DE2053746A1 - Bactericidal and fungicidal agent for industrial use - Google Patents

Description

2053746 Andrejewski & Honke patent attorneys

Physicist Dr. Walter Andrejewski Graduate engineer Attorney's file: 35 8? 5 / Kle- _Df _ _{| ng}

Essen, October 30, 1970 Kettwiger Strasse 36 ( ^t )

Patent application

Rikkihappo Oy (|

Malminkatu 50,

Helsinki 10, Finland

Bactericidal and fungicidal agent for industrial use.

In water circulation systems, such as in cooling towers, heat recovery systems and the water system in the wood pulp and paper industry usually results in an abundance of the most diverse microorganisms, which, if the water is not treated with appropriate protective agents, in the Operation of the systems can cause considerable disruptions and unpleasant side effects. The main condition What must be asked of such protective means is that their scope is very broad, while their effectiveness by environmental influences, such as the pH value

109820/2298

Patent attorneys Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strafte 36

Temperature and others entered into the piping system at the same time Active ingredients must be influenced as little as possible. As a result of these requirements for the effectiveness of the protective equipment Such active ingredients can generally also be used for the treatment or processing of the water in water circulation systems for other purposes such as for the treatment of textiles, skins, plastics and oils and also as condoms use for latex paints.

In order to prevent fly ^ imtstehung of microorganisms and is caused by their accumulation of mucus, has been λ a plurality verschiedenster bactericidal and fungicidal agents used, such as organic mercury compounds, chlorinated phenol derivatives, thiocarbamates, Thiocaynate, quaternary ammonium compounds, organic tin compounds and bromine compounds. Of the last-mentioned compounds, esters of aliphatic alcohols and bromine-substituted organic acids were used to a large extent, in particular to prevent slime in the treatment of waste water in the wood pulp and paper industry. Such compounds are, for example, 1-bromoazetojcyl-2-ethanol and 1-bromoazetoxylpropanol-2 according to US Pat. No. 5 39Z ₁ I ² ^ and 1-bromoazetoxyl ^ -butylene-A-ol, 1-bromoazetoxyl -2-butene-4-chloride and 1,4-bis-bromoacetoxyl-2-butylene according to US Pat. No. 2,840,598. Even if the mode of action of these bactericidal and fungicidal agents has not yet been fully clarified, so much seems to be the case to be clear that their effectiveness is due to the bromoacetoxyl group. On this basis various efforts have been made like them

109820/2298

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Patent attorneys Pr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse 36

for example, in U.S. Patent J5.196 071 to improve the effectiveness of these agents by adding the polyhydric alcohol in addition to the bromoacetoxyl group an aldehyde group is incorporated to give another active group in the same molecular chain.

The invention now creates a bactericidal and fungicidal agent suitable for industrial use, which essentially is characterized in that it is used as an active ingredient

1 2

an ester with the general formula R -CO-O-R of an aliphatic Contains nitro alcohol with an organic halogen acid,

where R is a halogen-substituted alkyl group with 1-4 C atoms

and R is a nitrogen-substituted alkyl group with 2-6 carbon atoms.

A particular field of application of the agent according to the invention is the treatment of water in water circulation systems the paper industry.

Namely, it was found that the nitrogen substituent a very beneficial influence on the effectiveness of the bromoazetoxy group exercises, so that the esters of aliphatic nitro alcohols with organic halogen acids in the invention Training results in excellent bactericidal and fungicidal agents.

The bactericidal and fungicidal agents according to the invention can be prepared from halogen-substituted substances by the usual esterification reaction organic acids such as monobromoacetic acid with nitrogen-substituted alcohols such as

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Patent attorneys Dr. W. Andrejewelcl, Dr. M. Honlce, 43 Essen, Kettwiger Strasse 36

2-nitroethanol-l, 2-nitropropanol-l, 2-nitro-2-methylpropanol-l, ■ 2-nitro-2-methyl-1,3-propanediol, 2-nitro-2-ethyl-1,3-propanediol, 2-nitrobutanol-1,> nitrobutanol-2, 3-nitro-> methylbutanol-2 and produce 5-nitropentanol-2.

