JPH03186391A - Slime control agent and slime control - Google Patents

Abstract

PURPOSE:To obtain a slime control agent which prevents contamination caused by algae and bacteria by allowing specific amine to react with epihalohydrine and dihalide into a water-soluble polymer of specific quality. CONSTITUTION:Amine shown by formula I (R1-3 is H or an alkyl group) is allowed to react with epihalohydrine shown by formula II (X is halogen), dihalide shown by X-B-X (X is halogen; B is a 1 to 20C alkylene group) and dihalogenoalkylene ether shown by X-R2-O-X (X is halogen; R3-4 is a 1 to 3C alkylene group). In addition, a slime control agent used is a water-soluble polymer which is a 2mol aqueous solution of KBr having an ultimate viscosity of 0.025 to 1.2. This slime control agent inhibits the generation of algae and filiform bacteria for a long time by adding only a small quantity of it.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a slime made of a specific polyamine that suppresses the growth of algae, filamentous bacteria, aqueous fungi, etc. in systems that use water as part of the system. The present invention relates to a control agent and a slime control method.

Furthermore, the present invention is applicable to systems that use water as part of a system, such as systems that circulate or reuse water or systems that use water for a relatively long period of time, such as industrial water supply systems and circulating systems for cooling towers in buildings. cooling system, paper making, dyeing, chemistry,
A slime control agent and slime that is substantially non-foaming, non-irritating to warm-blooded animals, and effectively inhibits the growth of algae, filamentous bacteria, and aqueous fungi in water supply systems of the steel industry, etc. Concerning control methods.

[Conventional technology]

In systems using water, algae such as green algae, blue-green algae, diatoms, and 5phaerotilus, Th1othrix, type 021N, type 0041, actinomycetes (e.g. Noca
Rdia amarae) and other filamentous bacterial groups (mouth, H0 Bikelbo.

m:Prog, l1ater Tech, Vol. 8, No. 6, pp. 153-161, as defined in 1977>
The growth of aqueous bacteria such as Bacillus and Bacillus causes serious problems such as clogging of water supply system pipes and deterioration of water quality, as well as stains on products and corrosion of water supply equipment and pipes. Problems caused by the occurrence of such algae, filamentous bacteria, and aqueous fungi have a serious impact on industrial production plans, and can also cause numerous problems in daily life, such as failures in cooling equipment. Therefore, it is socially important to prevent this.

Slime is a slimy ooze-like substance that is mainly composed of algae, mold, filamentous bacteria, actinomycetes, water-borne bacteria, etc. that occurs in water or on the surface of water, and is added to water to suppress them. The substance is called a slime control agent.

In general, slime control agents include chlorine, sodium hypochlorite, chlorine compounds such as chlorinated isocyanuric acid, organic nitrogen sulfur compounds, organic bromine compounds, organic sulfur compounds, and quaternary ammonium salt compounds. Commonly used.

Among these, compounds other than quaternary ammonium salt compounds are:
Although it generally has excellent film thickness, it is highly toxic and there is a risk that users may lose their eyesight due to splashing.

In addition, quaternary ammonium salt compounds have foaming properties, so the conditions under which they can be used are limited, and many of them have poor film thinness for boat fishing. Conventional quaternary ammonium salt compounds of this kind generally have low molecular weights and are not polymeric compounds, but there have been a few reports of cases in which polymeric compounds of quaternary ammonium salts are used as membrane thinners. Special Public Service, 1977
Publication No. 23377 proposes a method of suppressing the growth of algae using a polymer poly[oxyethylene (dimelimino) ethylene (dimethylimino) ethylene dichloride].

However, this method has a problem in that it is effective against both filamentous bacteria and aquatic fungi, which are substantially the same or more problematic than algae, and the raw materials used are relatively expensive.

Report by Yajima et al. (pp. 3-5. Water and wastewater, Vol. 30
No.

5, 1988 and pp. 9-12. Water and wastewater, Vol.
, 31 No. 3゜1989), a certain molecular weight polyamine sulfone is said to be useful as a membrane thinner, but it needs to be used at a relatively high concentration, and its effectiveness against filamentous bacteria has not been compared. There is a problem of lack of focus.

