JPS5822003B2 - Aquatic organism repellent and its manufacturing method - 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 the petrochemical industry. A new antifouling agent for aquatic pests that prevents harmful aquatic organisms from adhering to water intake channels for cooling water, etc. of heat exchangers, etc. and a method for producing compounds that have an antifouling effect It provides:

Parts that are in constant contact with water, such as the bottom of a ship, underwater equipment, underwater structures, and cooling water intake channels.
Fujibbo, oyster, mussel, hydromushi, cellupa, bryozoan, sea squirt, bryozoan, sea lettuce, green laver,
It is well known that shellfish and algae, such as snails, propagate adherently.1 These adherent organisms cause an increase in fluid resistance and a decrease in thermal conductivity, reducing the functionality of equipment and causing undesirable conditions.

For example, in ships, this not only causes a decrease in sailing speed and wasted fuel, but also causes the ship to suspend operations to clean the bottom of the ship (causing economic losses such as losses and cleaning costs), and requires handling and operation of underwater structures. (This causes an inconvenience.) In the intake channels for condenser cooling water and heat exchanger cooling water, the intake amount not only decreases and the cooling efficiency decreases, but also water that falls off the channel wall and is washed away. The biomass is trapped, causing a decline in the performance of condensers and heat exchangers, resulting in large economic losses.

Conventionally, in order to prevent problems caused by adherent propagation 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 have been used. , antifouling paints containing arsenic compounds such as phenarsazine chloride are used, and chlorine or formalin is directly added to the intake channels F for cooling water to prevent aquatic organisms from attaching and breeding. was prevented.

However, antifouling paints containing heavy metal compounds such as copper oxides and mercury oxides have poor storage stability because the metal oxides contained tend to react with varnish components in the paint.

In addition, in contaminated sea areas such as ports where industrial sewage flows, 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 Fujibbo and Hoya.

It is effective against marine organisms such as coelomates and bryozoans, but has little effect on algae.

(The disadvantage of this antifouling paint is aluminum. When applied to light metal materials mainly made of magnesium etc.
Metals such as copper and mercury in the paint precipitate on the material, electrochemically promoting corrosion of the material.

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

Also, if a large amount is used, the performance of the coating film will deteriorate and the odor will be bothersome when handled.

Antifouling paints containing organic chlorine or organic sulfur compounds are much more effective (inferior) than any of the above antifouling paints; It has a selective effect on living organisms and is hardly of practical use.

Sarawoko, phenarsazine chloride (Adamsite)
However, phenarsazine chloride is extremely irritating to the mucous membranes of the human body.
Paint manufacturing and painting work are not easy.

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 various FA problems of conventionally used antifouling paints and agents as described above, and have found that bismaleimides have extremely low toxicity and have been shown to be effective against humans and animals. There is almost no toxic effect on fish, and the toxicity to fish is extremely low, so it can be used safely.
Antifouling paints containing this compound as an active ingredient have a stable effect in preventing the adhesion of aquatic organisms over a long period of time even in contaminated sea areas, and can be applied to light metal materials mainly made of aluminum, magnesium, etc. It does not electrochemically corrode metal materials at all, and by coating the walls of intake channels for cooling water, etc., there is no risk of corrosion of cooling equipment, and the adhesion and propagation of harmful aquatic organisms is sufficiently prevented. This discovery led to the completion of the present invention.

That is, the first invention of the present invention is based on the general formula (wherein R1 and R4 are a hydrogen atom, a lower alkyl R2 group, or a halogen atom, and A represents →〒23 arm-5-S- or -8O2-, When A is -C- and 3, R2 is a hydrogen atom, a lower alkyl group or a phenyl group, and R3 is a hydrogen atom or a lower alkyl group.

In the formula, n is an integer of 0 or l, and m is 0, 1, 2
, 3 or 4 integers.

), and the second invention relates to an aquatic organism repellent containing bismaleimides represented by t n and m have the same meanings as above.

) The bismaleamide acids produced by reacting with the aromatic diamines represented by (1) are produced without isolating and purifying (this method is used to produce bismaleimides (1) through a dehydration ring-closing reaction). This is the way to do it.

Examples of bismaleimides represented by general symbols used as active ingredients of the aquatic pest-adhering antifouling agent in the present invention are as follows.

Note that the compound numbers are referred to in Examples below.

