KR950011502B1 - Hydrolysis monomer for antifoulling paint and producing metho thereof - Google Patents

Abstract

The hydrolyzable monomer of formula (I) for an antipollutive paint binder is prepared. In (I), R and R' are -H, -CH3 of Cl respectively; M is at least 2 valent metal of IIA-VIIA, IB-VB of VIII group; n is metal ion number; Y is (a); Q1 and Q2 are -C6H5, -CN or NO2 respectively; R1-R8 is H or C1-20 linear or branched alkyl; X and X' are -CO-, -SO2- or -SOC6H4- respectively. The binder for the antipollutive paint is prepd. by (co) polymerizing the monomer and/or a radical reactive monomer with a radical initiator i.e. benzoyl peroxide or azobisisobutyronitrile in the presence of a solvent i.e. xylene, toluene, butylacetate, methylethyl ketone or n-butanol at 50-120 deg.C. The radical monomer is pref. methyl acrylate, methyl methacrylate, styrene, vinylacetate, vinylchloride, etc.

Description

Hydrolyzable monomer for antifouling paint binder, preparation method thereof, and method for preparing binder for antifouling paint using this monomer

1 is a stainless specimen to be coated with an antifouling paint binder.

2 is a simple rotatester for measuring the wear rate of the antifouling paint binder.

* Explanation of symbols for main parts of the drawings

1: motor 2: tank

3: specimen support 4: stainless specimen

5: seawater

The present invention relates to a hydrolyzable monomer for an antifouling paint binder, a method for preparing the same, and a binder for an antifouling paint using the monomer for preventing aquatic contaminants adhered to surfaces of ships, boats, and marine structures.

Recently, as the most frequently used type of hydrolysis, self-polishing type binders containing hydrolyzable leaving bodies such as those described in British Patent No. 1447590 and the like are used. This binder is a polyorganic polymer pendant triorganotin compound, and the surface layer is easily hydrolyzed in seawater to elute the triorganotin compound, and the remaining part is dispersed and solubilized in the seawater to fall off. It has an iterative mechanism that protrudes.

The biggest advantage of such a binder is that the surface roughness is lower than that at the time of coating, and thus it is possible to use it over a long period of time by having the maximum fuel economy as well as uniform wear property.

However, the binder has been required to develop a new non-toxic or low-toxic self-polishing binder by accelerating marine pollution due to the high cost and excessive toxicity.

SUMMARY OF THE INVENTION The present invention has been completed to solve these problems, and has an object of the present invention to provide a novel hydrolytic monomer for self-polishing type binders, which is suitable for use in antifouling paints and has low toxicity. Another object is to provide a method for producing the hydrolyzable monomer, and another object is to provide a method for producing a novel antifouling paint binder using the monomer.

The hydrolyzable monomer of the present invention for achieving the above object is represented by the following general formula (I). Hereinafter, the monomer is referred to as hydrolyzable monomer D.

In formula (I), R and R 'are the same, -H, -CH ₃ or -Cl, M is IB, II A, II B, III A, III B, IV A, IV B, VA, on the periodic table VB, VI A, VII A, VIII is one of the divalent or higher metals, n is the corresponding metal ion number, and Y is Q ¹ and Q ² are the same or different, -C ₆ H ₅ , -CN or -NO ₂ , R ¹ to R ¹⁰ are the same or different, hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, X is or And X 'is or ego,

R ¹¹ to R ¹⁴ are the same or different and are hydrogen or a linear or branched alkyl group of 1 to 10 carbon atoms, and Z ¹ and Z ² are the same or different and are linear or branched alkyl groups of 1 to 6 carbon atoms.

These hydrolyzable monomers D are easily hydrolyzed by seawater, and are easier to manufacture than the conventional triorganotin-type unsaturated monomers to which an alkyl group is directly added to the metal, various metals can be selected, and binder toxicity can be easily controlled. There is an advantage.

As another object of the present invention, a method for producing the hydrolyzable monomer comprises one mole (n equivalent; n is the number of ions of the metal) of the polyvalent metal or polyvalent metal oxide containing an anion group represented by the following general formula (III). To a metal-containing ester (B) represented by the following formula (IV) prepared by esterification using n equivalents of an unsaturated monomer (A) containing an organic acid, an inorganic acid or a salt thereof represented by the following general formula (II) The nucleophilic monomer (C) represented by the following general formula (V) is n-1 equivalent Michael addition reaction, and it is comprised from preparing the hydrolysable monomer (D) represented by the said general formula (I).

