CN105165829A - Composition of dibromomalonamide and applications of composition as biocidal agent - Google Patents
Composition of dibromomalonamide and applications of composition as biocidal agent Download PDFInfo
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- CN105165829A CN105165829A CN201510500505.9A CN201510500505A CN105165829A CN 105165829 A CN105165829 A CN 105165829A CN 201510500505 A CN201510500505 A CN 201510500505A CN 105165829 A CN105165829 A CN 105165829A
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Abstract
Provided are a composition of dibromomalonamide and applications of composition as a biocidal agent. The composition is a biocidal agent composition used for controlling microorganisms in an aqueous or water-containing system. The composition comprises dibromomalonamide and biocidal agents containing electrophilic reagents and selected from the following groups: (2-bromo-2-nitrovinyl)benzene, dithiocyano-methane and 1,2-dibromo-2,4-dicyanobutane. Provided are application of the composition in control of microorganisms in aqueous and water-containing systems.
Description
Patent application of the present invention is international application no is PCT/US2010/050880, international filing date is on September 30th, 2010, the application number entering National Phase in China is 201080069381.9, the divisional application of the application for a patent for invention that name is called " composition of dibromo malonamide and the purposes as biocide thereof ".
Technical field
The present invention relates to biocidal composition and in water-based and Aquo System for controlling method of microorganism.Described composition comprises 2,2-dibromo malonamide and comprises the Biocidal compounds of at least one electrophilic part.
Background technology
Water body is algae, bacterium, virus and fungi (some of them can be pathogenic) provide fertile breeding spot.Microbial contamination can produce various problem, comprises aesthetic property difference (such as muddy Green Water), serious health risk (such as fungi, bacterium or virus infections) and mechanicalness problem (comprising blocking, the corrosion of equipment and the minimizing of heat transfer).
In water-based system and Aquo System, biocide is usually used to sterilize and control microbial growth.But, and the biocide of not all is effective to various microorganism and/or temperature, and some biocides are incompatible with other chemical treatment additive.In addition, some biocides can not provide control of microorganisms enough for a long time.
Although by using relatively large biocide can overcome a part in above-mentioned shortcoming, the method can bring self problem, comprises that cost increases, waste increases and adds biocide by the possibility of character needed for handled for interference medium.In addition, because the activity of many commercially available biocide compound to the microorganism of some type is weak or certain micro-organisms has resistance to these compounds, even if therefore use relatively large biocide, these biocide compound still can not provide effective control.
There is provided a kind of like this Biocidal composition for aqueous systems process will be a major progress in this area, said composition can produce one or more following benefits: under low concentration, effect improves; Compatible with other additive in physical condition and handled medium; Effective to the microorganism of wide region; And/or the short-term control to microorganism and long-term control can be provided simultaneously.
Summary of the invention
In one aspect, the invention provides a kind of biocidal composition.Said composition can be used for controlling the microorganism in water-based or Aquo System.Said composition comprises: 2,2-dibromo malonamide and the Biocidal compounds (" biocide containing electrophilic reagent ") comprising at least one electrophilic part, wherein, the described biocide containing electrophilic reagent is selected from lower group: 2-bromo-2-nitropropane-1,3-glycol, bromo nitrobenzene ethene, dithiocyano-methane and 1, bromo-2, the 4-dicyanobutanes of 2-bis-.
In second, the invention provides a kind of method of microorganism controlled in water-based or Aquo System.The method comprises the biocidal composition as herein described of use effective dose to process described system.
Detailed Description Of The Invention
As mentioned above, the invention provides a kind of biocidal composition and use this compound to control method of microorganism.Said composition comprises: 2,2-dibromo malonamide and the biocide containing electrophilic reagent being selected from lower group: 2-bromo-2-nitropropane-1,3-glycol, bromo nitrobenzene ethene, dithiocyano-methane and bromo-2, the 4-dicyanobutanes of 1,2-bis-.We find surprisingly, and when 2,2-dibromo malonamide and the combination containing the biocide of electrophilic reagent as herein described being used for the control of microorganisms in water-based or water-bearing media with certain weight ratio, the combination of these two kinds of materials has synergy.That is, the biocidal properties of described combined material is than being improved based on the biocidal properties desired by its independent performance.This synergy makes the quantity of material for realizing required biocidal properties effect reduce, and therefore, decreases the problem caused by growth of microorganism in industrial treatment water, may reduce environmental influence and material cost simultaneously.