Compound I N,N'-(1,2-phenylene)bismaleimide compound 2 N,N'-(1,3-phenylene)bismaleimide compound 3 N,N'-(1,4-phenylene)bismaleimide compound 4 N, N'-(4-methyl-1,3-)J nylene) bismaleimide compound 5 N, attached-(2,3,5,6-titramethyl-1,4-phenylene) bismaleimide compound 6 bis(4- Maleimidophenyl)methane compound 7 Bis(3-chloro-4-maleimidophenyl)methane compound 82,2-bis(4-maleimidophenyl)propane compound 92,2-bis(3-methyl-4-maleimidophenyl)propane compound 10 Bis(4-maleimidophenyl)phenylmethanoi\, Compound 11 Bis(4-maleimidophenyl)phenylnidine, Compound 122,2'-Dinaobisphenylmaleimito Compound 134,4'-Sulfonylbisphenylmaleimide9 9 These compounds As shown in the following reaction formula (1), the bismaleimides represented by the general symbol used as the active ingredient of the aquatic pest-adhering antifouling agent in the present invention are prepared by reacting maleic anhydride ( 9) and aromatic diamines l] at a temperature range of 0°C to 100°C for 1 to 2 hours, and the resulting reaction solution was reacted with an acid catalyst without isolating the bismaleamic acids (IV) produced. It can be produced in high yield by reacting in the presence of [this] for 1 to 5 hours at a temperature range of 80° C. to 200° C., followed by dehydration and ring closure.

Reaction formula l tD)- (RI R4A t n and m in the formula have the same meanings as above.

) The reaction solvent may be any polar solvent, specifically acetonitrile.

10) Nitriles such as IJ and benzonitrile, ketones such as acetone, methyl ethyl ketone, and methyl isobunal ketone, and methyl alcohol.

Alcohols such as ethyl alcohol, furoyl alcohol, and methyl alcohol; esters such as methyl formate, ethyl formate, ethyl acetate, and ethyl propionate; and dimenal sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, and ethylene glycol. Aprotic polar solvents such as diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetramenalene glycol dimethyl ether, etc. can be used, and among them, dimenal sulfoxide, dimethylformamide, dimenal acetamide, and hexamenal phosphorus can be used. If an aprotic polar solvent such as Roamide is used, the desired product can be obtained in high yield.

Furthermore, when a non-polar solvent such as benzene, toluene, xylene or hexane is used, a reaction occurs and a large amount of a blackish brown resinous substance is produced, making it impossible to obtain the desired product, which is unsuitable.

As the acid catalyst, any acid catalyst that is normally used as a dehydrating agent may be used, but specific examples include hydrochloric acid, sulfuric acid, sulfuric anhydride, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, and acetic anhydride. , thionyl chloride, phosphorus oxychloride, toluenesulfonic acid, etc., and are used in an amount of 0.01 to 0.3 times the mole of maleic anhydride used as the raw material.

The aromatic diamines represented by the general formula [■] used as raw materials include, for example, 0-phenylenediamine, m-phenylenediamine, p-phenylenediamine,
-phenylenediamine, 2,4-diaminotoluene, 2
, 6-diaminotoluene, 4-chloro-〇-phenylenediamine, 4-chloro-m-phenylenediamine, 2
-chloro-p-phenylenediamine, 4,5-dumenal-0-phenylenediamine, 4,5-cyclo-p-phenylenediamine.

2.3,5.6-natramenal-p-phenylenediamine, 2,3,5,6-rtrachloro-p-phenylenediamine, 4,4-diaminodiphenylmethane, 3-
Methyl-44 diamino diphenylmethane, 3.3'
-diethyl-4,4-diaminodiphenylmethane.

3.3'-dichloro-4,4'-diaminodiphenylmethane, 2,2', 5.5-tetrachloro-4,4'
-diaminodiphenylmethane, 4,4'-diaminodiphenyl disulfide, 3,3'-dimethyl-4,4 diamino diphenyl disulfide, 2,2'-dichloro-
4,4'-diaminodiphenyl disulfide, 2.2
'-Diamino diphenyl disulfide, 4,4-diaminodiphenylsulfone, 3.3'-dimethyl-4,4
'-Diaminodiphenylsulfone, 3,3'-zenal-4,4'-diaminodiphenylsulfone, 3,3'
-dichloro-4,4'-diaminodiphenylsulfone,
2.2',3.3'-tetrachloro-4,4'-diaminodiphenylsulfo7,2,2-his(4-aminophenyl)propane.

