JPS5822004B2 - aquatic creature repellent - Google Patents

Description

Detailed Description of the Invention The present invention is applicable to the bottom of ships, fishing nets, equipment placed in the sea such as wave power generation buoys, underwater structures such as dam auxiliary equipment, condenser cooling water of thermal power plants, and stone and oil. This invention relates to a new antifouling agent for aquatic pests that prevents harmful aquatic organisms from adhering to, living in, and breeding in water intake channels for heat exchanger cooling water in the chemical industry.

Parts that are in constant contact with water, such as the bottom of ships, equipment placed in the sea, underwater structures, and cooling water intake channels, are exposed to fujibo, oysters, mussels, hydrobugs, serpura, bryozoans, sea squirts, sea breams, sea lettuce, and green laver. It is well known that shellfish such as , diocitro, and algae grow adherently.

These attached organisms cause an increase in fluid resistance and a decrease in thermal conductivity, resulting in a decrease in equipment functionality and an undesirable situation.

For example, in ships, this not only causes a reduction in cargo speed and wasted fuel, but also causes economic losses such as losses due to ship suspension and cleaning costs due to cleaning the bottom of the ship, and in the case of underwater structures, it is inconvenient to handle and operate. cause
Furthermore, the intake amount of water for condenser cooling water, heat exchanger cooling water, etc. in the intake channels decreases, and not only does the cooling efficiency decrease, but also the condenser, heat exchanger, etc. This will cause a decline in the performance of the exchanger, resulting in large economic losses.

Conventionally, in order to prevent problems caused by the adherent growth of seawater and freshwater harmful organisms, heavy metal compounds such as copper oxide and mercury oxide, organotin compounds such as tributyltin oxide, organochlorine or organosulfur compounds, phenyl Antifouling paints containing arsenic compounds such as sagin chloride are used, and in intake channels for cooling water, etc., chlorine is directly added to formalin, etc. to prevent aquatic life.
Prevented adherent propagation.

However, antifouling paints containing heavy metal compounds such as copper oxide and mercury oxide have poor storage stability because the metal oxides that are not contained tend to react with the surface components in the paint.

In addition, in contaminated sea areas such as ports and harbors where industrial sewage is present, hydrogen sulfide generated by the action of microorganisms in the contaminated water causes discoloration and deterioration, resulting in inconveniences such as loss of efficacy.

In addition, copper and mercury-based inorganic compounds are effective against sea creatures such as barnacles, ascidians, and bryozoans, but have little effect on algae.

Furthermore, the disadvantage of this antifouling paint is that when applied to light metal materials such as aluminum magnesium, metals such as copper and mercury in the paint precipitate on the material, electrochemically accelerating corrosion of the material. It is to be.

Antifouling paints containing organotin compounds such as tributyltin oxide are less effective and more expensive than antifouling paints containing oxides of copper and mercury.

In addition, if used in large quantities, the coating performance will deteriorate and the odor will be bothersome when handled.

Antifouling paints containing organic chlorine or organic sulfur compounds are far less effective than any of the above antifouling paints,
For example, the effect on harmful organisms is selective, such as being effective against bryozoans but not against barnacles, and is therefore hardly of practical use.

Furthermore, antifouling paints containing phenarsazine chloride (Adamsite) have been used, but phenarsazine chloride is extremely irritating to human mucous membranes, making it difficult to manufacture and paint the paint.

Furthermore, if chlorine or formalin is added to the cooling water intake channel, the cooling device will be corroded, and the effect of preventing the attachment of organisms in the water will not be excellent.

All of the above compounds are highly toxic to humans and fish.
There are some serious restrictions on its use.

The present inventors have conducted various studies on antifouling paint agents that solve the drawbacks of conventionally used antifouling paints and agents as described above. It has low toxicity, almost no toxic effects on humans and livestock, and extremely low toxicity on fish, making it safe to use. Antifouling paints containing this compound as an active ingredient are stable even in contaminated waters. It has a long-term effect in preventing the adhesion of aquatic organisms, and even when applied to light metal materials such as aluminum and magnesium, it does not electrochemically erode metal materials, making it suitable for use in intake channels for cooling water, etc. The present invention has been completed by discovering that by applying it to the wall, the adhesion and propagation of harmful aquatic organisms can be sufficiently prevented without fear of corroding the cooling device.