For example, l-bromoacetoxyl-2-nitrobutane can be produced in the following way:

A 500 ml glass flask with a vapor discharge tube, a reflux condenser and an agitator is charged with 119 g of 2-nitrobutanol-1 (1 mol), 139 g of monobromoacetic acid (1 mol) and 250 ml of benzene. This reaction mixture is heated at a temperature of 80-90 ° C preferably below 85 ⁰ C for about 8-I6 hours until the water formation ceases. Small amounts of sulfuric acid or para-toluenesulfonic acid can be used as the catalyst. As soon as the esterification reaction is complete, the benzene is distilled off and the remaining 1-bromoacetoxyl-2-nitrobutane is purified by vacuum distillation at a pressure of 1-2 mm Hg. The yield is 80-95% of finished product with a boiling point of 117-118 ⁰ C, a specific gravity of 1.582 at 20 ⁰ C and a Refractionsindex of 1.4790 at 20 ⁰ C.

The following list shows the corresponding physical properties of a number of other synthetic properties according to the invention produced nitro-bromoacetoxyl compounds.

109820/2298

20537A6

Potentanwälte Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse

Kp ₁ mm Hg dg ₀ ngQ

l-bromoacetoxyl-2-nitro-

2-methylpropane 117-117.5 ° C 1.502 1.4755

1,3-bromoacetoxyl-2-nitro

-2-Äthy propane 182-190 ⁰ C 1.675 l, 5O4O

1-bromoacetoxyl-2-nitro-

butane 111-116 ° C 1.498 1.475

2-bromoacetoxyl-2-nitro-

butane 108-111.5 ° C 1.508 1.474

2-bromoacetoxyl-3-nitro-

3-methylbutane 114.5-U6.5 ° C 1.410 1.4702

2-bromoacetoxyl-5-nitro-

pentan 114-121 ⁰ C 1,438 1.4712

To determine the effectiveness of the aforementioned agents according to the invention, for example, the laboratory-appropriate Apply the method described by J.H. Conkey and J.A. Carlsson is described in the publication Tappi 46 (1965) (5) 23-24, this method measuring the effectiveness of the active ingredient which is added to a substrate on which a Organism was transferred by determining the amount of active ingredient which is required to prevent the growth of a bacterial or fungus organism which is on the substrate was transferred.

The results of the efficacy determinations in relation to Aerobacter aerogens on Bacto-Tryptone Glucose Extract Agar with an incubation time of one day are shown in Table 1 below laid down.

109820/2298

Patent attorneys Dr. W, Andmjew »kl, £ r. M. Honke, 49 i ** en, Kettwiger Strafe

Tabel

Aerofoacter aerogens

Active ingredient concentration (mg / 1) 25 50 100 200

1-bromoacetoxyl-2-nitrobutane

2-bromoacetoxyl-3-nitrobutane

1-bromoacetoxyl-2-nitropropane

2-bromoacetoxyl-3-propentane

1-bromoacetoxyl-2-nitro-2-methylpropane

2-bromoacetoxyl-3-nitro-3-methylbutane

1, ^ - Bromoacetoxyl-2-nitro-2-ethyl-1,3-propanediol

x) It means:

- no growth + little growth 4 · + strong growth.

With corresponding measurements regarding the effectiveness, in which the test organisms Penicillium expansum and Aspergillus niger were used, the amount for preventing the growth of these organisms was 50-200 mg / l. For Penicillium expansum was used as substrate Czapek agar and for Aspergillus niger potatoes! dextrose Used agar.

109820/2298

Patent attorneys Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse

The laboratory tests show that the required amount of monobromoacetic acid esters of the nitrogen-substituted Alcohols related to Aerobacter Aerogene, Penicillium expansum and Aspergillus niger is between 25 and 200 mg / l.

Compared to the corresponding monobromoacetic acid esters of non-nitrogen-substituted alkanols, those are according to the invention Compounds clearly superior in their effectiveness.

Compounds used to treat circulating water must have a very wide bactericidal and fungicidal range of action, since the active ingredient is less effective compared to some special species, these species resisting the active substance are enriched in the treated conduit system can be. The effectiveness of these active ingredients can therefore only be determined with extreme difficulty through laboratory tests. A more reliable picture naturally results from tests carried out under normal working conditions as described in the example below.