In the formula (II), R and X are the same as the general formula (I), Z is -OH, -ONa, -OK, -OLi or -CI,

In the formula (III), M and n are the same as the general formula (I), and A is -OH, -CN, -SCN, -NO ₃ , -F, -CI, -Br, -I or -O and m Is the ionized water of A.

In the formula (IV), R, M, X and n are R ¹ to R ¹⁰ are the same as the general formula (I).

In Formula (V), Q ¹ , Q ² and R ¹ to R ¹⁰ are the same as those of General Formula (I).

Specific examples of the unsaturated monomer (A) that can be represented by the general formula (II) include acrylic acid, methacrylic acid, 2-chloroacrylic acid, acryloyl chloride, methacryloyl chloride, vinyl sulfonic acid Sodium salt, p-styrene sulfonic acid sodium salt, vinyl phosphoric monoexoxide, acrylic acid sodium salt, methacrylic acid sodium salt, 2-acrylamide 2-methylpropanesulfonic acid, and the like. It does not limit the scope of.

Specific examples of the polyvalent metal or polyvalent metal oxide containing an anion group which can be represented by the general formula (III) according to the present invention include calcium hydroxide, calcium chloride, magnesium hydroxide, magnesium chloride, aluminum chloride, aluminum Hydroxide, aluminum nitrate, kappa hydroxide, capacyanate, carpacciocyanate, zinc hydroxide, zinc chloride, zinc thiocyanate, zinc cyanate, tetrachloro titanate, tetrachlorosilane, strontium hydride There are a lockside, germanium hydroxide, nickel chloride, calcium oxide, magnesium oxide, kappa (II) oxide, zinc oxide and the like, these examples do not limit the scope of the present invention.

The metal-containing ester (B) represented by the general formula (IV) is 1 mol of a polyvalent metal or polyvalent metal oxide containing an anion group represented by the general formula (III) (n equivalent: n is the number of ions of the metal) N) an equivalent amount of the unsaturated monomer (A) containing an organic acid, an inorganic acid or a salt thereof is esterified, and distilled water or organic solvents such as xylene, n-butanol, methyl isobutyl ketone, and ethyl acetate are used. It is obtained by making it react at -150 degreeC. At this time, if the reaction temperature is too high, such as 150 ℃ or more severe damage to the double bond, it is preferable to use 0.1 to 0.5 parts by weight of a polymerization inhibitor such as hydroquinone based on 100 parts by weight of unsaturated monomer to prevent this. When the anionic group uses a polyvalent metal other than a hydroxyl group, when the unsaturated monomer (A) is subjected to the metathesis method of a salt with an alkali of an IA group on the periodic table such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, You can easily proceed with the reaction.

When the reaction is represented by the reaction scheme, it is the same as Scheme 1.

The group description in the above scheme is as described.

The nucleophilic monomer (C) which may be represented by the general formula (V) according to the present invention is used for the purpose of controlling the hydrolysis rate of the hydrolyzable monomer (D) and improving solubility. Butylamine, diisopropylamine, dioctylamine, diamylamine, butylmercaptan, octylmercaptan, amylmercaptan, diethylmalonate, dibutylmalonate, dioctylmalonate, ethyl acetoacetate, diethyl force Pit, dibutyl phosphite, dioctyl phosphite, dibutyl phosphate monoexoxide, dioctyl phosphate monoexoxide, octyl octyl phosphonate monoexoxide, and the like, but these examples do not limit the scope of the present invention.

The nucleophilic monomer (D) according to the present invention is a carbon-carbon double bond of a metal-containing ester (B) capable of reacting with 1 mole (n equivalent: nucleophilic monomer (C) of the metal-containing ester (B). Equivalents) to the nucleophilic monomer (C) by n-1 equivalent Michael addition (MICHAEL ADDITIOH), wherein an aromatic solvent such as benzene, toluene, and xylene, an acetate solvent such as ethyl acetate, butyl acetate or chloroform, Halogenated hydrocarbon solvents such as carbon tetrachloride can also be used. When Michael adds the nucleophilic monomer (C) to the metal-containing ester (B), the reaction temperature is suitably 20 ° C to 150 ° C, and preferably 30 ° C to 120 ° C. In addition, in order to prevent excessive damage of the double bond in the metal-containing ester (B), it is preferable to use a polymerization inhibitor such as hydroquinone in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the metal-containing ester (B). In particular, when a malonate system is used as the nucleophilic monomer (C), it is effective to add a small amount of amine as a catalyst.

When reaction which Michael adds the said nucleophilic monomer (C) to said metal containing ester (B) is represented by Reaction Formula, it is the same as Reaction Formula 2.

The description in Scheme 2 is as described above.

Another object of the present invention is a method for producing a binder for an antifouling paint according to the present invention, consisting of homopolymerizing the hydrolyzable monomer (D) or copolymerizing a known radical reactive monomer.

The hydrolyzable monomer (D) according to the present invention is benzoyl peroxide and azobisiso under solvents such as xylene, toluene, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and n-butanol to form a film forming polymer (E). It is polymerized at 50-120 degreeC by a well-known solution polymerization method using radical initiators, such as butyronitrile.

At this time, the film forming polymer (E) is prepared as a homopolymer using a hydrolyzable monomer (D) alone or as a copolymer using a comonomer.

The comonomer is a known radical reactive unsaturated monomer, which is used for the purpose of granting flexibility, solubility control, and self-polishing property of a film. Specific examples of such radical reactive unsaturated monomers include methyl acrylate, cetyl methacrylate, and butyl acryl. Butyl methacrylate, styrene, lauryl methacrylate, acrylonitrile, vinyl acetate, vinyl chloride, phenyl methacrylate, cyclohexyl acrylate, N, N'-dimethylaminoethyl methacrylate, 2 -Ethylhexyl acrylate, 2-hydroxy ethyl cetacrylate, and the like, and these examples do not limit the scope of the present invention. In the preparation of the film-forming polymer (E), the content of the hydrolyzable monomer (D) is preferably used at least 20 parts by weight or more based on 100 parts by weight of the polymer, and less than 20 parts by weight of the self-polishing property occurs. .

The film-forming polymer (E) may provide an antifouling coating having excellent antifouling performance as the polymer itself, but it is also preferable to use an antifouling paint composition (F) by mixing known antifouling agents and additives.

For example, the present invention will be described in more detail with reference to Preparation Examples and Examples.

[Production example of metal-containing ester (B): B-1 (Zinc Diacrylate)]

81 parts by weight of zinc oxide, 100 parts by weight of toluene and 0.2 parts by weight of hydroquinone were added to a 114-neck flask and heated to 100 ° C. 173 parts by weight of acrylic acid was uniformly added dropwise over 2 hours to produce zinc diacrylate. The excess acrylic acid is then removed by distillation under reduced pressure, cooled to room temperature, filtered and dried.

165 parts by weight of white zinc diacrylate was obtained. Yield 80%.

IR; 1463, 1573, 1522.5, 1434.4, 1371.5, 1273.9, 1068.7, 978.2, 831.5, 689.8

[Production example of metal-containing ester (B): B-2 (Zinc Dimrethacrylate)]

136 parts of zinc chromide and 300 parts by weight of distilled water were added to a 114-neck flask and dissolved well. 237 parts by weight of sodium methacrylate is dissolved in 300 parts by weight of distilled water, and the solution is added dropwise to the zinc chloride solution over 2 hours. Subsequently, the mixture was stirred for further 1 hour, filtered and dried to obtain 170 parts by weight of white zinc dimethacrylate. Yield 75%.

IR; 2958.8, 1648, 1568, 1456.3, 1410.8, 1390, 1369, 1236, 1006, 934, 833, 666.7, 622.7.

[Production Example of Hydrolyzable Monomer (D): D-1]

41.4 parts by weight of zinc diacrylate, 55.8 parts by weight of toluene and 0.3 parts by weight of hydroquinone are added to a 114-neck flask, and heated to 80 ° C while adding nitrogen. A mixed solution of 28.4 parts by weight of dibutylamine and 14 parts by weight of toluene is added dropwise to the zinc diacrylate solution over 1 hour. When the solution became clear, it heated up at 100 degreeC, stirred for 1 hour, and toluene was removed by distillation under reduced pressure, and 65.7 weight part of yellow hydrolyzable monomer D-1 with a very high viscosity was obtained. Yield 98%.

IR; 2959, 2931.5, 2873, 1643, 1591, 1456, 1416, 1363, 1283, 1207, 1080, 1059, 991, 953, 830, 684.

NMR (CDCL ₃ ); 6.24, 5.62, 2.82, 2.59, 2.35, 1.53, 1.33,-1.25, 0.94, 0.90.

[Production Example of Hydrolyzable Monomer (D): D-2]

Except for using 28.4 parts by weight of diisobutylamine instead of dibutylamine in Preparation Example D-1, 63.0 (yield 94%) parts by weight of high-viscosity yellow hydrolyzable monomer D-2 was obtained.

[Example of Preparation of Hydrolyzable Monomer (D): D-3]

Except that 53.0 parts by weight of diethylhexylamine was used instead of dibutylamine in Preparation Example D-1, 87.8 parts (yield 98%) parts of high viscosity yellow hydrolyzable monomer D-3 was obtained.

[Production Example of Hydrolyzable Monomer (D): D-4]

Except for using 47.0 parts by weight of zinc dimethacrylate instead of zinc diacrylate in Preparation Example D-1 to obtain 71.3 parts by weight (yield 94%) of a semi-solid yellow hydrolyzable monomer D-4.

[Example of Preparation of Hydrolyzable Monomer (D): D-5]

47 parts by weight of zinc dimethacrylate, 94 parts by weight of toluene and 0.3 parts by weight of hydroquinone were added to a 114-neck flask, and heated to 50 ° C while adding nitrogen. A mixture of 35 parts by weight of ethyl acetoacetate, 35 parts by weight of toluene, and 1 part by weight of triethylamine was added dropwise to the zinc dimethacrylate solution over 2 hours and reacted for 2 hours. When the solution became clear, the temperature was raised to 80 ° C. for 1 hour. After stirring, toluene was removed by distillation under reduced pressure to obtain 66.4 parts by weight of semisolid yellow hydrolyzable monomer (D-5). Yield 98%.

IR; 2985.4, 2917.2, 2847, 1736.6, 1714.7, 1643, 1577.6, 1559, 1541, 1435.7, 1367, 1272.5, 1153.5, 989.1, 831.2, 668.7.

NMR (CDCl ₃ ); 6.33, 6.29, 6.19, 6.17, 6.13, 5.70, 5.67, 4.16, 4.15, 3.19-3.90, 2.32, 2.23, 2.10, 1.30-1.23

[Production Example of Hydrolyzable Monomer (D): D-6]

The same procedure was followed as in Production Example D-5 except that 23.0 parts by weight of acetylacetone was used instead of ethyl acetoacetate to give 63.7 parts (95% yield) of a semi-solid yellow hydrolyzable monomer D-6.

[Production Example of Hydrolyzable Monomer (D): D-7]

47.0 parts by weight of zinc diceta acrylate, 117.0 parts by weight of toluene and 0.3 parts by weight of hydroquinone are added to a 114-neck flask, and heated to 30 ° C while adding nitrogen. 74.0 parts by weight of dioctylphosphate monoacid is added dropwise to the zinc dimethacrylate solution over 2 hours. When the solution became clear, it heated up at 80 degreeC, stirred for 1 hour, and toluene was removed by distillation under reduced pressure, and 79.9 weight part of semi-solid colorless hydrolysable monomers D-7 were obtained. Yield 90%.

IR; 2950, 2875, 2680, 1650, 1596, 1575, 1461, 1425, 1378, 1247, 1189.9, 1099, 1034, 985, 885, 830, 619, 527.8, 490.

NMR (CDCL ₃ ); 6.48, 6.43, 6.20, 6.17, 6.14, 5.80, 3.85, 1.70, 1.65, 1.49, 1.45-1.30, 0.95-0.80.

[Example of Preparation of Hydrolyzable Monomer (D): D-8]

Except for using 67.32 parts by weight of dioctyl phosphonate mono-exchange instead of dioctylphosphate monoexoxide in Preparation Example D-7 was obtained 99.5 parts by weight (yield 92%) of a high viscosity colorless transparent hydrolyzable monomer.

[Example of Preparation of Hydrolyzable Monomer (D): D-9]

The preparation was carried out in the same manner as in Example D-8, except that 96.2 parts by weight of didecyl phosphate monoacid was used instead of dioctylphosphate monoexoxide to obtain 101.6 parts by weight (yield 84%) of a high viscosity colorless and transparent hydrolyzable monomer.

[Example of Preparation of Hydrolyzable Monomer (D): D-10]

Except for using 46.2 parts by weight of dioctyl phosphate monoacid instead of dioctylphosphate monoacid in Preparation Example D-8 82.7 parts by weight (yield 93%) of a high viscosity colorless transparent hydrolyzable monomer.