That is, the present invention relates to the general formula (wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and Y represents a morpholino group, a piperidino group, an N-methylbiperazino group, or 〉N-1 2 R1 is a hydrogen atom or a lower alkyl group, R2 is a lower alkyl group, R3 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a trifluoromethyl group, R4 is a lower alkyl group, R5 is a hydrogen atom or The halogen atom R6 represents a hydrogen atom, a halogen atom or a nitro group.

This invention relates to an antifouling agent against adhesion of underwater pests, which contains an N-aryl-disubstituted maleimide represented by the following as an active ingredient.

Table 1 shows an example of the N-aryl-2 monosubstituted maleimide represented by the general formula CII which is used as an active ingredient of the aquatic pest-adhering antifouling agent of the present invention.

In addition, the compound numbers are referred to in the formulation examples and examples of the coating materials described later.

Including these compounds, general formula C used as an active ingredient of the present invention
The N-aryl-disubstituted maleimide represented by II can be easily produced by a known method using the corresponding raw materials.

According to one embodiment of such a method, the general formula (In the formula, X represents a halogen atom.

) 2-halogen maleic anhydride and the general formula (In the formula, R has the same meaning as above.

) is reacted with an aromatic amine represented by the general formula (wherein X and R have the same meanings as above).

) is dehydrated without isolating the N-aryl-2-halogenomaleic acid monoamide represented by the general formula (wherein X and R have the same meanings as above).

) is produced, and then this N-aryl-2-halogenomaleimide is combined with the general formula % formula % (wherein Y has the same meaning as above).

) by reacting with the compound represented by
Aryl-2 monosubstituted maleimides CI) can be obtained.

The reaction between the 2-halogenomaleic anhydride of general formula CIII and the aromatic amine of general formula Cll0 is carried out in an organic solvent at a temperature of 20 to 100° C. for 1 to 2 hours.

This is done by stirring.

Suitable organic solvents used in this case include benzene, toluene, xylene, refloin, chlorobenzene, chlorotoluene, diisopropyl ether, dioxane, acetonitrile, methyl ethyl ketone, and the like.

Examples of the 2-halogen maleic anhydride represented by the general formula CIII used as a raw material include 2-fluoro maleic anhydride, 2-chloromaleic anhydride, and 2-bromomaleic anhydride.

In addition, aromatic amines represented by the general formula [rabbit] used as the other raw material include, for example, aniline, o-, m+,
or p-fluoroaniline, 'o-am- or p-
Chloroaniline, o +.

Halogenoanilines such as m- or p-bromoaniline, o, m- or p-iodoaniline, lower alkylanilines such as o-, m- or p-toluidine, o-, m- or /dp-ethylaniline, o , m- or p-
Examples include lower alkoxyanilines such as anisidine, o-, m- or p-phenetidine.

Further, the dehydration ring-closing reaction of N-aryl-2-halogenomaleic acid monoamide of general formula [IV') can be carried out by adding a dehydrating agent such as sulfuric acid, acetic anhydride or thionyl chloride to the reaction mixture for 70 minutes.
The reaction is carried out at a temperature range of -200°C for 2 to 10 hours.

After completion of the reaction, the solvent is distilled off from the obtained reaction mixture, and if necessary, the mixture is washed and dried to obtain N-aryl-2-halogenomaleimide of the general formula [V].

The reaction between the N-aryl-2-halogenomaleimide of general formula [v] and the compound represented by general formula [VI] is carried out at 0°C to 100°C in the presence of a dehydrohalogenating agent in an organic solvent.
This is carried out by stirring for 2 to 10 hours at a temperature in the range of .

Suitable organic solvents used in this case include ligine, benzene, toluene, xylene, chlorobenzene, chlorotoluene, diisopropyl ether, dioxane, acetonitrile, methyl ethyl ketone, and the like.

