WO2002014293A1 - Quaternary ammonium salts of 1,2-benzisothiazolin-3-one. preparation and use as biocides - Google Patents
Quaternary ammonium salts of 1,2-benzisothiazolin-3-one. preparation and use as biocides Download PDFInfo
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- WO2002014293A1 WO2002014293A1 PCT/DK2000/000453 DK0000453W WO0214293A1 WO 2002014293 A1 WO2002014293 A1 WO 2002014293A1 DK 0000453 W DK0000453 W DK 0000453W WO 0214293 A1 WO0214293 A1 WO 0214293A1
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- quaternary ammonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
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- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
Definitions
- BIT 1 ,2-Benzisothiazolin-3-one, referred to hereinafter as BIT, is known to possess bacteriacidal and fungicidal properties, for which reason it to a large extent is used as a biocide for preservation of technical formulations. This is necessary where the technical formulation does not possess antibacterial and antifungal properties.
- BIT is used in different physical states, either as a dispersion or in solution as salts where the cation might be ammonium or alkali metals, typically sodium.
- organic solvents like glycols are used.
- a BIT solution as the sodium salt, can contain up to 20% BIT by weight, if the solution except for water contains 60% by weight of dipropyleneglycol. The solution is stable down to - 3°C without crystallisation.
- a water solution of BIT as the lithium salt in a concentration of 10% by weight, does not show crystallisation down to 5°C, like the sodium salt.
- a more concentrated solution of BIT as the lithium salt can be obtained by addition of hydroxylic organic solvents.
- Ri represents alkyl, substituted alkyl, aryl or substituted aryl
- R 2 , R 3 and R 4 represents alkyl or substituted alkyl, where the substituent is an aryl-, halogene-, hydroxyl-, nitro-, alkoxy- or acyl-group, or R-, and R 2 together represents an alkylene group which together with the nitrogen atom forms a tree-, four-, five- or six-membered heterocyclic ringsystem.
- Quaternary ammonium salts of BIT can be prepared by mixing BIT and quaternary ammonium hydroxide as solid or in solution, typically water, in equimolar proportion 1 : 1.
- quaternary ammonium salts of BIT in different concentrations, depending on the concentration of the quaternary ammonium hydroxide used.
- the solution can be diluted with water or concentrated by evaporation of water so that the concentration of quaternary ammonium salt of BIT is from 5% to 60% by weight, calculated as BIT.
- another salt can be used, represented by phosphate, carbonate, hydrogencarbonate, sulphate, hydrogensulphate or halogenide, either as a solid or solution, typically water solution.
- BIT in solid form can be brought together with a quaternary ammonium salt in the molar ratio 1:1, in a suitable solvent.
- the slurry or solution has then to be neutralised with the equimolar amount of an alkaline compound, typically alkali metal hydroxide.
- a solution of BIT as a metal salt, typically alkali salt in water, can also be used to produce a 1 : 1 molar mixture with a quaternary ammonium salt.
- the quaternary ammonium salt of BIT may separate directly from the solution, or be extractet with a suitable solvent, like a non water miscible organic solvent of alifatic or aromatic origin containing polar groups like hydroxy, carbonyl, alkoxycarbonyl, amido, nitrilo, or ether.
- a suitable solvent like a non water miscible organic solvent of alifatic or aromatic origin containing polar groups like hydroxy, carbonyl, alkoxycarbonyl, amido, nitrilo, or ether.
- Organic solvents which are miscible with water may in some cases be used, as a high concentration of inorganic salt will make separation possible.
- Acetonitril is an example.
- the quaternary ammonium salt of BIT can be isolated by evaporation of water and extraction, from the residue, into an organic solvent.
- the stability of the solution of quaternary ammonium salt of BIT in water can, at lower temperatures be improved by addition of water miscible organic solvents which are known to lower the freezing point of water and are used as such. This might be lower alcohols or glycols, as methanol, ethanol, propanol, ethyleneglycol, diethyleneglycol, 1,2-dipropyleneglycol or dipropyleneglycol.