2.2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl)propane, 2,2-bis(2,3-dichloro-4-aminophenyl) ) Propane, bis(4-aminophenyl)
Phenylmethane, bis(3-ethyl-4-aminophenyl)phenylethane, bis(2,3-dimethyl-4-aminophenyl oligophenylethane, bis(2,5-dichloro-4-aminophenyl)phenylethane, etc. The raw material maleic anhydride (usually used in equimolar amounts, but even if it is used in an equimolar or more amount, the reaction will not be affected).

Next, the manufacturing method of the present invention will be explained in detail with reference to synthesis examples.

;Synthesis Example 1 30 equipped with a thermometer, cooling tube, dropping funnel and stirrer
0go four-eyed flask cloudy dimethylformamide 1001
This (maleic anhydride 19.69
(0.2 mol) was added and dissolved.

Next, add 70 ml of dimethylformamide to this.
- A solution in which 10.8 g (0.1 mol) of phenylenediamine was dissolved was added dropwise at room temperature while stirring.

It generates heat at the same time as dropping, but after dropping, the temperature rises to 68-71℃.
(The reaction was continued for 2 hours with constant stirring.

Then, 0.5 g (0,0048 mol) of sulfuric acid was added, heated, and reacted for 4 hours with stirring while maintaining the temperature at 120 to 130°C.

After the reaction is completed, the reaction solution is mixed with 500771. theory on l water,
The precipitated crystals were collected by filtration, recrystallized with ethanol, and
N-(1,2-phenylene)bismaleimide (m, 92
36-237°C) at 22. sg (yield 85.2%) was obtained.

Synthesis Examples 2 to 13 In the same manner as in Synthesis Example 1, maleic anhydride and various aromatic diamines were reacted in various polar solvents, and then subjected to a dehydration ring-closing reaction to obtain various hismaleimides.

The results are shown in Table 1.

Comparative Examples 1 to 3 Same as Synthesis Example 1 using benzene, toluene or xylene as the reaction solvent (maleic anhydride and various aromatic diamines were reacted, and then a dehydration ring-closing reaction was carried out, but the target bis No maleimides were obtained, and a blackish brown resinous substance was produced.

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 of the compounds of the general formula (1) with a film forming agent (to prepare an antifouling paint and applying it 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 CI) is incorporated in a proportion of 5 to 80%, preferably 10 to 50%, based on the weight of the film-forming agent.

For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel (Kooke), the compound of general formula [I] may be added to the intake channel 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 the aquatic pest-adhering antifouling agent of the present invention is applied to fishing nets, the compound (general formula 〇) is dissolved together with a resin in an organic solvent to form a resin solution, and this resin solution is used to clean fishing nets. Impregnate and dry.

When preparing this resin solution, the compound of General Hiki I] is 1 to 10% by weight, preferably 1 to 6% by weight, and the resin is 5 to 10% by weight.
It is dissolved in an organic solvent at a concentration of 15% by weight, preferably 7-12% by weight.

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

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

In addition, benzene, toluene, xylene, chloroform, etc. are used as organic solvents, but they do not dissolve the resin.
In the case of a heavy-duty case, 5 to 15% by volume of dimethylformamide, dimethylacetamide or dimenal sulfoxide is added.
can be mixed within the range of

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

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

Next, examples of formulations of paints and examples of antifouling tests against aquatic organisms using paints based on such formulations will be given, and the manufacturing method of the present invention will be described. Shows preventive effect.

Formulation Example of Paint 1 Compound 1: N,N'(1,2-phenylene)bismaleimide was blended in the following proportions, thoroughly ground in a pocket mill, and mixed to prepare an antifouling paint.

(% indicates weight percentage.

Same below) Compound of Synthesis Example 1 20.0% Bengara 1000% Tarri 15.
0% barium sulfate 20.0%, vinyl resin 5.5% resin 5.5% tricresyl phosphate 2.0% methyl isofusal ketone 11.0% xylene 11.0% Total 100.0% of paint Synthesis Example 2 Compound 2: N,N'(1,3-phenylene)bismaleimide was blended in the following proportions, thoroughly ground in a pocket mill, and mixed to obtain an antifouling paint.