As the dehydrohalogenating agent, triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc. are suitable, but when the compound represented by the general formula [VI] is an organic base, it is preferable to dehalogenate the compound. It may also be used as a hydrogen agent.

Compounds represented by the general formula [VD] used as raw materials include heterocyclic compounds such as morpholine, piperidine, and N-methylpiperazine;
2 represents a lower alkyl group.

), an aliphatic amine represented by the general formula (wherein R3 represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a trifluoromethyl group).

) aromatic amine represented by the general formula %formula% (In the formula, R4 represents a lower alkyl group.

), an alkyl mercaptan represented by the general formula (where R
5 represents a hydrogen atom or a halogen atom.

) or the general formula (wherein R6 represents a hydrogen atom, a halogen atom or a nitro group).

) is the phenol represented by

Examples of aliphatic amines represented by the general formula [■-a] include methylamine, ethylamine, propylamine,
Examples include butylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine.

Aromatic amines represented by the general formula CVI-b include aniline, fluoroaniline, chloroaniline, bromoaniline, iodoaniline, toluidine, ethylaniline, propylaniline, anisidine, phenetidine, propoxyaniline, nitroaniline, and trifluoromethylaniline. etc. can be mentioned.

Examples of the alkyl mercaptan represented by the general formula CVI-cl include methyl mercaptan, ethyl mercaptan, propyl mercaptan, and butyl mercaptan.

Examples of the thiophenol represented by the general formula CVI-d include thiophenol, fluorothiophenol, chlorothiophenol, bromothiophenol, and iodothiophenol.

Examples of the phenol represented by the general formula CVI-e'l include phenol, fluorophenol, chlorophenol, bromophenol, iothophphenol, and nitrophenol.

Next, a synthesis example of the N-aryl-2-monosubstituted 7-reimide represented by the general formula [■] used as an active ingredient of the present invention (Kokero aquatic harmful organism adhesion prevention agent) is shown below.

Synthesis Example 1 Compound No. (4): N -(m-chlorophenyl)-
Synthesis of 2-diethylaminomaleimide (1) A fourth flask equipped with a thermometer, condenser, dropping funnel, and stirrer was charged with 400 kg of xylene, and 53.1 mm of 2-bromomaleic anhydride was placed in it. (0
, 3 mol) was added and dissolved.

Next, add 200 g of xylene to 38.3 g of m-chloroaniline? (0.3 mol) was added dropwise at room temperature while stirring.

Heat is generated at the same time as dropping, but after the dropping is completed, 55-60℃ (
The reaction was continued for 2 hours with constant stirring.

Next, 3.0 f (0,029 mol) of sulfuric acid was added, heated, kept at 135-138°C, stirred, and reacted for 4 hours while azeotropically removing water produced by the reaction with xylene.

After the reaction was completed, xylene was distilled off, and 1.5 t of the reaction solution was
The precipitated crystals were collected by filtration, recrystallized with ethanol, and 73.91% of N (m-chlorophenyl)-2-bromomaleimide (the 2-bromo maleimide used as a raw material) with a melting point of 86 to 87' A yield of s6.o% (based on maleic anhydride) was obtained.

2) In a fourth flask similar to (1) above, add 28.7 f/(0.1 mol) of N (m-'70-phenyl)-2-bromomaleimide obtained in (1) above and 300 g of benzene. 14.6 f (0.2 mol) of diethylamine was added dropwise to the mixture under stirring at a temperature below 40°C.

After the dropwise addition was completed, the reaction was carried out at 40° C. to room temperature for 2 hours while stirring.

After the reaction is complete, transfer 1 of the obtained reaction solution to a separating funnel,
150 g of water was added and washed three times.

After washing with water, the resulting benzene solution was dehydrated and dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to distill off the benzene.

The obtained concentrate was allowed to cool to room temperature and crystallized, and then recrystallized with ethanol to obtain N-(m-'70
phenyl)-2-diethylamino 7-reimide 23.6
y [N (m-chlorophenyl)- used as raw material
A yield of 85.0 So based on 2-bromo 7-reimide was obtained.