Examples

2 kg of a solution of 25 % 1-bromoacetoxyl-2-nitrobutane and 25 % 1,2-bromoacetoxyl-ethane in a total amount of 50 % of solvents and dispersants added. For the measurement, the respective amount was fed into the machine box of the paper machine for about 20 minutes, which was about

109820/2298

Patent attorneys Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse

.30 m covered. During a test period of 4 weeks the effectiveness of the toxin treatment is monitored in such a way that water samples are given to the main machine box once a week, namely 1, 2, 4 and 8 hours after the measurement were taken and the organism population in the samples was determined. Additionally was The condition of the water system is tracked by observing the cleanliness of the pipes, boxes and other parts. The obtained results were compared with the conditions before the addition of the bactericidal and fungicidal agent prevailed, which contained l-bromoacetoxyl-2-nitrobutane. That Circulating water had previously been treated with an agent which only contained 1,2-bromoazetoxyl-ethane, while the The concentration of the active ingredient and the manner in which it was added corresponded to the conditions prevailing during the test period ruled.

The results of the microbiological determinations in the water samples taken are set out in Table 2 below.

Table 2

Organism inventory (number / ml)

Sampling after
Measurement before the test! .Week 2nd week 5th week 4th week

900 000 242 000 \ 164 000 46 000 6th 800 2 915 000 110 000 138 000 9 400 18th 600 4th 6oo 000 235 000 271 000 12th 800 18th 700 3 130 000 930 000 302 000 90 000 34 600

109820/2298

Patent attorneys Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse 36

From the table above it can be seen that the effectiveness of the agents according to the invention is unambiguously known to date is superior and that the organism population in the water system was clearly reduced during the test period of 4 weeks, so that (Sas pipeline system was cleaned. The inspection of the Parts of the water system also showed that the accumulation of mucus caused by microorganisms, which before the Could be observed in the experiment, so that the system remained clean during the entire test period.

For the use of the bactericidal and fungicidal agents according to the invention for treating the water in circulation systems, these agents generally have to be converted into a more easily dispersible form. For this purpose, various aliphatic alcohols or aliphatic and aromatic solvents can be used as diluents. For example, sulfonated nonionic emulsifiers, polyoxyalkylene ethers or their derivatives and sulfonated oils can be added as dispersants of 5-50 % of compounds.

Claims t

109820/2298

Claims (8)

Patent attorneys Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse / o Claims. 1. Bactericidal and fungicidal agent for industrial use, characterized in that it is an ester as the active ingredient with the general formula R -CO-O-I ^ of an aliphatic nitro alcohol with an organic halogen acid, where R is a halogen-substituted alkyl group with 1-4 C atoms and R denote a nitrogen-substituted alkyl group with 2-6 carbon atoms. 2. Bactericidal unß fungicidal agent according to claim 1, characterized characterized in that the active ingredient consists of l-bromoacetoxyl-2-nitropropane consists. 3. Bactericidal and fungicidal agent according to claim 1, characterized in that the active ingredient consists of l-bromoacetoxyl-2-nltrobutane consists. 4. Bactericidal and fungicidal agent according to claim 1, characterized in that the active ingredient consists of 2-bromoacetoxyl-j5-nitrobutane consists. 5. Bactericidal and fungicidal agent according to claim 1, characterized in that the active ingredient consists of one of the in one of claims 1-4 and another bactericidal and / or fungicidal active ingredient. 6. Bactericidal and fungicidal agent according to claim 5, characterized characterized in that the active ingredient consists of a mixture of l-bromoacetoxyl-2-nitropropane with 1,2-bromoazetoxylethane. 1098ZÖ / 2298 Patent attorneys Dr. W. Andrejewski, Dr. M. Honice, 43 Essen, Kettwiger Strasse 7. bactericidal and fungicidal agent according to any one of claims 1-6, characterized in that the active ingredient with liquid solvents and emulsifiers is diluted. 8. Use of the bactericidal and fungicidal agent according to any one of claims 1-7 for the industrial processing of Water in water circulation systems. PAe Dr Andrejewski, Dr Honke. 109820/2298 QRKäJHAi INSPECTED