Compound of Synthesis Example 2 15.0% Bengara 18.0% Tal
10.0% Aluminum Stearate 0.5% Ri Graphite 0.5%
Gin 26.0% Boil oil 12.0% Solvent naphtha 18.0% Total 100.0% Example 1 Marine organism antifouling immersion test) Preparation of test plate and test method Once with wash brimer, rust preventive paint Each steel plate (300 x 100 x 1) that had been primed once was coated with each antifouling paint twice with a brush, fitted into a wooden frame, suspended underwater from a dipping raft, and placed in a trench 1.5 m deep. maintain.

(2) Test results After straining as described in (1) above, the coated plate immersed in seawater was pulled up at specified intervals, and the adhering dust of living things adhering to it was expressed as a percentage of the total adhering area. I showed you the table.

The control was treated with wash primer and anti-rust paint.

The results are shown in Table 2.

Example 2 Antifouling treatment of fishing nets (1) (1) Preparation of resin solution Compound 1: N,N'(1,2-phenylene)bismaleimide was blended in the following proportions, stirred thoroughly, and the resin solution was Prepared.

Compound of Synthesis Example 1 8% Chlorinated rubber 5% Rosin 2% Total
En 85% Total 100% (2) Processing method Eleven sections (3, A fishing net (03CrfL mesh) was dipped, thoroughly impregnated, and then air-dried for 12 hours for antifouling treatment.

Example 3 Antifouling treatment of fishing nets (2) (1) Preparation of resin solution Compound 3: N, N'-(1,4-phenylene)
Bismaleimide was blended in the following ratio and thoroughly stirred to prepare a resin solution.

Compound part (3) of Synthesis Example 3 5% Vinyl resin 5% Rosin 5% Xylene
85% Total 100% (2) Processing method The resin solution prepared in (■) above was subjected to antifouling treatment in the same manner as in (2) of Example 1.

Example 4 Fishing net treatment and its antifouling test An antifouling test was conducted using a fishing net treated with antifouling treatment in the same manner as in Example 2 using each of the bismaleimides synthesized according to the above-mentioned synthesis examples. .

(1) Test method Cut a test piece to a size of 50 x 50 cm from a fishing net treated with antifouling treatment, set up a 60 x 60 iron frame, and hang it underwater from a dipping raft to a depth of 1.5 m in the sea. (2) Test results As described in (1) above, the fishing nets immersed in sea water are pulled out at regular intervals to determine the state of adhesion of seaweed, sea lettuce, grass moss, hydro, sea squirt, etc., and the condition of the fishing nets. The weight increase rate was 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 adhesion + A small amount of adhesion throughout the entire net The entire net is broken, a large amount of adhesion The boat has a large amount of adhesion throughout the entire net, making it impossible for most water to pass through. The ratio of the increase in the weight of the fishing net after a predetermined period of time to the weight is expressed as a percentage.

The weight of these items was determined after the soaked items were lifted out of the sea and drained for 1 hour.

Claims (1)

[Claims] 1 General formula (wherein R1 and R4 are a hydrogen atom, a lower alkyl group, or a halogen atom, and A is 10-2■ 3 or -5-S- or -8O□- When A is -C- and 3, R2 is a hydrogen atom, a lower alkyl group or a phenyl group, and R3 is a hydrogen atom or a lower alkyl group. In the formula, n is an integer of 0 or l, m is 0, 1, 2
．． An integer of 3 or 4. ) An antifouling agent against adhesion of underwater harmful organisms, characterized by containing a bismaleimide represented by the following as an active ingredient. 2 Maleic anhydride in a polar solvent and the general formula (where R1 and R4 are hydrogen atoms, lower alkyl groups, 2 groups, or halogen atoms, and A is -C-23, -5-S- or -502-). In the formula, when A is 10-3, R2 is a hydrogen atom, a lower alkyl group, or a phenyl group, and R3 is a hydrogen atom or a lower alkyl group. In the formula, n is O or an integer of 1, and m is 0,1,2
, 3 or 4 integers. ) is reacted with aromatic diamines represented by the general formula (in the formula R4s R4p A
y n and m have the same meanings as above. ) A method for producing an antifouling agent for adhesion of aquatic harmful organisms, characterized by obtaining a bismaleimide represented by