As described above, at present, there is no conventional slime control agent that has a long-term growth inhibiting effect on both algae and filamentous bacteria, ease of handling, and economic efficiency.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a slime control agent and a slime control method that specifically prevent or remove damage caused by specific algae and bacteria that occur in water or on the surface of water.

[Means to solve the problem]

The slime control agent of the present invention comprises an amine represented by the following formula (I) and one or more compounds selected from epihalohydrin, dihalide, and dihalogeno alkylene ether represented by the following formula (n). It is characterized by containing as a component a water-soluble polymer obtained by reaction and having an intrinsic viscosity of 0°025 or more and 1.2 or less when measured in an aqueous solution at 25°C (hereinafter referred to as measurement of intrinsic viscosity). (The conditions are the same.)

Formula (I) (In the formula, Rls L and R2 each represent hydrogen or an alkyl group.) Formula (n) ■, Epihalohydrin (X represents a halogen) ■, Dihalide-B-X (In the formula, represents a halogen, and B represents a straight chain or branched alkylene group having 1 to 20 carbon atoms.) ■, dihalogenoalkylene ether R4 and R3 have 1 to 3 carbon atoms
represents a straight or branched alkylene group, respectively.

) The slime control method of the present invention is characterized by adding 0.1 to 400 parts by weight of the slime control agent in terms of solid content per 1 million parts by weight of water, and bringing the mixture into contact with the slime. It is something to do.

The objects of the present invention include water supply systems that use water as a main component, such as industrial water supply systems, circulating cooling systems for building cooling towers, water supply systems for paper manufacturing, dyeing, chemicals, steel manufacturing, etc., water storage, swimming pools, etc. Algae such as green algae, blue-green algae, and diatoms that occur and grow in water or on the surface of water in pools, etc. For example, algae such as Phormidium, Ringvia, Osciladoria, and other algae such as Phormidium, Lingbia, Osciladoria, and other algae, Futoaomidoro, and Muremikazukimo, which grow in the water or on the water surface. , but not limited to. Also, bacterial groups that form filaments, such as, )i.

Bikelboom: Frog, l1ater T
ech, Volume 8, No. 6, No. 153 (Page 61, 197
Classified according to the 7 year definition, 5 phaerotil
us (suf, tl chills), Th1othrix (
Thiothrix), type 021N, type 0041.
Filamentous bacteria such as actinomycetes (represented by Nocardia amarae) and Bacillus 5ubtil
is, and other aquatic bacteria.

The slime control agent of the present invention is a water-soluble polymer obtained by reacting one or more compounds selected from epihalohydrin, dihalide, and dihalogenoalkylene ether with an amine.

The amines include ammonia and alkylamines, and the alkylamines are preferably amines containing an alkyl group having 1 to 3 carbon atoms, such as methylamine, ethylamine, propylamine, dimethylamine, dipropylamine, methylethylamine, methylpropyl. Examples include amine, ethylpropylamine, and the like. These amines can be used in combination.

The epihalohydrin is generally one in which the halogen is fluorine, chlorine, bromine or iodine, and epichlorohydrin is preferred for economic reasons.

Examples of the dihalide include dichloroethane, dichloropropane, dichlorobutane, dichlorohexane, dibromoethane, bromochloroethane, bromochloropropane, dibromopropane, dibromohexane, dichlorononane, and the like.

Dihalogenoalkylene ethers are generally those in which the halogen is fluorine, chlorine, bromine atom, or iodine, but those using chlorine are preferred at least for economic reasons, such as dichloromethyl ether, dichloroethyl ether, etc. , dichloromethyl ethyl ether, dichloropropyl ether, etc.

Epihalohydrin, dihalide, and dihalogenoalkylene ether may be used singly or in combination of two or more thereof.

Further, the mixing ratio of the epihalohydrin, dihalide, and dihalogenoalkylene ether is not particularly defined as long as the sum of the moles of these mixtures is approximately equal to the mole number of the amine.

In the polymerization reaction, the number of moles of the above-mentioned mixture of one or more of epihalohydrin, dihalide, and dihalogenoalkylene ether (referred to as an amine-reactive compound for convenience) is approximately equal to the number of moles of the amine. It is preferable to use a closed type reaction vessel equipped with a stirrer and set the internal temperature of the reaction vessel to a range of 30 to 100°C under an inert gas atmosphere.