Synthesis Example 2 Compound No. (12): N-(m-chlorophenyl)-2
- Synthesis of ethylthiomaleimide 25 units equipped with a thermometer, cooling tube, dropping funnel and stirrer
8.7P of ethyl mercaptan in a 0m1 four-bottle flask (
0,14 mol) and 10% sodium hydroxide solution 56
．． OS' (0.14 mol) was charged, and the mixture was stirred for 50 min.
The N-(m-chlorophenyl)-2-bromo7reimide 40.1S'(
A solution of 0.14 mol) dissolved in 150 m² of benzene was added dropwise.

After the dropwise addition was completed, the reaction was carried out at 50° C. to room temperature for 3 hours.

After the reaction is completed, the resulting reaction solution is heated at 500 mA! It was transferred to a separatory funnel and washed three times with 150 rnl of water.

After washing with water, the resulting benzene solution was dehydrated and dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to distill off the benzene.

The obtained concentrate was cooled to room temperature and crystallized, and then recrystallized with ligroin to give a melting point of 94-96°C (O)N-(m'
70 phenyl)-2-ethylthiomaleimide 26.3
N-(m-chlorophenyl) used as yC raw material
-2--j Yield 70.1 based on romomaleimito
%'] was obtained.

The aquatic pest-adhering antifouling agent of the present invention is prepared and used in the form of a paint, solution, emulsion, or the like.

For example, by blending one or more compounds of the general formula [1] with a film forming agent to prepare an antifouling paint, and applying this to the bottom of a ship, underwater structures, and walls of cooling water intake channels. Adhesive propagation of aquatic organisms can be prevented.

Examples of the film forming agent used in this case include oil varnish, synthetic resin, and artificial rubber.

Pigments and extender pigments can be added to the antifouling paint as desired.

In this case, the compound of general formula [1'l is blended in an amount of 5 to 80%, preferably 10 to 50%, based on the weight of the coating film forming agent.

For the purpose of preventing the growth of aquatic organisms in the cooling water intake channels, a compound of general formula CII may be added into the intake channels in the form of a solution or emulsion.

However, in order to maintain the antifouling effect for a long time, it is desirable to apply it in the form of a paint.

In addition, when applying the aquatic pest-adhering antifouling agent of the present invention to fishing nets, the compound of general formula [I] is dissolved in an organic solvent together with a resin to form a resin solution, and this resin solution is used to impregnate fishing nets. ,dry.

When preparing this resin solution, the compound of general formula CI) is contained in an amount of 1 to 10% by weight, preferably 1 to 6% by weight, and the resin is contained in an amount of 5% by weight.
Dissolved in an organic solvent at a concentration of ~15% by weight, preferably 7-12%.

Within this range, the effect hardly changes even if the concentration of the compound of general formula CI'l is changed.

Examples of resins used for preparing the resin solution include vinyl chloride resin, phenol resin, alkyd resin, and chlorinated rubber.

In addition, as an organic solvent, benzene, toluene, xylene, chloroform, etc. are used, but if the resin is difficult to dissolve, dimethylformamide, dimethylacetamide or dimethyl sulfoxide may be mixed in a range of 5 to 15% by volume. I can do it.

There are no particular restrictions on the material of fishing nets that can be treated with the aquatic pest-adhering antifouling agent of the present invention.

Fishing nets made of natural fibers such as cotton, linen, silk, wool, synthetic fibers such as polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile. It can be applied to

Next, examples of formulations of paints and examples of antifouling tests against aquatic organisms using paints based on such formulations will be given. 1 shows the outstanding effect of preventing the attachment of aquatic pests.

Formulation Example of Paint 1 Compound No. (4): N-(m-chlorophenyl fragment-diethylaminomaleimide) was blended in the following proportions, thoroughly ground in a pot mill, and mixed to prepare an antifouling paint.