- the water solution is stable for more than 24 hours at -15°C.
- stable means, referred to and hereinafter, that no crystallisation occurs after seeding with crystalline material used for the solution, at the temperature stated.
- Table 1 shows examples of quaternary ammonium salts of BIT, Q.BIT, which forms stable water solutions. R is referring to Formula 1.
- Q.BIT are also soluble in polar organic solvents as acetonitril or dipropyleneglycol. This might be of interest of one was forced not to use formulations of BIT in water.
- the solubility of BIT in e.g. dipropyleneglycol is less than for the corresponding quaternary ammonium salts.
- Table 2 shows examples of the solubility of quaternary ammonium salts of BIT, and BIT, calculated as % per weight as Q.BIT and % per weight as BIT, at the lowest temperature where the solution is stable, in water and dipropyleneglycol. The examples refers to the numbering in Table 1.
- R1 R2 R3 R4 (1) C CHH 3 3 C CHH33 C CHH 3 3 CH 3 (2) C CHH33 C CHH33 C CHH33 CH2CH2OH
- the content of (1) is 39% corresponding to 26% calculated as BIT.
- the prepared solution might be concentrated by evaporation of water, 53 g, to a strength of 40% as BIT. Which is stable at 3°C.
- sulfuric acid (1) can be isolated quantitatively.
- (1) is soluble in dipropyleneglycol, and as an example a 36% is stable at room temperature.
- Benzalkonium chloride (95%, 30g) is dissolved in water (100ml) at 40°C.
- BIT water content 20%, purity dried 98%, 16.3g
- sodium hydroxide (32%, 13.5g)
- quaternary ammonium salts of BIT in some examples of salts have shown a surprisingly higher biocidal effect than the sodium salt of BIT, and also an synergetic effect between the BIT part and particular the benzalkonium part.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
Preparation and characterisation of new ammonium salts of 1,2,benzisothiozolin-3-one, and their use for preparation of highly concentrated solutions with biocidal properties. Quaternary ammonium salts are prepared by reacting 1,2-benzisothiazolin-3-one with either quaternary ammonium hydroxide, or a quaternary ammonium salt, where typically the anion is represented by halogenide, sulphate, phosphate or carbonate with simultaneous addition of metal hydroxide, typically alkali. Quaternary ammonium salts of 1,2-benzisothiazolin-3-one can be formulated in water solutions or solutions of water miscible solvents, solutions of organic solvents containing water, in proportions by weight between the ammonium salt of 1,2-benzisothiazolin-3-one, water and the organic solvents as (10-90):(0-90). 1,2-benzisothiazolin-3-one is shown to exhibit its known biocidal effect after transformation to the ammonium salt.
Description
Quaternary Ammonium Gaits of 1 , 2-Benzisothiazolin-3-one ,
Preparation and use as biocides.
1 ,2-Benzisothiazolin-3-one, referred to hereinafter as BIT, is known to possess bacteriacidal and fungicidal properties, for which reason it to a large extent is used as a biocide for preservation of technical formulations. This is necessary where the technical formulation does not possess antibacterial and antifungal properties. BIT is used in different physical states, either as a dispersion or in solution as salts where the cation might be ammonium or alkali metals, typically sodium. To stabilise the solutions, organic solvents like glycols are used.
The mentioned formulations of BIT exhibits different unwanted properties.
By using dispersions, BIT might settle out on standing, giving problems in charging the material. As disclosed in patent WO 94/16564, a BIT solution, as the sodium salt, can contain up to 20% BIT by weight, if the solution except for water contains 60% by weight of dipropyleneglycol. The solution is stable down to - 3°C without crystallisation. As disclosed in patent DK 165865 B, a water solution of BIT as the lithium salt, in a concentration of 10% by weight, does not show crystallisation down to 5°C, like the sodium salt. As mentioned earlier a more concentrated solution of BIT as the lithium salt can be obtained by addition of hydroxylic organic solvents.