For purposes of the present invention, term " microorganism " includes but not limited to: bacterium, fungi, algae and virus.Term " control " should broadly be interpreted as including but not limited to following implication: suppress microbial growth or breeding, kills microorganism, sterilization and/or anticorrosion.Some preferred embodiment in, " control " refers to and suppresses microbial growth or breeding.In other embodiments, " control " refer to and kill microorganism.
Term " 2,2-dibromo malonamide " refers to by the compound of following chemical formulation:
2,2-dibromo malonamide and the biocide containing electrophilic reagent of the present invention all commercially, and/or can easily use the technology known to prepare by those skilled in the art.
In certain embodiments of the present invention, the weight ratio of 2,2-dibromo malonamide and the described biocide containing electrophilic reagent is about 100:1 to 1:100.
In some embodiments, the weight ratio of 2,2-dibromo malonamide and the described biocide containing electrophilic reagent is about 40:1 to 1:30.
In some embodiments, the weight ratio of 2,2-dibromo malonamide and the described biocide containing electrophilic reagent is about 32:1 to 1:20.
In some embodiments, the described biocide containing electrophilic reagent is the bromo-2-nitropropane-1 of 2-, 3-glycol, 2, the weight ratio of 2-dibromo malonamide and 2-bromo-2-nitropropane-1,3-glycol is about 100:1 to 1:20, or is about 70:1 to 1:10, or be about 40:1 to 1:5, or be about 32:1 to 1:2.In some embodiments, this weight ratio is about 9:1 to 3:1.
In some embodiments, the described biocide containing electrophilic reagent is bromo nitrobenzene ethene, 2, the weight ratio of 2-dibromo malonamide and bromo nitrobenzene ethene is about 100:1 to 1:20, or be about 70:1 to 1:10, or be about 40:1 to 1:5, or be about 32:1 to 1:2.
In some embodiments, the described biocide containing electrophilic reagent is dithiocyano-methane, and the weight ratio of 2,2-dibromo malonamide and dithiocyano-methane is about 40:1 to 1:10, or is about 32:1 to 1:1, or is about 32:1 to 4:1.
In some embodiments, the described biocide containing electrophilic reagent is bromo-2, the 4-dicyanobutanes of 1,2-bis-, 2,2-dibromo malonamide and 1,2-bis-bromo-2, the weight ratio of 4-dicyanobutane is about 20:1 to 1:10, or is about 10:1 to 1:1, or is about 8:1 to 2:1.
Composition of the present invention can be used for controlling the microorganism in various water-based and Aquo System.The example of this type of system includes but not limited to: paint and coating, water-based emulsion, latex, binder, ink, pigment dispersion, family expenses and industrial cleaners, detergent, dish washing detergent, mineral slurry, polymer emulsion, gap filler and adhesive, tape seam blend, disinfectant, bactericide, metal working fluids, building products, personal care product, weaving fluid (such as spinning oil), industrial treatment water (such as oil field water, paper pulp and paper water, cooling water), oil field functional fluid (such as drilling mud and fracturing fluid), fuel, air washing agent, waste water, water ballast, filtration system and swimming pool and thermal water.Preferred water-based system is metal working fluids, personal nursing, family expenses and industrial cleaners, industrial treatment water and paint and coating.Particularly preferably be industrial treatment water, paint and coating, metal working fluids and weaving fluid (such as spinning oil).
The effective dose that those of ordinary skill in the art do not need too much experiment to be just easy to determine for the described composition that provides control of microorganisms to use in any embody rule.As explanation, in the gross weight of described water-based or Aquo System for benchmark, suitable active material concentration (2,2-dibromo malonamide and the total containing the biocide of electrophilic reagent) be usually at least about 1ppm, or be at least about 3ppm, or be at least about 7ppm, or be at least about 10ppm, or be at least about 30ppm, or be at least about 100ppm.In some embodiments, in the gross weight of described water-based or Aquo System for benchmark, the suitable upper limit of active material concentration is about 1000ppm, or about 500ppm, or about 100ppm, or about 50ppm, or about 30ppm, or about 15ppm, or about 10ppm, or about 7ppm.
The component of described composition can be added in described water-based or Aquo System respectively, or carry out premix before interpolation.Those of ordinary skill in the art are easy to determine suitable adding method.Described composition can with other additive coupling in described system, and described additive is such as but not limited to surfactant, ion/non-ionic polymers and incrustation scale and corrosion inhibitor, oxygen scavenger and/or other biocide.
Following examples for illustration of the present invention, instead of are used for limiting its scope.Except as otherwise noted, ratio used herein, percentage, number etc. are by weight.
