benzoazole as defined in claim 1.
8. A composition according to claim 7 in which the weight ratio of dithiolan to benzoazole is from 3:1 to 1:3.
9. A composition according to claim 7 which comprises 0.1 to 10% by weight of each of the dithiolan and benzoazole.
10. A composition according to claim 9 which comprises 0.25 to 3% by weight of each of the dithiolan and benzoazole.
11. A composition according to claim 7 which comprises one or more solvents.
12. A composition according to claim 11 which comprises methyl carbitol, butyldiglycol, N-methylpyrrolidone, tripropylene glycol n-butyl ether, dimethylformamide or diethylene glycol monoethyl ether.
13. A composition according to claim 7 which comprises 1 to 10% by weight of a biodispersant.
14. A composition according to claim 13 in which the biodispersant is a phenol ethoxylate.
15. A composition according to claim 7 which comprises 0.1 to 10% by weight of each of a dithiolan in which X and Y both represent chlorine and a benzoazole in which A represents hydrogen and n is 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9100170.1 | 1991-01-04 | ||
| GB9100170A GB2253841B (en) | 1991-01-04 | 1991-01-04 | Biocide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2058688A1 true CA2058688A1 (en) | 1992-07-05 |
Family
ID=10687979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058688A Abandoned CA2058688A1 (en) | 1991-01-04 | 1992-01-02 | Biocide for aqueous based systems |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA2058688A1 (en) |
| GB (1) | GB2253841B (en) |
| ZA (1) | ZA9232B (en) |
-
1991
- 1991-01-04 GB GB9100170A patent/GB2253841B/en not_active Expired - Fee Related
-
1992
- 1992-01-02 CA CA002058688A patent/CA2058688A1/en not_active Abandoned
- 1992-01-03 ZA ZA9232A patent/ZA9232B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2253841A (en) | 1992-09-23 |
| GB2253841B (en) | 1994-11-09 |
| GB9100170D0 (en) | 1991-02-20 |
| ZA9232B (en) | 1992-09-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |