JPH09309866A - Beta-(meth)acryloyloxy-alkylamine derivative, its polymer and preventing agent for attachment of marine organism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative useful as a stable preventing agent for attachment of marine organisms in order to prevent the marine attached organisms from attaching to fishing nets, ship bottoms, seawater inlet channel walls, etc., for a long period. SOLUTION: This β-(meth)acryloyloxy-alkylamine derivative is represented by the formula R<1> is H or a 1-4C alkyl, with the proviso that R<2> is [(CH2 )n NH]m H [(n) is 1-4; (m) is 1-5] when R<1> is H and R<2> is a 1-4C alkyl; R<3> is an 8-28C alkyl; R<4> is H or methyl when R<1> is a 1-4C alkyl}, e.g. an N,N- dimethyl-β-methacryloyloxy-alkyl (55% dodecyl and 45% tetradecyl)amine. The compound represented by the formula is obtained by reacting, e.g. a β- hydroxyalkyl-amine with (meth)acryloyl chloride. Furthermore, a polymer, formed by polymerizing the compound represented by the formula and having 10000-1000000 weight-average molecular weight (measured by a gel permeation chromatography using polystyrene as a standard) is useful as a preventing agent for the attachment of the marine organisms.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a β- (meth) acryloyloxy-alkylamine derivative and a polymer thereof, and a marine organism adhesion-preventing agent. More specifically, the present invention relates to a stable marine organism adhesion preventive agent for preventing marine adherent organisms from adhering to fishing nets, ship bottoms, seawater intake channel walls, etc. for a long period of time.

[0002]

2. Description of the Related Art In recent years,
Aquaculture and fishery and construction of marine facilities have become popular, and the habitat of marine attached organisms is expanding. For this reason, the bottom of ships, underwater structures, aquaculture nets, buoys or set nets, etc., are retained in seawater for a long period of time, so many adherent organisms such as barnacles, magnolias, mussels attach,
These cause various obstacles.

Conventionally, various anti-adhesion agents for marine organisms have been proposed and put into practical use in order to prevent the adhered organisms from adhering to fishing nets, ship bottoms, seawater intake channels, etc. and causing adverse effects. For example, an anti-adhesion agent containing an active ingredient such as an organic tin compound, an organic or inorganic copper compound or an organic chlorine compound, and a specific acrylic acid polymer has been proposed. However, these active ingredients are highly toxic enough to cause marine pollution and have the property of accumulating in the living body. For this reason, particularly when handling edible aquatic organisms in the aquaculture industry, there is a risk that the human body may be affected and that the worker who directly handles the anti-adhesion agent may be affected.

In order to improve safety, an anti-adhesion agent using a polyisocyanate compound or a metal compound capable of chelating with a carboxyl group instead of the above-mentioned highly toxic compound has been proposed. However, these highly safe anti-adhesion agents cannot be said to have sufficient anti-adhesion effects over a long period of time. Therefore, an anti-adhesion agent has been proposed which contains a specific higher aliphatic amine compound having low toxicity and good biodegradability and a film-forming agent comprising a specific carboxyl group-containing copolymer (special feature: Kaihei 1-103672, JP-A-3
-252462 and JP-A-3-252436).

However, in the anti-adhesion agent formed by the reaction product of the higher aliphatic amine compound and the carboxyl-containing polymer, the polycarboxylic acid copolymer has a weak ability to immobilize the amine compound, so that the elution amount of the amine compound is increased. When it is not sufficiently adjusted and it is immersed in seawater for a long period of time by applying it to fishing nets, ship bottoms, seawater intake channels, etc., the elution amount of amine compounds immediately after immersion becomes large and the elution amount tends to decrease with the passage of time. there were. For this reason, in a sea area with few adherent organisms, the anti-adhesion effect is maintained for a considerable period,
The long-term (for example, 6 months) anti-adhesion effect in high-temperature water areas and sea areas with many adherent organisms has not yet been sufficiently satisfactory. In addition, in order to have a wider biological spectrum, N-phenylmaleimide compounds, 3
-We examined the blending of known active ingredients such as isothiazolone derivatives and tetraalkylthiuram compounds with higher aliphatic amine compounds. However, when both were mixed in an organic solvent, they reacted and gelled, or crystalline substances were precipitated. In addition, the harmful gas is generated, the long-term storage stability of the product is poor, and the anti-adhesion effect is significantly lowered. Therefore, an anti-adhesion agent that is highly safe and has a long-lasting anti-adhesion effect has been desired.