During the search for BIT salts with a high solubility in water without addition of stabilising. „ water miscible organic solvents, surprisingly it was found that quaternary ammonium salts of BIT with a structure represented by Formula 1 , shows a high solubility in water compared to what has been found for other known salts of BIT. For economical and environmental reasons it would be desirable to prepare solutions of BIT without using organic solvents.
Formula 1
In Formula 1 Ri represents alkyl, substituted alkyl, aryl or substituted aryl, and R2, R3 and R4 represents alkyl or substituted alkyl, where the substituent is an aryl-, halogene-, hydroxyl-, nitro-, alkoxy- or acyl-group, or R-, and R2 together represents an alkylene group which together with the nitrogen atom forms a tree-, four-, five- or six-membered heterocyclic ringsystem. Quaternary ammonium salts of BIT, according to Formula 1 , can be prepared by mixing BIT and quaternary ammonium hydroxide as solid or in solution, typically water, in equimolar proportion 1 : 1.
In this way it is possible to prepare solutions of quaternary ammonium salts of BIT in different concentrations, depending on the concentration of the quaternary ammonium hydroxide used. The solution can be diluted with water or concentrated by evaporation of water so that the concentration
of quaternary ammonium salt of BIT is from 5% to 60% by weight, calculated as BIT. If the quaternary ammonium hydroxide is not readily available, another salt can be used, represented by phosphate, carbonate, hydrogencarbonate, sulphate, hydrogensulphate or halogenide, either as a solid or solution, typically water solution.
BIT in solid form, can be brought together with a quaternary ammonium salt in the molar ratio 1:1, in a suitable solvent. The slurry or solution has then to be neutralised with the equimolar amount of an alkaline compound, typically alkali metal hydroxide. A solution of BIT as a metal salt, typically alkali salt in water, can also be used to produce a 1 : 1 molar mixture with a quaternary ammonium salt. The quaternary ammonium salt of BIT may separate directly from the solution, or be extractet with a suitable solvent, like a non water miscible organic solvent of alifatic or aromatic origin containing polar groups like hydroxy, carbonyl, alkoxycarbonyl, amido, nitrilo, or ether. Organic solvents which are miscible with water may in some cases be used, as a high concentration of inorganic salt will make separation possible. Acetonitril is an example.
Instead of extraction, the quaternary ammonium salt of BIT can be isolated by evaporation of water and extraction, from the residue, into an organic solvent. The stability of the solution of quaternary ammonium salt of BIT in water can, at lower temperatures be improved by addition of water miscible organic solvents which are known to lower the freezing point of water and are used as such. This might be lower alcohols or glycols, as methanol, ethanol, propanol, ethyleneglycol, diethyleneglycol, 1,2-dipropyleneglycol or dipropyleneglycol.
Characterisation of the prepared of the prepared quaternary ammonium salts of BIT by the described methods, were for selected examples done by isolating the compounds in a pure form and obtain PMR spectra for verification of the molecular structure.
Solubility in water was estimated by dissolving the pure compounds in water, and examining the the stability at different temperatures. Surprisingly it was shown that solutions of quaternary ammonium salts of BIT were stable below 0°C at a much higher concentration, calculated as BIT, than for other known BIT salt solutions. In the example where the quaternary ammonium ion is 2-hydroxyethyltrimethylammonium
( Ri , R2, R3 = CH3 and R4= CH2CH2OH ), the water solution is stable for more than 24 hours at -15°C. By stable means, referred to and hereinafter, that no crystallisation occurs after seeding with crystalline material used for the solution, at the temperature stated.
Table 1 shows examples of quaternary ammonium salts of BIT, Q.BIT, which forms stable water solutions. R is referring to Formula 1.
Q.BIT are also soluble in polar organic solvents as acetonitril or dipropyleneglycol. This might be of interest of one was forced not to use formulations of BIT in water.
The solubility of BIT in e.g. dipropyleneglycol is less than for the corresponding quaternary ammonium salts.
Table 2 shows examples of the solubility of quaternary ammonium salts of BIT, and BIT, calculated as % per weight as Q.BIT and % per weight as BIT, at the lowest temperature where the solution is stable, in water and dipropyleneglycol. The examples refers to the numbering in Table 1.