[Example of Preparation of Hydrolyzable Monomer (D): D-11]

Except for using 41.4 parts by weight of zinc diacrylate instead of zinc dimethacrylate in Preparation Example D-5, 97.3 parts by weight (yield 92%) of a highly viscous colorless transparent hydrolyzable monomer was obtained.

[Example of Preparation of Hydrolyzable Monomer (D): D-12]

Except for using the dibutyl phosphite 42.7 parts by weight of dibutyl phosphite and 0.5 parts by weight of sodium methoxide in Preparation Example D-8, 66.0 parts by weight (yield 77%) was obtained.

[Preparation liquid of film forming polymer liquid (E): E-1]

75 parts by weight of xylene and 75 parts by weight of methyl isobutyl ketone are respectively added to a four-necked flask, and the temperature is raised to 80 ° C. while injecting nitrogen. A mixed solution of 60 parts by weight of hydrolyzable monomer D-1, 16 parts by weight of methyl methacrylate, 24 parts by weight of butyl acrylate, and 0.75 parts by weight of azobis isobutyronitrile was added dropwise uniformly over 5 periods, and then maintained for 1 hour. After the reaction, the mixture was heated up and held at 100 ° C. for 30 minutes, and then cooled to room temperature to prepare a film type polymer liquid E-1.

[Production liquid of film forming polymer liquid (E): E-2 to E-9]

75 parts by weight of xylene and 75 parts by weight of methyl isobutyl ketone are respectively added to a four-necked flask, and the temperature is raised to 80 ° C. while injecting nitrogen.

The mixture of the monomers and the azobis isobutyronitrile 0.75 parts by weight of the component ratios shown in Table 1 was added dropwise uniformly over 5 hours, and then reacted for 1 hour. After heating, the mixture was kept at 100 ° C for 30 minutes and cooled to room temperature. Film-type polymer liquids E-2-E-9 are manufactured.

TABLE 1

Seawater abrasion test of the film-forming polymer E1-E9 and the conventional TIN-containing antifouling paint (Tin-containing resin) prepared by the above method was carried out. The seawater abrasion test was performed by spray coating a 20 x 100 x 0.2 mm stainless steel specimen, such as film 1, with a film-forming polymer solution E1-E9 and a tin-containing resin, followed by drying for 3 days at room temperature. After the abrasion test for a certain period of time, the specimens were collected and dried, and the weight loss was measured to compare and evaluate the abrasion.The results are shown in Table 2. Collected from.)

TABLE 2

Claims (15)