Embodiment
The result provided in embodiment uses growth inhibition test or sterilize experiment to produce.The details of each test is as follows.
sterilize experiment.This test is used as the synergistic preliminary assessment between described active substance.The method is as follows: pseudomonas aeruginosa (Pseudomonasaeruginosa) ATCC10045 of use equivalent (about 100CFU/ml) and the mixture of staphylococcus aureus (Staphylococcusaureus) ATCC6538 are to mineral salt solution (0.2203 gram of CaCl
2, 0.1847 gram of MgSO
4with 0.2033 gram of NaHCO
3in 1L water, pH is about 8) inoculate.Then use 2,2-dibromo malonamide (" DBMAL "), process with the described cell suspension of the combination of various levels to equal portions containing the biocide of electrophilic reagent and they.Hatch 2 hours under 37 DEG C of conditions after, determine biocidal efficacy based on the minimum biocide density (MBC) killed completely etc. in increment needed for bacterial cell.Then use this MBC value to calculate index of cooperation (SI) value.
The summary of described sterilize experiment result is as shown in each embodiment.In each table, list each biocide of test and the MBC value of mixture.Equally, index of cooperation (" the SI ") value of described combination is listed.Following formula is used to calculate SI:
Index of cooperation=M
dBMAL/ C
dBMAL+ M
b/ C
b
In formula,
C
dBMAL: the concentration of DBMAL when being used alone DBMAL needed for bacteria growing inhibiting;
C
b: the concentration of the biocide (B) when being used alone biocide (B) needed for bacteria growing inhibiting;
M
dBMAL: the concentration of DBMAL when DBMAL and biocide (B) coupling needed for bacteria growing inhibiting;
M
b: the concentration of the biocide (B) when biocide (B) and DBMAL coupling needed for bacteria growing inhibiting.
Described SI value is explained as follows:
SI<1: synergistic combination
SI=1: additivity combines
SI>1: antagonism combines
growth inhibition test.The growth inhibition test used in embodiment measures the growth inhibition (or lacking growth) of microorganism consortium.The suppression of growth can be the result of following situation: cell is killed (therefore not growing); A large amount of most cells group thus regrowth of being killed needs long time; Or inhibit growth and do not kill (static state).No matter be what mechanism of action, the impact of biocide (or combination of biocide) can be measured in time based on the increase of group's size.
This experiment measuring is the effect of one or more biocides in the growth preventing bacterial consortium in dilution mineral salts medium.Described medium comprises (in mg/litre) following component: FeCl
3.6H
2o (1); CaCl
2.2H
2o (10); MgSO
4.7H
2o (22.5); (NH
4)
2sO
4(40); KH
2pO
4(10); K
2hPO
4(25.5); Yeast extract (10); And glucose (100).Until all components being added into after in deionized water, the pH of this medium is adjusted to 7.5.After filtration sterilization, the equal sample of 100 microliter amount is dispensed in sterile microplates hole.Then the dilution of DBMAL and/or " biocide B " is added in this microwell plate.After the combination of active substance as follows to be prepared, with the cell suspension of 100 microlitres, each hole is inoculated, in this cell suspension every milliliter pseudomonas aeruginosa, pneumobacillus (Klebsiellapneumoniae), staphylococcus aureus and bacillus (Bacillussubtilis) mixture comprise an about 1x100 cell.In each hole, the final total volume of medium is 300 microlitres.As shown in table 1, when after as described herein being prepared, the concentration of each active substance is 25 to 0.19ppm.Gained medium can test 8 kinds of concentration of each active substance, namely with 64 kinds of the active substance of (active substance) different proportion combinations.
The template that the synergy based on microwell plate that table 1. shows each active material concentration is tested.The ratio of each active substance is in weight (ppm).
Control sample (not shown) comprises the medium not adding biocide.After the combination of active substance as implied above to be prepared, with the cell suspension of 100 microlitres, each hole is inoculated, in this cell suspension every milliliter pseudomonas aeruginosa, pneumobacillus, staphylococcus aureus and bacillus mixture comprise an about 1x100 cell.In each hole, the final total volume of medium is 300 microlitres.
After microwell plate is got ready in advance, under 580 nanometers, measure optical density (OD) reading in each hole immediately, then make this plate hatch 24 hours at 37 DEG C.After incubation period, at OD
580be worth collected before, gentle agitation is carried out to this plate.Use T
24the OD at place
580value deducts T
0the OD at place
580value is to determine the total amount of the growth (or lacking growth) occurred.These values are used to calculate owing to there is each biocide and each 64 kinds of combinations and the growth inhibition percentage that causes.In conjunction with following formula, use 90% growth inhibition as the threshold value calculating index of cooperation (SI) value:
Index of cooperation=M
dBMAL/ C
dBMAL+ M
b/ C
b
In formula,
C
dBMAL: suppress the DBMAL concentration needed for bacterial growth of about 90% when being used alone DBMAL;
C
b: the concentration suppressing the biocide (B) needed for bacterial growth of about 90% when being used alone biocide (B);
M
dBMAL: the concentration suppressing the DBMAL needed for bacterial growth of about 90% when DBMAL and biocide (B) coupling;
M
b: the concentration suppressing the biocide (B) needed for bacterial growth of about 90% when biocide (B) and DBMAL coupling.