Table 1
R1 R2 R3 R4 (1) C CHH33 C CHH33 C CHH33 CH3 (2) C CHH33 C CHH33 C CHH33 CH2CH2OH
(3) CH3(CH2)3 CH3(CH2)3 CH3(CH2)3 CH3(CH2)3
(4) CH3 CH3 C6H5CH2 0.6 CH3(CH2)11
0.4 CH3(CH2)13
Table 2
Solution in water Solution in dipropyleneglycol
Q.BIT BIT% Q.BIT% °C BIT% Q.BIT% °C
(1) 40 59 3 30 44 -10
(2) 45 76 -15 30 51 -10
(3) 30 75 0 25 65 18
(4) 26 79 -5 19 58 -10
BIT 7 7
BIT 10 20
Examples Example 1.
(1) in Table 1. Tetramethylammonium salt of BIT.
To a solution in water of tetramethylammonium hydroxide (25%, 101.6 g), BIT(water content 20%, purity dried 98%, 54.6), is added, with agitation and simultaneously measuring of pH, to pH reached 9.58.
The content of (1) is 39% corresponding to 26% calculated as BIT. The prepared solution might be concentrated by evaporation of water, 53 g, to a strength of 40% as BIT. Which is stable at 3°C.
By total evaporation of water in vacou, and keeping the material over cone, sulfuric acid, (1) can be isolated quantitatively. (1) is soluble in dipropyleneglycol, and as an example a 36% is stable at room temperature.
Characterisation of (1) by PMR spectroscopy:
1H NMR (250 MHz, DMSO) d: 3.14 (s, 12H, 4CH3), 7.11 (t, 1H, J=7.0 Hz, ArH), 7.25
(t, 1H, J=7.0 Hz, ArH), 7.57 (d, 1H, J=7.8 Hz, ArH), 7.64 (d, 1H, J=7.6 Hz, ArH).
Example 2
(2) in Table 1. 2-hydroxyethyltrimethylammonium salt of BIT.
A solution of cholin hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, (100g, 50%), is added, with stirring and pH monitoring, BIT (water content 17.4%, purity dried 99.0%, 79 g) to pH 9.2. The solution is filtered clear. The content of (2) is 59% corresponding to 35% as BIT. By evaporation of water, the solution can be concentrated to 85% as (2) or 51% calculated as BIT, without separation of solids at 20°C. By evaporation of water and drying over cone, sulfuric acid (2) can be isolated quantitatively as a white crystalline product. Characterisation of (2) by PMR spectroscopy:
1H NMR (250 MHz, DMSO) d: 3.16 (s, 9H, 3CH3), 3.48 (m, 2H, CH2), 3.91(m, 2H, CH2), 7.17 (m,
1H, ArH), 7.32 (m, 1H, ArH), 7.65 (m, 1H, ArH), 7.72 (m, 1H, ArH)
Example 3
(3) in Table 1. tetrabutylammonium salt of BIT.
BIT (water content 20%, purity dried 98%, 18.7g) is stirred witk tetrabutylammoniumhydrogen sulphate (31.4g) in 100ml water. A solution in water of sodium hydroxide (27%, 23.5g) is added to pH 11.5, whereby an oily top phase separates. The oil phase is separated, dried in vacuo over cone, sulfuric acid yielding (3) as light yellow crystals. The yield of (3) is 31.9 g, 88% of theory. Characterisation of (3) by PMR spectroscopy:
1H NMR (250 MHz, DMSO) d: 0.91 (t, 12H, J=7.3 Hz, 4CH3), 1.29 (m, 8H, 4CH2), 1.55 (m, 8H, 4CH2), 3.18 (m, 8H, 4CH2), 7.07 (td, 1H, J=7.3; 0.9 Hz, ArH), 7.21 (td, 1H, J=7.4; 1.2 Hz, ArH), 7.52 (d, 1H, J=7.8 Hz, ArH), 7.56 (d, 1H, J=7.2 Hz, ArH)
Example 4
(4) in Table 1. Benzalkonium (benzyldimethyl-dodecyl(60%)/tetradecyl(40%)ammonium) salt af
BIT.