[0006]

SUMMARY OF THE INVENTION The inventors of the present invention have
From this point of view, as a result of studying the long-term sustainability of the anti-adhesion effect, an anti-adhesion agent containing a novel β- (meth) acryloyloxy-alkylamine derivative as an active ingredient exerts the anti-adhesion effect continuously over a long period of time. The present invention has been completed and the present invention has been completed.

Thus, according to the present invention, the general formula (I):

[0008]

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[Wherein R ¹ is a hydrogen atom or a carbon number of 1 to 4]
When R ¹ is a hydrogen atom, R ² is — [(CH ₂ ) _n NH] _m H (n is an integer of 1 to 4, m is an integer of 1 to 5), and R ¹ is When it is a lower alkyl group having 1 to 4 carbon atoms, R ² represents a lower alkyl group having 1 to 4 carbon atoms,
R ³ Is an alkyl group having 8 to 28 carbon atoms, R ⁴ Represents a hydrogen atom or a methyl group], and a β- (meth) acryloyloxy-alkylamine derivative is provided.

According to the present invention, the derivative is polymerized and has a weight average molecular weight (gel permeation chromatography analysis using polystyrene as a standard, hereinafter abbreviated as GPC) of 10,000 to 1,000,000. Is provided.

Furthermore, according to the present invention, it is obtained by copolymerizing the above derivative with an ethylenically unsaturated monomer and has a weight average molecular weight (GPC) of 10,000 to 1,000,
000 is provided.

Further, according to the present invention, there is provided a marine organism adhesion-preventing agent containing the above derivative, polymer or copolymer as an active ingredient.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The β- (meth) acryloyloxy-alkylamine derivative of the present invention is represented by the general formula (I). In the formula, examples of the lower alkyl group having 1 to 4 carbon atoms of R ¹ and R ² include a straight chain or branched chain alkyl group. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
Examples thereof include tert-butyl, and among them, methyl and ethyl are more preferable. Also, R ³ Examples of the lower alkyl group having 8 to 28 carbon atoms include a linear or branched alkyl group, and a linear alkyl group is preferable. Specifically, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl and the like. Among them, dodecyl, tetradecyl, hexadecyl and octadecyl are preferable. Further, two or more kinds of these alkyl groups may be mixed.

Specific examples of the β- (meth) acryloyloxy-alkylamine derivative represented by the general formula (I) include N, N-dimethyl-β-acryloyloxydodecylamine and N, N-dimethyl-β-acryloyl. Loyloxytetradecylamine, N, N-dimethyl-β-acryloyloxyhexadecylamine, N, N-dimethyl-β-acryloyloxyoctadecylamine, N, N-dimethyl-
β-acryloyloxy-alkyl (dodecyl = 55%,
Tetradecyl = 45%) amine, N, N-dimethyl-β
-Acryloyloxy-alkyl (hexadecyl = 57
%, Octadecyl = 43%) amine; N, N-diethyl-β-acryloyloxydodecylamine, N, N-diethyl-β-acryloyloxytetradecylamine, N,
N-diethyl-β-acryloyloxyhexadecylamine, N, N-diethyl-β-acryloyloxyoctadecylamine, N, N-diethyl-β-acryloyloxy-alkyl (dodecyl = 55%, tetradecyl = 45
%) Amine, N, N-diethyl-β-acryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 4)
3%) amine; N, N-dimethyl-β-methacryloyloxydodecylamine, N, N-dimethyl-β-methacryloyloxytetradecylamine, N, N-dimethyl-β
-Methacryloyloxyhexadecylamine, N, N-dimethyl-β-methacryloyloxyoctadecylamine,
N, N-dimethyl-β-methacryloyloxy-alkyl (dodecyl = 55%, tetradecyl = 45%) amine,
N, N-Dimethyl-β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine; N, N-diethyl-β-methacryloyloxydodecylamine, N, N-diethyl-β-methacryloyl Roxytetradecylamine, N, N-diethyl-β-methacryloyloxyhexadecylamine, N, N-diethyl-β
-Methacryloyloxyoctadecylamine, N, N-diethyl-β-methacryloyloxy-alkyl (dodecyl = 55%, tetradecyl = 45%) amine, N, N-diethyl-β-methacryloyloxy-alkyl (hexadecyl = 57 %, Octadecyl = 43%) amine.

In the general formula (I), R¹Is a field of hydrogen atoms
If R^TwoIs-[(CH_Two)_nNH] _mH (n is 1 to 4
Even if it is a substitution part represented by an integer, m is an integer of 1 to 5)
Good. Examples of this substitution include ethylene amyl,
Diethylene diamyl, triethylene triamyl, terra
Examples include ethylene tetramil and pentaethylene pentamil.
You can As a compound having this substitution, for example,
For example, β-methacryloyloxy-alkyl (dodecyl = 5
5%, tetradecyl = 45%) ethylenediamine, β-
Methacryloyloxy-alkyl (hexadecyl = 57
%, Octadecyl = 43%) ethylene diamine
It is.

Among the above compounds, the β- (meth) acryloyloxy-alkylamine derivative represented by the general formula (I) includes N, N-dimethyl-β-methacryloyloxy-alkyl (dodecyl = 55%, tetradecyl). = 4
5%) amine, N, N-dimethyl-β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine, N, N-dimethyl-β-acryloyloxy-alkyl (dodecyl = 55%, tetradecyl =
45%) amine, N, N-diethyl-β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine, β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) ethylenediamine Is preferred.

The β- (meth) acryloyloxy-alkylamine derivative of the present invention can be synthesized by using a known reaction process. For example, β-hydroxyalkyl-amine was synthesized and the obtained β-hydroxyalkyl-amine
It is obtained by reacting an amine with (meth) acrylic acid chloride. The β-hydroxyalkyl-amine is, for example, an α-olefin which is reacted with an organic peracid or other peroxide in an inert solvent under mild conditions to form an α-olefin.
It can be obtained by obtaining an olefin epoxide and reacting this α-olefin epoxide with an alkylamine. Here, examples of the inert solvent include benzene, chloroform, carbon tetrachloride and the like. Examples of the organic peracid or other peroxide include perbenzoic acid, peracetic acid, performic acid, perphthalic acid, perpropionic acid, perbutyric acid, and trifluoroperacetic acid, and perbenzoic acid and peracetic acid are preferably used. To be
Examples of β-hydroxydimethylamine are shown below.

First, α-in an inert solvent under mild conditions.
The olefin and peracetic acid are reacted and purified to obtain α of the following formula.
-Olefin epoxide is obtained.

[0019]

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(In the formula, R represents a hydrogen atom or a methyl group) Then, the obtained α-olefin epoxide is reacted with dimethylamine in the presence of an inert solvent to remove the solvent, and β-hydroxy of the following formula: Obtain dimethylamine.

[0021]

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(In the formula, R represents a hydrogen atom or a methyl group) Further, the obtained β-hydroxyalkyl-amine is reacted with (meth) acrylic acid chloride to obtain the desired β- (meth) acryloyloxy-alkyl. An amine derivative is obtained.
The reaction temperature at this time is appropriately set depending on the solvent used for the synthesis, but is 15 to 70 ° C., preferably 20 to 40 ° C.
It is. After the reaction, the obtained derivative was filtered to remove the precipitate, and the filtrate was washed with 9% anhydrous sodium carbonate aqueous solution and the like and dried with magnesium sulfate and the like, and a small amount of hydroquinone monoethyl ether or the like was added to prevent polymerization. After that, the solvent is removed to obtain.

According to another aspect of the present invention, it is obtained by polymerizing a β- (meth) acryloyloxy-alkylamine derivative represented by the general formula (I) and has a weight average molecular weight (GPC) of 10,000 to. A polymer of 1,000,000 is provided. Further, there is provided a copolymer obtained by copolymerizing the above derivative with an ethylenically unsaturated monomer and having a weight average molecular weight (GPC) of 10,000 to 1,000,000.

The above-mentioned derivative can be polymerized by itself or can be copolymerized with an ethylenically unsaturated monomer. The ethylenically unsaturated monomer is not particularly limited as long as it can be copolymerized with the derivative. Specific examples of this monomer include methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate. , (Meth) acrylic ester-based unsaturated monomers such as cyclohexyl acrylate; 2-hydroxyethyl acrylate, 2-
Hydroxy lower alkyl (meth) acrylates such as hydroxypropyl acrylate, diethylene glycol monoacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; other (meth) acrylic acid, crotonic acid, vinyl benzoic acid, α-cyanoacrylic acid, malein Hydrophilic unsaturated monomers such as acids, fumaric acid, itaconic acid; styrene, α-methylstyrene, butadiene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl butyrate, methyl vinyl ether, octyl vinyl ether, acrylonitrile, Methacrylonitrile, acrylamide, methacrylamide, etc. are mentioned. Among the above monomers, (meth) acrylic acid and its ester, and styrene are preferable.
As the derivative and the monomer, one compound may be used alone, or two or more compounds may be used in combination.

The proportion of the monomer used is in the range of 0 to 90% by weight based on the total weight of the derivative and the monomer of 100% by weight, if necessary. When the ratio is within the above range, an effective marine organism adhesion preventing effect can be obtained, which is preferable. The weight average molecular weight (GPC) of the polymer is 1
10,000-1,000,000, preferably 20,0
The weight average molecular weight (GPC) of the copolymer is 10,000 to 1,000,000,
It is preferably 20,000 to 600,000. When the weight average molecular weight is within the above range, the form of the coating agent can be maintained in seawater, and a coating agent having an appropriate viscosity and good coating workability can be obtained.

The polymer and copolymer in the present invention are
It can be carried out by a known method using a polymerization initiator, such as polymerization in a solution or bulk polymerization. As the solvent used at that time, water; alcohols such as methyl alcohol, ethyl alcohol, butanol; ethers such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether, dioxane; toluene, xylene, ethylbenzene, methylnaphthalene, etc. And aromatic hydrocarbons; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isoamyl ketone.

As the polymerization initiator, persulfates such as ammonium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, t-butyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo Aliphatic azo compounds such as bisisobutyronitrile, azobisisophthalonitrile and azobisdimethylvaleronitrile can be used. The polymerization temperature is appropriately set depending on the solvent used and the polymerization initiator, but is usually set in the range of 40 to 120 ° C, preferably 45 to 80 ° C.

Further, according to another aspect of the present invention, there is provided a marine organism adhesion preventing agent comprising the above derivative, polymer or copolymer as an active ingredient. The marine organism adhesion preventing agent of the present invention is usually a polymer obtained as described above,
It is prepared in the form of a solution by dissolving it in a suitable solvent for improving the coating workability. Examples of the solvent include methyl alcohol, ethyl alcohol, xylene, toluene, cyclohexanone, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, naphtha, ethylene glycol monoethyl ether, propylene glycol monoethyl ether (PGM), and the like. Other than this, various solvents and additives used in the field of paints can be used, and some water may be contained.

When used as a marine organism adhesion-preventing agent for fishing nets, the concentration of the active ingredient is 20 to 99% by weight, preferably about 25 to 95% by weight, in terms of solid content, to prevent the adhesion of marine organisms. , In terms of film-forming property, film strength, etc., to improve the adhesion to the net, the stiffness of the net, etc., compound dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate, polybutene, etc. Good to do. For application to a fishing net, a conventional method such as a dipping method is used.

The above-mentioned derivative, polymer or copolymer is
It can be used as a paint formulated into a coating form.
When used as this marine organism adhesion preventing paint, the active ingredient is contained in a solid content of 20 to 99% by weight, preferably 25.
Approximately 95 wt% is mixed and dissolved in a suitable solvent, and a pigment, a plasticizer, a surfactant, a coating film preparation vehicle and the like are mixed to prepare a paint. As pigments, talc, white titanium, yellow lead,
Examples include dark blue, red iron oxide, and phthalocyanine blue. Examples of the plasticizer include dioctyl phthalate, diadipate phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate, liquid paraffin and the like. The vehicle for adjusting the coating strength and the like, rosin, boil oil, chlorinated rubber, polybutene,
Examples thereof include vinyl chloride resin, acrylic resin, epoxy resin and coumarone resin. When it is used as paint, it is applied by brushing, roller coating, spraying, or the like.

Further, the marine organism adhesion preventive agent of the present invention may optionally contain copper powder, cuprous oxide, copper rhodanide, copper naphthenate, copper oleate, dimethyldithiocarbamate, tetraethylthiuram disulfide, zinc pyrithione,
4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one, 2-thiocyanomethylthiobenzothiazole, tetrachloroisophthalonitrile, 2,3-dichloro-2,6-diethylphenylmaleimide, pyridinetri Phenylborane; higher aliphatic alkylamines (having 8 to 22 carbon atoms) such as N, N-dimethyl-β-hydroalkylamine, tallow alkyldimethylamine, tallow alkylpropylenediamine, tallow alkyldipropylenetriamine, and tallow alkyltripropylenetetramine. Known anti-adhesion active ingredients such as the above can be appropriately used in combination.

[0032]

【Example】

(Synthesis of Derivative) Synthesis Example 1 N, N-dimethyl-β-methacryloyloxy-alkyl (dodecyl = 55%, tetradecyl = 45%) amine (Compound 1) Dichloromethane 7 containing 2.65 g of anhydrous sodium carbonate.
In 7.74 ml, N, N-dimethyl-β-hydroxy-alkyl (dodecyl = 55%, tetradecyl =
45%) 5.35 g of amine (oxyamine DML manufactured by Daicel Chemical Industries, Ltd.) and 4.02 of methacrylic acid chloride.
g, and stirred at room temperature for 48 hours. After stirring, 5
Refluxed for hours. Then, the precipitate was filtered off and the filtrate was washed with 9
% Aqueous sodium carbonate solution and washed 3 times. After washing
After drying over magnesium sulfate and adding 2 drops of hydroquinone monoethyl ether, the solvent was removed to obtain 3.83 g of the target compound (yield 58%).

This compound was a pale yellow oily substance, and the following analytical data were obtained. ¹³ C-NMR (CDCl ₃ : 22.4 MHz) δ: 13.84, 1
8.08, 22.42, 25.00, 29.09, 2
9.26, 29.35, 29.41, 31.68, 3
2.55, 45.38, 62.14, 71.72, 12
4.89, 136.40, 166.65 (71.72 belongs to β-position carbon) IR (NaCl) wave number: 1718 cm ^-1 (ester absorption)

Synthesis Example 2 N, N-dimethyl-β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine (Compound 2) Dichloromethane 7 containing 2.65 g of anhydrous sodium carbonate.
In 7.74 ml, 6.53 g of N, N-dimethyl-β-hydroxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine (manufactured by Daicel Chemical Industries, oxyamine DMN) and methacrylic acid chloride 4.
02 g was added and stirred at room temperature for 48 hours. After completion of stirring, the mixture was refluxed for 5 hours. Then, the precipitate was filtered off, and the filtrate was washed with 9% anhydrous sodium carbonate aqueous solution three times. After washing, it was dried over magnesium sulfate, 2 drops of hydroquinone monoethyl ether was added, and then the solvent was removed to obtain 3.44 g (yield 43%) of the target compound.

This compound was a pale yellow oily substance, and the following analytical data were obtained. ¹³ C-NMR (CDCl ₃ : 22.4 MHz) δ: 13.90, 1
8.14, 22.52, 25.09, 29.20, 2
9.50, 31.77, 32.61, 45.61, 6
2.44, 71.96, 124.80, 136.52,
166.77 (71.96 is assigned to carbon at β-position) IR (NaCl) wave number: 1716 cm ^-1 (absorption of ester)

Synthesis Example 3 N, N-dimethyl-β-acryloyloxy-alkyl (dodecyl = 55%, tetradecyl = 45%) amine (Compound 3) Dichloromethane 7 containing 2.65 g of anhydrous sodium carbonate.
In 7.74 ml, N, N-dimethyl-β-hydroxy-alkyl (dodecyl = 55%, tetradecyl =
45%) amine (manufactured by Daicel Chemical Industries, oxyamine DML) 5.35 g and acrylic acid chloride 3.48 g
Was added and stirred at room temperature for 48 hours. After completion of stirring, the mixture was refluxed for 5 hours. Then the precipitate was filtered off and the filtrate was
It was washed with anhydrous sodium carbonate aqueous solution of 3 times. After washing
After drying with magnesium sulfate and adding 2 drops of hydroquinone monoethyl ether, the solvent was removed to obtain 3.35 g (yield 51%) of the target compound.

This compound was a pale yellow oily substance, and the following analytical data were obtained. ¹³ C-NMR (CDCl ₃ : 22.4 MHz) δ: 13.84, 2
2.46, 25.09, 29.12, 29.29, 3
1.71, 32.55, 62.71, 71.93, 12
8.79, 129.87, 165.55 (71.93 belongs to β-position carbon) IR (NaCl) wave number: 1725 cm ^-1 (ester absorption)

Synthesis Example 4 N, N-diethyl-β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine (Compound 4) Dichloromethane 7 containing 2.65 g of anhydrous sodium carbonate.
In 7.74 ml, 7.15 g of N, N-diethyl-β-hydroxy-alkyl (hexadecyl = 57%, octadecyl = 43%) ein (Oxyamine DEN, manufactured by Daicel Chemical Industries Ltd.) and methacrylic acid chloride 4.
02 g was added and stirred at room temperature for 48 hours. After completion of stirring, the mixture was refluxed for 5 hours. Then, the precipitate was filtered off, and the filtrate was washed with a 9% anhydrous sodium carbonate aqueous solution three times.
After washing, it was dried over magnesium sulfate, 2 drops of hydroquinone monoethyl ether was added, and then the solvent was removed to obtain 3.44 g (yield 40%) of the target compound.

This compound was a pale yellow oily substance, and the following analytical data were obtained. ¹³ C-NMR (CDCl ₃ : 22.4 MHz) δ: 11.72, 1
3.87, 18.14, 22.52, 25.18, 2
9.20, 29.35, 29.53, 31.77, 3
2.52, 47.61, 55.97, 72.61, 12
4.56, 136.67, 167.77 (72.61 belongs to β-position carbon) IR (NaCl) wave number: 1716 cm ^-1 (absorption of ester)

Synthesis Example 5 β-methacryloyloxy-alkyl (hexadecyl = 5
7%, octadecyl = 43%) Ethylenediamine (Compound 5) Dichloromethane 7 containing 2.65 g of anhydrous sodium carbonate
To 7.74 ml, β-hydroxy-alkyl (hexadecyl = 57%, octadecyl = 43%) ethylenediamine (manufactured by Daicel Chemical Industries, Ltd., load pole 2)
N) 6.86 g and methacrylic acid chloride 4.02 g were added, and the mixture was stirred at room temperature for 48 hours. After completion of stirring, the mixture was refluxed for 5 hours. Then, the precipitate was filtered off, and the filtrate was washed with a 9% anhydrous sodium carbonate aqueous solution three times. After washing, it was dried over magnesium sulfate, and after adding 2 drops of hydroquinone monoethyl ether, the solvent was removed and the desired compound 1.
07 g (yield 13%) was obtained.

This compound was a pale yellow semi-solid and the following analytical data were obtained. ¹³ C-NMR (CDCl ₃ : 22.4 MHz) δ: 13.81, 1
8.05, 18.26, 22.40, 29.09, 2
9.41, 31.65, 48.36, 53.16, 5
4.89, 71.69, 125.60, 135.86,
168.38 (71.69 is assigned to the β-position carbon) IR (NaCl) wave number: 1717 cm ^-1 (absorption of ester)

Synthesis Example 6 N, N-dimethyl-β-methacryloyloxy-dodecylamine (Compound 6) Dichloromethane 7 containing 2.65 g of anhydrous sodium carbonate
5.07 g of N, N-dimethyl-β-hydroxy-dodecylamine and 4.02 g of methacrylic acid chloride were added to 7.74 ml, and the mixture was stirred at room temperature for 48 hours.
After completion of stirring, the mixture was refluxed for 5 hours. Then, the precipitate was filtered off, and the filtrate was washed with a 9% anhydrous sodium carbonate aqueous solution three times. After washing, it was dried over magnesium sulfate, 2 drops of hydroquinone monoethyl ether was added, and then the solvent was removed to obtain 4.12 g (yield 63%) of the target compound.

This compound was a pale yellow oily substance, and the following analytical data were obtained. ¹³ C-NMR (CDCl ₃ : 22.4 MHz) δ: 13.87, 1
8.14, 22.49, 25.09, 29.15, 2
9.32, 29.47, 31.74, 32.55, 4
5.73, 62.53, 72.08, 124.77, 1
36.55, 166.77 (72.08 is assigned to carbon at β-position) IR (NaCl) wavenumber: 1718 cm ^-1 (absorption of ester) N, N-dimethyl-β-hydroxy-dodecylamine as a raw material Is N, N-dimethyl-β-hydroxy-
Alkyl (dodecyl = 55%, tetradecyl = 45%)
Amine (Oxyamine DML manufactured by Daicel Chemical Industries, Ltd.)
Obtained by distilling.

(Production of Polymer) A polymer was prepared by using the compound of the synthesis example as an example. Polymerization a 300 equipped with stirrer, thermometer, reflux tube and nitrogen introduction tube
In a milliliter separable flask, add Compound 1
g, and then 55 g of xylene was added, and the mixture was stirred while being replaced with nitrogen and heated to 70 ° C. in a water bath. After stirring for 1 hour, 10 g of xylene in which 0.2 g of the polymerization initiator azobisisobutyronitrile was dissolved was added dropwise while again substituting with nitrogen, and the temperature of the reaction vessel was kept at 70 ° C. in a water bath. After stirring for 5 hours, a polymer a was obtained. The weight average molecular weight of the obtained polymer a was 100,000 by gel permeation chromatography analysis (GPC) using polystyrene as a standard. Table 1 shows the results.

[0045]

[Table 1]

In Table 1, the abbreviations in the column of ethylenically unsaturated monomers used for polymer production are as follows. BA: n-butyl acrylate 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate MA: methacrylic acid AA: acrylic acid ST: styrene

Polymers b to c Polymers b to c were prepared in the same manner as the polymer a except that the compound 3 or 5 was used in place of the compound 1 and the polymerization ratios shown in Table 1 were used.
I got

Polymerization d 300 equipped with a stirrer, thermometer, reflux tube and nitrogen introducing tube
4 g of compound 2 in a milliliter separable flask,
Further, 50 g of xylene was added. Next, 22 g of n-butyl acrylate and 14 g of methyl methacrylate were gradually added dropwise. After completion of dropping, the mixture was stirred while being replaced with nitrogen and heated to 70 ° C. in a water bath. After stirring for 1 hour, 10 g of xylene in which 0.2 g of the polymerization initiator azobisisobutyronitrile was dissolved
Was added dropwise while substituting with nitrogen again, and the temperature of the reaction vessel was maintained at 70 ° C. in a water bath. After stirring for 5 hours, polymer d was obtained.
The weight average molecular weight of the obtained polymer d is 25 in GPC.
It was 0000. Table 1 shows the results.

Polymers e to f Polymers e to f were prepared in the same manner as the polymer d except that the compound 4 or 1 was used in place of the compound 2 and the polymerization ratios shown in Table 1 were used.
I got Without using the compound of the present invention as a comparative example,
I made a polymer.

Polymers g to h Polymers e to f were obtained in the same manner as the polymer d except that the compounds of the synthesis examples were not used and the polymerization ratios shown in Table 1 were used.

(Test of Compounds for Marine Biocide Ability) The Ambo stage larvae of Mytilus edulis were collected by plankton net, and the bactericidal efficacy of each compound against them was tested by the following procedure. That is, petri dish (caliber 90 mm x height 15 m
m) was added with 30 ml of filtered seawater to which the test solution was added so as to have the predetermined concentration shown in Table 2. An instrument in which Mueller Gauze NXXX-25 was attached to one side of a thick glass tube (diameter 60 mm x height 15 mm) was put therein. Next, ten Ambo stage larvae of mussels were placed.
After leaving this petri dish in a constant temperature bath of 22 ± 1 ° C for 6 hours, it was replaced with filtered seawater and left in the constant temperature bath for 24 hours, and then swimming larvae were counted under a microscope to determine the efficacy of the test solution. did. Table 2 shows the results. In the table, when the number of swimming larvae is 0, it means that all the larvae are dead.

[0052]

[Table 2]

The test solution was prepared by mixing 5 parts of the compound with 90 parts of methanol and nonionic surfactant (manufactured by Sanyo Chemical Industry Co., Ltd.,
Ionette T-80) was formulated into 5 parts and diluted with filtered sea water to prepare a test solution.