Described SI value is explained as follows:
SI<1: synergistic combination
SI=1: additivity combines
SI>1: antagonism combines
In the examples below, in solution, the amount of biocide is unit metering with the solution of mg/litre (mg/l).Because solution density is about 1.0, therefore mg/litre tolerance corresponds to weight ppm.Therefore, Liang Zhong unit is used interchangeably in an embodiment.
Embodiment 1
dBMAL and bronopol (bronopol)
Sterilize experiment result.Table 2 summarizes the result of the test being used alone DBMAL and DBMAL and 2-bromo-2-nitropropane-1,3-glycol (" bronopol " or " BNPD ") coupling.The results show that the synergy (table 2) between active substance.
The MBC of table 2.DBMAL, bronopol and combination thereof.
Developing restraint result of the test.Table 3 shows the Developing restraint result of the test of DBMAL, THPS and combination thereof.In this experiment, the Cmin (I of the DBMAL needed for growth fraction control sample at least low 90% of consortium
90value) be 12.5 mg/litre.The I of bronopol
90value is 6.25 mg/ml.
After table 3.24 hour incubation period, the growth inhibition percentage in the microorganism consortium that the species produced by the combination of independent bronopol (BNPD), independent DBMAL and these two kinds of active substances limit.Compared with optical density measurements when numeric representation is 0 with the time, the growth inhibition percentage of time measured by 24 little optical density measurements (580 nanometer) constantly.
Table 4 shows under growth inhibition test, finds the ratio with synergistic DBMAL and bronopol (BNPD).
Table 4.
Embodiment 2
dBMAL and BNS
Developing restraint result of the test.The Developing restraint result of the test that table 5 shows DBMAL, bromo nitrobenzene ethene (" BNS ") and combines.The I of DBMAL and BNS
90value is respectively 12.5 mg/litre and 6.25 mg/litre.
After table 5.24 hour incubation period, the growth inhibition percentage in the microorganism consortium that the species produced by the combination of independent BNS, independent DBMAL and these two kinds of active substances limit.Compared with optical density measurements when numeric representation is 0 with the time, the growth inhibition percentage of time measured by 24 little optical density measurements (580 nanometer) constantly.
Table 6 shows under growth inhibition test, finds the concentration with synergistic DBMAL and BNS.This ratio is based on the concentration of active substance.
Table 6
Embodiment 3
dBMAL and MBT
Developing restraint result of the test.The Developing restraint result of the test that table 7 shows DBMAL, dithiocyano-methane (" MBT ") and combines.The I of DBMAL and MBT
90value is respectively 12.5 mg/litre and 0.78 mg/litre.
After table 7.24 hour incubation period, the growth inhibition percentage in the microorganism consortium that the species produced by the combination of independent DBMAL, independent MBT and these two kinds of active substances limit.Compared with optical density measurements when numeric representation is 0 with the time, the growth inhibition percentage of time measured by 24 little optical density measurements (580 nanometer) constantly.
Table 8 shows the concentration finding to have synergistic DBMAL and MBT.This ratio is based on the concentration of active substance.
Table 8
Embodiment 4
dBMAL and DBDCB
Developing restraint result of the test.The Developing restraint result of the test that table 9 shows DBMAL, 1,2-bis-bromo-2,4-dicyanobutanes (" DBDCB ") and combines.The I of DBMAL and DBDCB
90value is 6.25 mg/litre.
After table 9.24 hour incubation period, the growth inhibition percentage in the microorganism consortium that the species produced by the combination of independent DBMAL, independent DBDCB and these two kinds of active substances limit.Compared with optical density measurements when numeric representation is 0 with the time, the growth inhibition percentage of time measured by 24 little optical density measurements (580 nanometer) constantly.
Table 10 shows the concentration finding to have synergistic DBMAL and DBDCB.
Table 10
Although according to the preferred embodiment of the present invention to invention has been above description, can to modify the present invention and these amendments comprise within the spirit and scope of the present invention.Therefore this application be intended to contain use general principle as herein described of the present invention any change, application or change.In addition, the application is intended to contain belong to the known of field belonging to the present invention or conventional practice and fall into and deviates part with the present invention in the restriction of appended claims.