Benzalkonium chloride (95%, 30g) is dissolved in water (100ml) at 40°C. BIT (water content 20%, purity dried 98%, 16.3g) together with sodium hydroxide (32%, 13.5g) to pH 11.
A bottom phase separates, is washed with water, 70 mL, dissolved in toluene, 50 g, and evaporated in vacou, dried over cone, sulfuric acid. Leaving crystalline (4) in 33g yield, 87% of theory.
Characterisation of (4) by PMR spectroscopy:
1H NMR (250 MHz, DMSO) d: 0.86 (t, 3H, J=6.7 Hz, CH2CH.3), 1.24 (s, 19.5H, 9.8CH2),
1.72 (m, 2H, N-CH2CH2), 2.98 (s, 6H, N-CH3), 3.26 (t, 2H, J=8.2 Hz, N-CH2), 4.61 (s, 2H,
N-CH2-Ar), 7.08 (t, 1H, J=7.2 Hz, ArH), 7.23 (t, 1H, J=7.2 Hz, ArH), 7.55(m, 7H, ArH).
Together with the possibility for preparing stable solutions of BIT in a higher concentration than known hitherto, quaternary ammonium salts of BIT, in some examples of salts have shown a surprisingly higher biocidal effect than the sodium salt of BIT, and also an synergetic effect between the BIT part and particular the benzalkonium part.
In Table 3 are shown the biocidal effect, of quaternary ammonium salts as water solutions, aginst bacteria as Eschericia coli and Bacillus subtilis, yeast as Candida albican, and fungi as Aspergillus niger. The results are given as the minimum inhibitory concentration (MIC) in parts per million (ppm), and calculated as BIT / Q.BIT. As a reference the sodium salt of BIT is included, calculated as BIT/Na.BIT. The numbering of the different salts are as referred to in Table 1.
Tabel 3
Q.BIT Esch.coli Bac.subt. Cand.albic. Asp.nigi
(1) 30/45 30/45 120/178 15/22
(2) 120/202 30/50 120/202 8/14
(3) 30/78 30/78 120/312 15/39
(4) 15/46 8/25 4/12 2/6
(Na) 120/137 30/34 120/137 15/17
Claims
1. Ammonium salts of 1 ,2-benzisothiazolin-3-one, according to Formula 1 ,
Formula 1 where Ri is represented by alkyl, substitutet alkyl, aryl or substituted aryl, and R2, R3 and R4 is represented by alkyl or substituted alkyl, where the substituent is an aryl group, a halogen atom, a hydroxyl group, a nitro group, an alkoxy group, an acyl group or Ri and R2 together represents an alkylene group which together with the nitrogen atom forms a tree-, four-, five- or six-membered heterocyclic ring system. 2. A liqiud composition which contains an ammonium salt of 1 ,2-benzisothiazolin-3-one, comprising a quarternary ammonium salt of 1 ,
2-benzisothiazolin-3-one and not less than 10% solvent.
3. The composition of claim 2, comprising not less than 10% quaternary ammonium salt of
1 ,2-benzisothiazolin-3-one.
4. A composition of claim 2 and/or 3, comprising a quaternary ammonium salt, water and a water miscible organic solvent in weight proportions (10-90) : (0-90) : (0-90).
5. A composition of claims 2 to 4, comprising the water miscible organic solvent is ethylene glycol or dipropyleneglycol.
6. A composition of claims 2 to 5, comprising that the quaternary ammonium cation is characterised by the formula RL R2, Ra.Rt N+, where R- represents alkyl, substituted alkyl, aryl or substituted aryl and R2, R3, > represents alkyl or substituted alkyl, as the substituent is a halogene atom, a hydroxyl group, a nitro group, an alkoxy group, an acyl group or an aryl group, or Ri and R2 together represents an alkylene group which together with the nitrogen atom forms a tree-, four-, five- or six-membered heterocyclic ring system.