Specifically, a 20 to 70% aqueous solution of an amine, for example, is charged into a closed reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, etc., the atmosphere inside the vessel is replaced with nitrogen gas, and the reaction vessel is heated while stirring. It is preferable to add the anti-amine reaction compound continuously or batchwise while adjusting the internal temperature to a predetermined value. Note that even 100% amine can be used as the amine.

The water-soluble cationic polymer obtained from a secondary amine and a counter-amine-reactive compound can be further prepared by replacing the halogen as a counter-ion (derived from the above-mentioned counter-amine-reacting compound) with another anion, or by removing the counter-ion. This polymer may be converted into a hydroxide.

In the water-soluble polymer thus obtained, the slime control agent of the present invention has an intrinsic viscosity [η] of 0.0.
It is 25 dl/g or more and 1.2 dl/g or less.

The intrinsic viscosity of a water-soluble polymer is controlled by reaction conditions such as reaction temperature.

If [η] in the slime control agent of the present invention is too small, not only will the pharmacological effect on algae, filamentous bacteria and aquatic fungi become small, but also the adsorption effect will be poor, and [η] will be too small. If it is large, the pharmacological effect will decrease,
The inhibitory effect on the growth of algae, filamentous bacteria, and aquatic fungi can be observed even when the appropriate [η] range is different, so there is no reason why it cannot be used.

Next, the slime control method of the present invention will be explained.

The slime control agent of the present invention is suitable for use in water storage systems such as reservoirs and pools, equipment that circulates water, such as industrial water supply systems, circulating cooling systems for pill cooling towers, paper manufacturing, dyeing, chemicals, steel manufacturing, etc. It is used in water supply systems, etc., either by adding it to water as it is, or by mixing it with other compounds for other purposes.

If the solvent is an organic solvent, remove it to form a solid, and dilute it with water to make an aqueous solution before use.If an aqueous solution has been produced, use it as it is, or dilute or concentrate as necessary and use it as an aqueous solution. is preferable and normal.

The amount added is 0.1 per 1 million parts by weight of water as solid content.
Parts by weight - 400 parts by weight, preferably 0.2 parts by weight - 50 parts by weight
Parts by weight. The slime control agent of the present invention substantially exterminates algae and filamentous bacteria that occur in water or on the surface of water, or from the viewpoint of preventing their occurrence for a long period of time, it does not cause any harmful effects even when added in large amounts. Although it can be used without causing any adverse effects, as mentioned above, a small amount is sufficient to have a sufficient effect, so the amount used within the above range is appropriate from the viewpoint of economical effects.

Usually, if there is no problem with actinomycetes, the amount added may be about 0.3 parts by weight to 30 parts by weight per 1 million parts by weight of water.

In systems where actinomycetes are likely to occur, it is necessary to use a relatively large amount, and it is desirable to vary the amount used within the above range depending on the type of bacteria that are likely to occur. It may also be used in combination with other chemicals that have bactericidal properties or film thinning properties, in which case the amount should be adjusted depending on the characteristics of the other chemicals.

[Effect]

The polyamine itself used as the slime control agent of the present invention is known, and its use as a sedimentation accelerator has been known, and it is also known to be effective in inhibiting the growth of filamentous bacteria. 60-43865, same 60
-295890, 62-49394, 62-49
395, 62-49396, 62-4939'il
, No. 62-49398, No. 62-49399, and Japanese Patent Application No. 1-44004 No. 1-44005.

However, it has been discovered that the slime control agent of the present invention is particularly effective in a specific range of intrinsic viscosity that is very different from the range of conventional sedimentation accelerators.

Furthermore, the slime control agent of the present invention is preferable from the viewpoints of safety, non-foaming properties, cost balance, etc. In particular, the slime control agent of the present invention can suppress the growth of algae, filamentous bacteria, and aquatic fungi in systems that use water. This is something that cannot be predicted.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

[Example 1] (1) Preparation of Sample A Epichlorohydrin was added to a 50% dimethylamine aqueous solution while maintaining the reaction temperature at 90°C until the molar ratio of epichlorohydrin and dimethylamine aqueous solution was 1:1.05. , stir and mix for 2 hours, add water and reduce purity to 50.
% aqueous solution.