(Test for preventing adhesion of marine organisms to polymers) The ability to prevent adhesion of marine organisms to each polymer was tested by the following procedure.
That is, the test net is made of polyethylene (100 pieces, 4 sections, 4
A 0 cm x 60 cm) aquaculture net was used. The test net was dipped in a blended composition containing a polymer, the polymer was attached to the net and air dried for 3 days. And 3 from May to July
For a month, it was hung at a depth of 1.0 to 1.5 m below the sea level from a raft in a natural bay (test site: Hozaura Bay, Mie Prefecture), and the ability to prevent adhesion to maggots and other adherent organisms was observed after 3 months. Table 3 shows the blending ratio of the blended composition, and Table 4 shows the test results. Table 4 shows the adhered area ratio (%) of each adherent organism and the weight (wet weight) of all adherent organisms.

[0055]

[Table 3]

[0056]

[Table 4]

(Test for preventing marine organisms from adhering to paint) The ability of the paint to prevent marine organisms from adhering was tested by the following procedure. That is,
A hard PVC plate (7 cm × 20 cm) was used as a test plate. A paint formulated into a paint form at a predetermined mixing ratio shown in Table 5 was applied twice to the test plate so that the applied amount was 1.5 to 2.0 kg / m ² . From May, one year below the sea level from the raft in the natural bay (test site: Hozaura Bay, Mie Prefecture).
Suspended at a depth of 5 to 2.0 m, the ability to prevent adherence to barnacles and magnolias attached organisms after 6 months and 12
Observed after a month. Table 5 shows examples of paint formulations, and Table 6 shows the test results. Table 6 shows the adhered area ratio (%) of all adherent organisms and the adhered area ratio (%) of each adherent organism to the test plate.

[0058]

[Table 5]

[0059]

[Table 6]

[0060]

INDUSTRIAL APPLICABILITY The β- (meth) acryloyloxy-alkylamine derivative, its polymer, and its copolymer of the present invention can prevent marine adherent organisms from adhering to fishing nets, ship bottoms, seawater intake channel walls and the like. It is possible to provide a stable agent for preventing adhesion of marine organisms over a period of time, and it is possible to extremely efficiently prevent damage due to organisms adhering to marine organisms for use as an anti-adhesion agent for fishing nets and as an anti-adhesion paint.

Claims (7)

[Claims] 1. A compound of the general formula (I): [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and when R ¹ is a hydrogen atom, R ² is-[(C
H ₂ ) _n NH] _m H (n is an integer of 1 to 4 and m is an integer of 1 to 5), and when R ¹ is a lower alkyl group having 1 to 4 carbons, R ² has 1 to 4 carbons. A lower alkyl group, R ³ Is an alkyl group having 8 to 28 carbon atoms, R ⁴ Represents a hydrogen atom or a methyl group], and is a β- (meth) acryloyloxy-alkylamine derivative. 2. N, N-Dimethyl-β-methacryloyloxy-alkyl (dodecyl = 55%, tetradecyl = 4
5%) amine, N, N-dimethyl-β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) amine, N, N-dimethyl-β-acryloyloxy-alkyl (dodecyl = 55%, tetradecyl 4
5%) amine, N, N-diethyl-β-methacryloyloxy-alkyl (hexadecyl 57%, octadecyl =
43%) amine and β-methacryloyloxy-alkyl (hexadecyl = 57%, octadecyl = 43%) ethylenediamine, at least one derivative being selected. 3. A polymer of the derivative according to claim 1, which has a weight average molecular weight (gel permeation chromatography analysis using polystyrene as a standard) of 10,000 to 1,000,000.
Polymer that is 0. 4. A copolymer of the derivative according to claim 1 and an ethylenically unsaturated monomer, having a weight average molecular weight (gel permeation chromatography analysis using polystyrene as a standard) of 1.
Copolymerization product of 10,000 to 1,000,000. 5. The copolymer according to claim 4, wherein the ethylenically unsaturated monomer is at least one selected from (meth) acrylic acid and its esters, and styrene. 6. A marine organism adhesion preventive agent comprising the derivative according to claim 1 or 2, the polymer according to claim 3 or the copolymer according to claim 4 as an active ingredient. 7. The agent for preventing adhesion of marine organisms according to claim 6, which is formulated in a coating form.