Claims (10)
1. one kind for controlling the biocidal composition of the microorganism in water-based or Aquo System, said composition comprises: 2,2-dibromo malonamide and the biocide containing electrophilic reagent being selected from lower group: bromo-2, the 4-dicyanobutanes of bromo nitrobenzene ethene, dithiocyano-methane and 1,2-bis-.
2. composition as claimed in claim 1, is characterized in that, the weight ratio of 2,2-dibromo malonamide and the described biocide containing electrophilic reagent is about 100:1 to 1:100.
3. composition as claimed in claim 1, is characterized in that, the described biocide containing electrophilic reagent is bromo nitrobenzene ethene, and the weight ratio of 2,2-dibromo malonamide and bromo nitrobenzene ethene is about 32:1 to 1:2.
4. composition as claimed in claim 1, is characterized in that, the described biocide containing electrophilic reagent is dithiocyano-methane, and the weight ratio of 2,2-dibromo malonamide and dithiocyano-methane is about 32:1 to 4:1.
5. composition as claimed in claim 1, is characterized in that, the described biocide containing electrophilic reagent is bromo-2, the 4-dicyanobutanes of 1,2-bis-, and the weight ratio of 2,2-dibromo malonamide and bromo-2, the 4-dicyanobutanes of 1,2-bis-is about 8:1 to 2:1.
6. the composition according to any one of claim 1-5, said composition is: paint, coating, water-based emulsion, latex, binder, ink, pigment dispersion, family expenses or industrial cleaners, detergent, dish washing detergent, mineral slurry polymer emulsion, gap filler, adhesive, tape seam blend, disinfectant, bactericide, metal working fluids, building products, personal care product, weaving fluid, spinning oil, industrial treatment water, oil field functional fluid, fuel, air washing agent, waste water, water ballast, filtration system, swimming pool or thermal water.
7. control a method for growth of microorganism in water-based or Aquo System, the method comprises and uses the composition according to any one of claim 1-5 of effective dose to water-based or Aquo System as described in processing.
8. method as claimed in claim 7, it is characterized in that, described water-based or Aquo System are paint, coating, water-based emulsion, latex, binder, ink, pigment dispersion, family expenses or industrial cleaners, detergent, dish washing detergent, mineral slurry polymer emulsion, gap filler, adhesive, tape seam blend, disinfectant, bactericide, metal working fluids, building products, personal care product, weaving fluid, spinning oil, industrial treatment water, oil field functional fluid, fuel, air washing agent, waste water, water ballast, filtration system, swimming pool or thermal water.
9. the method according to any one of claim 7-8, is characterized in that, described composition suppresses microbial growth in described water-based or Aquo System.
10. the method according to any one of claim 7-8, is characterized in that, described composition kills the microorganism in described water-based or Aquo System.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710538261.2A CN107251902A (en) | 2010-09-30 | 2010-09-30 | The composition of dibromo malonamide and its purposes as biocide |
| CN201510500505.9A CN105165829A (en) | 2010-09-30 | 2010-09-30 | Composition of dibromomalonamide and applications of composition as biocidal agent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201080069381.9A CN103200818B (en) | 2010-09-30 | 2010-09-30 | Compositions of dibromomalonamide and their use as biocides |
| CN201510500505.9A CN105165829A (en) | 2010-09-30 | 2010-09-30 | Composition of dibromomalonamide and applications of composition as biocidal agent |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080069381.9A Division CN103200818B (en) | 2010-09-30 | 2010-09-30 | Compositions of dibromomalonamide and their use as biocides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105165829A true CN105165829A (en) | 2015-12-23 |
Family
ID=54979339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510500505.9A Pending CN105165829A (en) | 2010-09-30 | 2010-09-30 | Composition of dibromomalonamide and applications of composition as biocidal agent |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839583A (en) * | 1973-06-28 | 1974-10-01 | Betz Laboratories | Slime control compositions and their use |
| WO2008091453A1 (en) * | 2007-01-22 | 2008-07-31 | Dow Global Technologies Inc. | Method to control reverse osmosis membrane biofouling in drinking water production |
-
2010
- 2010-09-30 CN CN201510500505.9A patent/CN105165829A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839583A (en) * | 1973-06-28 | 1974-10-01 | Betz Laboratories | Slime control compositions and their use |
| WO2008091453A1 (en) * | 2007-01-22 | 2008-07-31 | Dow Global Technologies Inc. | Method to control reverse osmosis membrane biofouling in drinking water production |
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Application publication date: 20151223 |