The intrinsic viscosity [η] of the obtained aqueous solution was 0.12 dl/g.

(2) Preparation of Sample B1 Sample C The same raw materials as those for Sample A were used, the reaction temperature and addition rate were varied, and water was added to form an aqueous solution with a purity of 50%.

Reaction temperature of epichlorohydrin to dimethylamine at 30
The aqueous solution obtained by adding the mixture while maintaining the temperature below ℃ and stirring and mixing for 30 minutes had an intrinsic viscosity [η] of 0゜019 dl/g as sample B, and added while maintaining the reaction temperature at 80℃. Sample C was obtained by stirring and mixing for 2 hours, and the resulting aqueous solution had an intrinsic viscosity [η] of 0.25 dl/g.

■ Preparation of sample In the preparation of sample A above, dimethylamine was reduced by 40%, and the same number of moles as the reduced number of moles was supplemented with diethylamine. After reacting at 100° C. for 30 minutes, water was added to make an aqueous solution with a purity of 50%.

The intrinsic viscosity [η] of the obtained aqueous solution is 0.025 dl/g
Met.

■Preparation of Sample E and Sample F Epichlorohydrin and 50% dimethylamine aqueous solution 2
The molar ratio of 8% ammonia aqueous solution is 1:0.95:0.0
50% dimethylamine aqueous solution and 28% until the ratio is 5%.
% ammonia aqueous solution, epichlorohydrin was added and stirred while maintaining the reaction temperature at 90° C., and water was added to obtain an aqueous solution with a purity of 50%. The intrinsic viscosity [η] of the obtained aqueous solution was 1.18 dl/g, and this was designated as Sample E.

In addition, the molar ratio of epichlorohydrin, 50% dimethylamine aqueous solution, and 28% ammonia aqueous solution is 1.05:
in the mixed amine until the ratio is 0.7:0.3.
Epichlorohydrin was added and stirred while maintaining the reaction temperature at 80° C., and water was added to obtain an aqueous solution with a purity of 50%. The intrinsic viscosity [η] of the obtained aqueous solution was 1°35 dl/g
This was designated as sample F.

(2) Preparation of Sample G1 and Sample H Methylamine and diethylamine were mixed at a molar ratio of 1:2, and epichlorohydrin was added to the 50% aqueous solution while maintaining the reaction temperature at 90°C or 70°C, followed by stirring and mixing. Water was added to form an aqueous solution with a purity of 50%. The molar ratio of epichlorohydrin and amine was 1:1.05.

(2) Preparation of Sample (2) and Sample J A mixture of epichlorohydrin and dichloropropane, the molar ratio of which was adjusted in advance at a ratio of 1:1, was heated until the molar ratio of the mixture and the dimethylamine aqueous solution became 1 = 1°05. Set the reaction temperature to 90°C or 70°C in a 50% aqueous solution.
Add water while maintaining the temperature, stir and mix, and add water to reduce the purity to 50.
% aqueous solution.

The intrinsic viscosity [η] of the obtained aqueous solution was 0.09 dl/g, which was 7eU□□1°□. , 25 dl/g1'A, V oblique sample J.

(2) Preparation of sample A mixture of epichlorohydrin and dichloroethyl ether, whose molar ratio was adjusted in advance at a ratio of 1=1, was heated to 50% until the molar ratio of the mixture and dimethylamine aqueous solution became 1:1.05. The mixture was added to a dimethylamine aqueous solution while maintaining the reaction temperature at 90° C., stirred and mixed, and water was added to obtain an aqueous solution with a purity of 50%.

The obtained aqueous solution whose intrinsic viscosity [η] was 0.22 dl/g was used as a sample.

(2) 50% aqueous solutions of Thiomaster C and Cationomaster G, both commercially available from Yokkapolymer AE, were used as Sample L1 and Sample M, respectively.

The structural formulas of Cation Master C1 and Cation Master G are described below.

(Cation master C1 intrinsic viscosity [η] is 0.21 dl/
g) (Catiomaster G1 intrinsic viscosity [η] is the pass fence d 1
/g) (Algal growth inhibition test)
rum capricornutum), Gorha
Culture the algae stock solution in 5 times dilution of 4×10”
cells/ml), and a test sample was added to the same medium,
Prepare different concentrations of each, add the algae stock solution to the test sample, and adjust the initial cell concentration to 5 x 10'calls.
/ml.