7. A composition of claims 6, comprising that the quaternary ammonium cation to be tetramethylammonium, 2-hydroxyethyltrimethylammonium, dodecyltrimethylammonium or benzalkonium.
8. A process to prepare the composition in one or several of claims 1 to 7, comprising that the quaternary ammonium salt of 1,2-benzisothiazolin-3-on, water and a water miscible organic solvent, is brought together in weight proportions (10-90) : (0-90) : (0-90).
9. A process according to claim 8 comprising reaction between 1 ,2-benzisothioazolin-3-one and quaternary ammonium hydroxide / ammonium carbonate in the equimolar ratio 1:1, in water or / and an organic solvent which is miscible with water to form a quaternary ammonium salt of 1 ,2-benzisothiazolin-3-one.
10. A process according to claim 8 comprising reaction of 1 ,2-benzisothiazolin-3-one or an alkali metal salt hereof with a quaternary ammonium salt as phosphate, hydrogencarbonate, carbonate, sulphate, hydrogensulphate or halogenide in the equimolar ratio 1:1, in water or / and an organic solvent which is miscible with water to form a quaternary ammonium salt of 1 ,2-benzisothiazolin-3-one. When 1 ,2-benzisothiazolin-3-one is used, an equimolar amount of alkali metal salt is added for neutralisation.
11. Use of the composition according to one or several of claims 2 - 8, as a technical biocide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/DK2000/000453 WO2002014293A1 (en) | 2000-08-15 | 2000-08-15 | Quaternary ammonium salts of 1,2-benzisothiazolin-3-one. preparation and use as biocides |
| AU2000265583A AU2000265583A1 (en) | 2000-08-15 | 2000-08-15 | Quaternary ammonium salts of 1,2-benzisothiazolin-3-one. preparation and use as biocides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/DK2000/000453 WO2002014293A1 (en) | 2000-08-15 | 2000-08-15 | Quaternary ammonium salts of 1,2-benzisothiazolin-3-one. preparation and use as biocides |
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| Publication Number | Publication Date |
|---|---|
| WO2002014293A1 true WO2002014293A1 (en) | 2002-02-21 |
| WO2002014293A8 WO2002014293A8 (en) | 2003-04-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DK2000/000453 Ceased WO2002014293A1 (en) | 2000-08-15 | 2000-08-15 | Quaternary ammonium salts of 1,2-benzisothiazolin-3-one. preparation and use as biocides |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU2000265583A1 (en) |
| WO (1) | WO2002014293A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2020178A1 (en) * | 2007-08-01 | 2009-02-04 | THOR GmbH | Biocidal composition comprising the potassium salt of benzisothiazolin-3-on and ethylene glycol |
| WO2013060485A1 (en) | 2011-10-27 | 2013-05-02 | Titan Chemicals Limited | Biocide |
| WO2013060764A1 (en) | 2011-10-27 | 2013-05-02 | Titan Chemicals Limited | Biocide composition |
| US9415009B2 (en) | 2009-05-29 | 2016-08-16 | Pearl Therapeutics, Inc. | Compositions, methods and systems for respiratory delivery of two or more active agents |
| US9463161B2 (en) | 2009-05-29 | 2016-10-11 | Pearl Therapeutics, Inc. | Compositions for pulmonary delivery of long-acting muscarinic antagonists and associated methods and systems |
| CN117776580A (en) * | 2023-12-26 | 2024-03-29 | 科之杰新材料集团有限公司 | Preservative for polycarboxylate water-reducing agent containing isothiazolinone composition and preparation method thereof |