Next, the hydrolyzable monomer for antifouling paint binder represented by the following general formula (I). In formula (I), R and R 'are the same, -H, -CH ₃ or -Cl, M is IB, IIA, IIB, IIIA, IIIB, IV A, IV B, VA, VB, VI A on the periodic table , VII A, VIII is one of the divalent or more metals, n is the number of metal ions of interest, Y is Q ¹ and Q ² are the same or different, -C ₆ H ₅ , -CN or NO ₂ , R ¹ to R ¹⁰ are the same or different, are hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, X is or And X 'is or ego, R ¹¹ to R ¹⁴ are the same or different and are hydrogen or a linear or branched alkyl group of 1 to 10 carbon atoms, Z ¹ and Z ² are the same or different and are linear or branched alkyl groups of 1 to 6 carbon atoms 1 mole (n equivalent; n is the number of ions of the metal) of the polyvalent metal or polyvalent metal oxide containing an anion group represented by the following general formula (III), an organic acid, an inorganic acid or a salt thereof represented by the following general formula (II) N-1 equivalent Michael addition reaction of a nucleophilic monomer represented by the following general formula (V) to a metal-containing ester represented by the following formula (IV) prepared by esterification using n equivalents of an unsaturated monomer containing The manufacturing method of the hydrolysable monomer for antifouling paint binder represented by following General formula (I) characterized by the above-mentioned. In formula (I), R and R 'are the same, -H, -CH ₃ or -Cl, M is IB, IIA, IIB, IIIA, IIIB, IV A, IV B, VA, VB, VI A on the periodic table , VII A, VIII is one of the divalent or more metals, n is the number of metal ions of interest, Y is Q ¹ and Q ² are the same or different, -C ₆ H ₅ , -CN or -NO ₂ , R ¹ to R ¹⁰ are the same or different, hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, X is or And X 'is or ego, R ¹¹ to R ¹⁴ are the same or different and are hydrogen or a linear or branched alkyl group of 1 to 10 carbon atoms, and Z ¹ and Z ² are the same or different and are linear or branched alkyl groups of 1 to 6 carbon atoms. In the formula (II), R and X are the same as the general formula (I), Z is -OH, -ONa, -OK, OLi or -Cl, In Formula (III), M and n are the same as those of Formula (I), and A is -OH, -CN, -SCN, -NO ₃ , -F, -Cl, -Br, -I, -O and m Is the ionized water of A. R, M, X in Formula (IV) And n Is the same as the general formula (I). In Formula (V), Q ¹ , Q ² and R ¹ to R ¹⁰ are the same as those of General Formula (I). The method of claim 2, wherein the unsaturated monomer is acrylic acid, methacrylic acid, 2-chloroacrylic acid, acryloyl chloride, methacryloyl chloride, vinyl sulfonic acid sodium salt, p-styrene sulfonic acid sodium A method for producing a hydrolyzable monomer, characterized in that the salt, vinyl phosphonate monoacid, acrylic acid sodium salt, methacrylic acid sodium salt or 2-acrylamido 2-methylpropanesulfonic acid. 3. The polyvalent metal or polyvalent metal oxide containing an anion group represented by the general formula (III) is calcium hydroxide, calcium chloride, magnesium hydroxide, magnesium chloride, aluminum chloride, aluminum hydroxide. , Aluminum nitrate, kappa hydroxide, capacyanate, carpacciocyanate, zinc hydroxide, zinc chloride, zinc thiocyanate, zinc cyanate, tetrachlorotyranate, tetrachlorosilane, strontum hydroxide Said, germanium hydroxide, nickel chloride, calcium oxide, magnesium oxide, kappa (II) oxide or zinc oxide method for producing a hydrolyzable monomer, characterized in that. The method of claim 2, wherein when the unsaturated monomer is esterified using n equivalents, the reaction is carried out at 10 to 150 ° C using distilled water or organic solvents such as xylene, n-butanol, methyl isobutyl ketone, and ethyl acetate. A method for producing a hydrolyzable monomer. The method according to claim 2, characterized in that 0.1 to 0.5 parts by weight of a polymerization inhibitor such as hydroquinone is used with respect to 100 parts by weight of the unsaturated monomer when esterifying using n equivalents of the unsaturated monomer and / or Michael addition. Method for producing a hydrolyzable monomer. The method of claim 2, wherein when the anionic group uses a polyvalent metal other than a hydroxyl group, the unsaturated monomer is subjected to the metathesis method of a salt with an alkali of an IA group on the periodic table such as lithium hydroxide, sodium hydroxide, or potassium hydroxide. Method for producing a hydrolyzable monomer, characterized in that applied. The nucleophilic monomer (C) which can be represented by the general formula (V) is dibutylamine, diisopropylamine, dioctylamine, diamylamine, butyl mercaptan, octyl mercaptan, amyl. Mercaptan, diethylmalonate, dibutylmalonate, dioctyl malonate, ethyl acetoacetate, diethyl phosphite, dibutyl phosphite, dioctyl phosphite, dibutyl phosphate monoexide, dioctyl phosphate monoexide or octyl Octyl phosphonate mono-excited, characterized in that the method for producing a hydrolyzable monomer. The method of claim 2, wherein when the nucleophilic monomer is a malonate system, a small amount of amine is added as a catalyst. The method for preparing a hydrolyzable monomer according to claim 2, wherein an aromatic solvent, an acetate solvent or a halogenated hydrocarbon solvent is used in the Michael addition reaction. The method for preparing a hydrolyzable monomer according to claim 2, wherein the Michael addition reaction has a reaction temperature of 20 ° C to 150 ° C. A method for producing a binder for protective coating, characterized in that it consists of homopolymerizing the hydrolyzable monomer of formula (I) of claim 1 or copolymerizing a known radically reactive monomer. 13. The method according to claim 12, wherein the polymerization is carried out using a radical initiator such as benzoyl peroxide, azobisisobutyronitrile in a solvent such as xylene, toluene, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, n-butanol and the like. Method for producing a binder for protective paint, characterized in that the polymerization in a solution polymerization method at 50 ~ 120 ℃. The method of claim 12, wherein the radical reactive monomer is methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, styrene, lauryl methacrylate, acrylonitrile, vinyl acetate, vinyl chloride, phenyl meth A method for producing a binder for protective paint, characterized in that acrylate, cyclohexyl acrylate, or 2-ethylhexyl acrylate. The method of claim 12, wherein the amount of the hydrolyzable monomer (D) during the polymerization is used at least 20 parts by weight based on 100 parts by weight of the polymer.