The test container was placed in a culture tank at 20±1° C. and shaken at 100 rpm with a shaker. Lighting is 80001ux
(fluorescent lighting).

After the start of the test, the number of cells was counted every 24 hours using a particle counter (call counter), and measurements were continued until 96 hours later to calculate the average specific growth rate.

The growth status was divided into four stages: good growth was classified as 1,000 years, growth was slightly poor as +, growth was very poor as 1, and no growth or death was classified as -.

The concentrations of the test samples were 0 (control), 0.2.0, respectively.
4.0.8.1.2.2.0, 5.0.10 aIg
/j! And so.

The results are shown in Table 1 below.

(Margins below) Table 1 Algal growth inhibition test results■, Oscillatria proliphylla
oriaprolifera) J3 and Polvox carteri (V.

IVOX carteri) was cultured in Chu No. 10 medium (with double the nitrogen source) and test samples were tested as described above. The amount of growth was visually evaluated every week, and the amount of growth after 21 days was divided into four levels, and the growth was evaluated in the same manner as above.

The concentration of the test sample is the same as in ■, and the evaluation results are shown below.
It is shown in Table 2.

Table 2 Algae growth inhibition test results (filamentous bacterial growth inhibition test) ■, Type 021N, H, Bikelboo
m: Frog.

Water Tech, Volume 8, No. 6, No. 153-
p. 161, Sphaeotilus (S) according to the 1977 definition
phaerotilus) was cultured at 25° C. in a YGA liquid medium (Mie University Institute of Biological Resources), each of the following sample concentrations was added, and the amount of growth over 3 days was observed using a microscope.

The growth status was divided into four stages as in the above algae growth inhibition test, with good growth as ++, slightly poor growth as +, very poor growth as , and no growth or death as -.

The concentrations of the test samples were 0 (control), 0.2.0, respectively.
4.0.8.1.2.2.0.5.0.10 mg/l
And so.

Regarding the evaluation results, Table 3 (a) shows the case of type 021N, and Table 3 (b) shows the case of Sphaerotilus.

Table 3 (a) Results of fungal growth inhibition test Table 3 (b) Results of fungal growth inhibition test (blank below) ① Actinomycetes (Nocardia amarae, above, HoBikelbo).

m) was cultured in YK liquid medium (@Science Research Institute Department) and otherwise evaluated in the same manner as the above filamentous bacteria.Table 4 shows the results.

As can be seen from Tables 1 to 4, it can be seen that the slime control agent of the present invention effectively prevents and removes not only algae but also filamentous bacteria and actinomycetes.

〔Effect of the invention〕

The slime control agent and slime control method of the present invention can suppress the generation of algae and filamentous bacteria for a long period of time by adding small amounts of algae and filamentous bacteria in water-using systems, and can provide stable operation in water-using systems. can be easily secured.

Furthermore, the slime control agent of the present invention has a long duration of effect even after being added twice, so it is extremely useful for process control in water-using systems.

Furthermore, the slime control agent of the present invention is substantially non-foaming, so it does not cause any adverse effects during use, and is extremely safe and non-irritating to mixed-breed animals, so it can be safely added. Furthermore, there are almost no restrictions on the operation of the water-using system, so it can be operated safely. In addition, the raw materials used are easily available, relatively inexpensive raw materials are used, and the amount used is small compared to similar products.

Claims (2)

[Claims] (1) An amine represented by the following formula (I) and the following formula (II)
) and 2 mol of KBr.
The intrinsic viscosity measured in an aqueous solution at 25°C is 0.025 or more,
A slime control agent containing a water-soluble polymer of 1.2 or less. Formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2 and R_3 each represent hydrogen or an alkyl group.) Formula (II) [1], Epihalohydrin ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (X represents halogen) [2], Dihalide ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, [3], dihalogenoalkylene ether X-R_4-O-R_5-X (wherein,
~3 linear or branched alkylene groups are shown, respectively. ) (2) The slime control agent according to claim 1,
A slime control method comprising adding at least 0.1 part by weight in terms of solid content to 1 million parts by weight of water and bringing the mixture into contact with slime.