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|---|---|---|---|---|
| US3300377A (en) * | 1962-01-16 | 1967-01-24 | Hollichem Corp | Biocidal quaternary ammonium aromatic cyclic imides |
| GB1460279A (en) * | 1973-05-10 | 1976-12-31 | Ici Ltd | Biocidal compositions |
| EP0231491A1 (en) * | 1986-01-08 | 1987-08-12 | CASSELLA Aktiengesellschaft | Aqueous 1,2-benzisothiazolin-3-one preparation |
| US4849438A (en) * | 1987-11-18 | 1989-07-18 | Agro-Kanesho Co., Ltd. | 1,2-benzoisothiazol-3(2H)-one 1,1-dioxide, ion(1-),2-hydroxy-N,N,N-trimethyl-ethanaminium which is plant protection agent for control of fungi and bacteria |
| WO1994016564A1 (en) * | 1993-01-19 | 1994-08-04 | Zeneca Limited | Stable liquid compositions and their use |
-
2000
- 2000-08-15 AU AU2000265583A patent/AU2000265583A1/en not_active Abandoned
- 2000-08-15 WO PCT/DK2000/000453 patent/WO2002014293A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3300377A (en) * | 1962-01-16 | 1967-01-24 | Hollichem Corp | Biocidal quaternary ammonium aromatic cyclic imides |
| GB1460279A (en) * | 1973-05-10 | 1976-12-31 | Ici Ltd | Biocidal compositions |
| EP0231491A1 (en) * | 1986-01-08 | 1987-08-12 | CASSELLA Aktiengesellschaft | Aqueous 1,2-benzisothiazolin-3-one preparation |
| US4849438A (en) * | 1987-11-18 | 1989-07-18 | Agro-Kanesho Co., Ltd. | 1,2-benzoisothiazol-3(2H)-one 1,1-dioxide, ion(1-),2-hydroxy-N,N,N-trimethyl-ethanaminium which is plant protection agent for control of fungi and bacteria |
| WO1994016564A1 (en) * | 1993-01-19 | 1994-08-04 | Zeneca Limited | Stable liquid compositions and their use |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2020178A1 (en) * | 2007-08-01 | 2009-02-04 | THOR GmbH | Biocidal composition comprising the potassium salt of benzisothiazolin-3-on and ethylene glycol |
| WO2009016252A1 (en) * | 2007-08-01 | 2009-02-05 | Thor Gmbh | Biocidal composition including the potassium salt of 1,2-benzisothiazolin-3-one and ethylene glycol |
| US9415009B2 (en) | 2009-05-29 | 2016-08-16 | Pearl Therapeutics, Inc. | Compositions, methods and systems for respiratory delivery of two or more active agents |
| US9463161B2 (en) | 2009-05-29 | 2016-10-11 | Pearl Therapeutics, Inc. | Compositions for pulmonary delivery of long-acting muscarinic antagonists and associated methods and systems |
| US10716753B2 (en) | 2009-05-29 | 2020-07-21 | Pearl Therapeutics, Inc. | Compositions for pulmonary delivery of long-acting muscarinic antagonists or long-acting B2 adrenergic receptor agonists and associated methods and systems |
| WO2013060485A1 (en) | 2011-10-27 | 2013-05-02 | Titan Chemicals Limited | Biocide |
| WO2013060764A1 (en) | 2011-10-27 | 2013-05-02 | Titan Chemicals Limited | Biocide composition |
| US8466184B2 (en) | 2011-10-27 | 2013-06-18 | Titan Chemicals Limited | Biocide |
| CN103209590A (en) * | 2011-10-27 | 2013-07-17 | 泰坦化工有限公司 | Biocide |
| JP2014530886A (en) * | 2011-10-27 | 2014-11-20 | チタン ケミカルズ リミテッドＴｉｔａｎＣｈｅｍｉｃａｌｓ Ｌｉｍｉｔｅｄ | Biocide |
| CN103209590B (en) * | 2011-10-27 | 2015-08-26 | 泰坦化工有限公司 | biocide |
| CN117776580A (en) * | 2023-12-26 | 2024-03-29 | 科之杰新材料集团有限公司 | Preservative for polycarboxylate water-reducing agent containing isothiazolinone composition and preparation method thereof |
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| AU2000265583A1 (en) | 2002-02-25 |
| WO2002014293A8 (en) | 2003-04-10 |
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