(% indicates weight percentage. Similarly below, 9 Compound of Synthesis Example 1
20.0% valve handle
10. O% tarri
15.0 difference barium sulfate
20.0% vinyl resin
5.0% gin
5.5% tricresyl phosphate 2.0% methyl isobutyl ketone 11.0% xylene
11.0% total
Formulation example of 100.0% paint 2 Compound number (12): N-(m-chlorophenyl)-2
- Ethylthiomaleimide was blended in the following proportions, thoroughly ground in a pot mill, and mixed to form an antifouling paint.

Compound of Synthesis Example 2 15.0% Valve
Pattern 1.8.0% tar
10.0 aluminum stearley 1- 0.5% graphite
0.5%
26.0% boiled oil
12.0% solvent naphtha
18.0% total
100.0% Example 1 Marine organism antifouling immersion test (1) Preparation of test plate and test method Each steel plate (300 x 100 x 1 mm) that had been primed once with wash primer and once with anti-corrosion paint was coated with each anti-fouling paint. The pieces were painted twice with a brush, fitted into wooden frames, and suspended in the sea from an immersion raft in a trench 1.5 m deep.

(2) Test results The coated plates immersed in seawater as described in (1) above were pulled up at predetermined intervals, and the results are shown in Table 2 as a percentage of the attached area of living organisms.

The control was treated with only wash primer and chemical-free boat bottom paint.

Example 2 Antifouling treatment of fishing net (1) (1) Preparation of resin solution Compound number (4): N (m-chlorophenyl)
-2-diethylaminomaleimide was blended in the following proportions and sufficiently stirred to prepare a resin solution.

Compound of Synthesis Example 1 Chlorinated rubber of 8th grade Rosin of 5th grade Toluene
85% Total 100 sections (2) Processing method In the resin solution prepared in (1) above, 11 sections (3,03c* Fishing nets (mesh size) were dipped, thoroughly impregnated, and then air-dried for 12 hours for antifouling treatment.

Example 3 Antifouling treatment of fishing nets (1) Preparation of resin solution Compound number (12): N (m '70 lophenyl)-2-ethylthiomaleimide was blended in the following proportions,
A resin solution was prepared by stirring thoroughly.

Compound of Synthesis Example 2 5% Vinyl resin 5-candy rosin 5-functional xylene 85% Total 1000 li (2) Processing method Using the resin solution prepared in (1) above, process in the same manner as in (2) of Example 1. Antifouling treated.

Example 4 Treatment of fishing net and its antifouling test N-aryl-2 synthesized according to each synthesis example described above
An antifouling test was conducted using fishing nets that had been antifouled in the same manner as in Example 2 using each monosubstituted maleimide.

(1) Test method Cut a test piece to a size of 50 x 50 Crn from each antifouling fishing net, stretch it on a 60 x 60 m iron frame, and hang it in the sea from an immersion raft at a seabed of 1.5 Crn. maintain it.

(2) Test results As described in (1) above, fishing nets immersed in seawater were pulled up at predetermined intervals, and the state of adhesion of seaweed, sea lettuce, sea moss, hydro, sea squirt, etc., and the weight increase rate of the fishing nets were observed and measured. .

The results are shown in Table-3.

The evaluation symbols in this table have the following meanings.

- No adhesion at all ± Scattered (this adhesion is ten) A small amount of adhesion on the mesh wire body ζ ← A large amount of adhesion throughout the mesh body + + A large amount of adhesion throughout the entire mesh body, making it almost impossible for water to pass through.Also, the weight increase rate of the fishing net is initially The ratio of the increase in the weight of the fishing net after a predetermined period of time to the weight of the fishing net is expressed as a percentage.

These weights were determined after immersing them in the sea, pulling them out, draining them for 1 hour, and then weighing them.

Claims (1)

[Claims] 1 General formula (wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and Y represents a morpholino group, a piperidino group, or an N-methylpiperazino group; in this case, R1 is a hydrogen atom or a lower alkyl group, R2 is a lower alkyl group, R3 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a trifluoromethyl group, R4 is a lower alkyl group, R5 is a hydrogen atom or A halogen atom, R6 represents a hydrogen atom, a halogen atom, or a nitro group.