Self-polishing zwitterionic anti-fouling resin having main chain degradability and preparation therefor and use thereof

Abstract

The present invention belongs to the technical field of marine anti-fouling materials, and discloses a self-polishing zwitterionic anti-fouling resin having a main chain degradability and the preparation therefor and the use thereof. The self-polishing zwitterionic anti-fouling resin is formed by copolymerizing the following three monomers (in the total mass of the monomers): 1% to 80% of an olefinic reactive monomer, 1% to 80% of a cycloketene acetal monomer, and 1% to 80% of a betaine type precursor. The anti-fouling resin has a main chain degradability and a side chain hydrolyzability, and the transition of a coating from being hydrophobic to being hydrophilic is achieved by the hydrolysis of a surface to produce a super-hydrophilic zwitterionic surface, in order to further enhance the anti-fouling ability of the system. The material not only overcomes the disadvantages of poor mechanical properties and poor solubility in an organic solvent of a zwitterionic material, but can also effectively control the long-term stable release of an anti-fouling agent, so as to achieve a synergistic anti-fouling effect of the anti-fouling agent and an anti-protein. The method of the present invention is simple, has a relatively low cost, and is suitable for industrial production. The material is used in the field of marine anti-fouling coatings.

Claims

1. A self-polishing zwitterionic anti-fouling resin having a main chain degradability, characterized in that: the resin is formed by copolymerizing the following three monomers (in the total mass of monomers): TABLE-US-00001 an olefinic reactive monomer 1% to 80% a cycloketene acetal monomer 1% to 80% a betaine type precursor 1% to 80% the cycloketene acetal monomer has one or more of the structural formulas 1 to 25: ##STR00016## ##STR00017## ##STR00018## ##STR00019## where m is an integer from 1 to 12; the olefinic reactive monomer is one or more of acrylate monomers, methacrylate monomers, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylol acrylamide, isopropyl acrylamide, styrene, vinyl pyrrolidone, and 4-vinylpyridine; the structural formula of the betaine type precursor is as follows: ##STR00020## where R.sub.1 represents H or CH.sub.3, and R.sub.2 represents an alkyl group having 2 to 10 carbon atoms, an organic anti-fouling group, a copper-containing group, a zinc-containing group, or a silicon-containing group.

2. The self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 1, characterized in that: the methacrylate monomers are one or more of methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, stearic methacrylate, polyethylene glycol methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; and the acrylate monomers are one or more of methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, isooctyl acrylate, dodecyl acrylate, stearic acrylate, and hydroxyethyl acrylate.

3. The self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 1, characterized in that: the organic anti-fouling a group has one of structural formulas 26 to 31, where “*” represents a junction: ##STR00021##

4. The self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 1, characterized in that: the structure of the zinc-containing group is *—Zn—O—C(O)—R.sub.3, where R.sub.3 is a benzene ring, or a saturated or unsaturated alkyl chain containing 1 to 10 carbon atoms, or a saturated or unsaturated cycloalkyl group, “*” represents a junction, and —O—C(O)— represents an ester group; the structure of the copper-containing group is *—Cu—O—C(O)—R.sub.4, where R.sub.4 is a benzene ring, or a saturated or unsaturated alkyl chain containing 1 to 10 carbon atoms, or a saturated or unsaturated cycloalkyl group, “*” represents a junction, and —O—C(O)— represents an ester group; and the structural formula of the silicon-containing group is ##STR00022## where C represents an alkyl group having 3 or 4 carbon atoms, and “*” represents a joint.

5. A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 1, characterized in that: the method comprises the following steps: (1) preparation of the betaine type precursor: the R.sub.2-containing acrylate and 2-(methylamino)ethanol are subjected to an addition reaction at 0° C. to 50° C. to obtain an addition product; the addition product is acylated with (meth)acryloyl chloride at 0° C. to 30° C. to obtain a betaine type precursor; wherein the (meth)acryloyl chloride means methacryloyl chloride or acryloyl chloride; the structural formula of the R.sub.2-containing acrylate is ##STR00023## where R.sub.2 is the same as R.sub.2 in the structural formula of the betaine type precursor of claim 1; (2) preparation of the anti-fouling resin: under anaerobic conditions, with an organic solvent as a medium, the olefinic reactive monomer, the cycloketene acetal monomer and the betaine type precursor are reacted at 60° C. to 150° C. for 24-48 h under the action of an initiator, and separation is performed to obtain a self-polishing zwitterionic anti-fouling resin.

6. The preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 5, characterized in that: the molar ratio of the R.sub.2-containing acrylate to 2-(methylamino)ethanol to (meth)acryloyl chloride in the step (1) is 1:(1 to 1.5):(1 to 2).

7. The preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 5, characterized in that: in the step (1), the addition reaction time is 6-12 h, and the acylation reaction time is 6-12 h.

8. The preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 5, characterized in that: the organic solvent in the step (2) is one or more of tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, n-butanol, toluene, and xylene; and the initiator in the step (2) is azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide or t-butyl hydroperoxide.

9. The preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 5, characterized in that: in the step (2), the initiator is used in an amount of 0.1% to 5% in the total mass of the olefinic reactive monomer, the cycloketene acetal monomer and the betaine type precursor.

10. A method for preventing fouling of a marine structure comprising applying the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 1 to at least one surface of the structure.

11. A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 2, characterized in that: the method comprises the following steps: (1) preparation of the betaine type precursor: the R.sub.2-containing acrylate and 2-(methylamino)ethanol are subjected to an addition reaction at 0° C. to 50° C. to obtain an addition product; the addition product is acylated with (meth)acryloyl chloride at 0° C. to 30° C. to obtain a betaine type precursor; wherein the (meth)acryloyl chloride means methacryloyl chloride or acryloyl chloride; the structural formula of the R.sub.2-containing acrylate is ##STR00024## where R.sub.2 is the same as R.sub.2 in the structural formula of the betaine type precursor of claim 1; (2) preparation of the anti-fouling resin: under anaerobic conditions, with an organic solvent as a medium, the olefinic reactive monomer, the cycloketene acetal monomer and the betaine type precursor are reacted at 60° C. to 150° C. for 24-48 h under the action of an initiator, and separation is performed to obtain a self-polishing zwitterionic anti-fouling resin.

12. A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 3, characterized in that: the method comprises the following steps: (1) preparation of the betaine type precursor: the R.sub.2-containing acrylate and 2-(methylamino)ethanol are subjected to an addition reaction at 0° C. to 50° C. to obtain an addition product; the addition product is acylated with (meth)acryloyl chloride at 0° C. to 30° C. to obtain a betaine type precursor; wherein the (meth)acryloyl chloride means methacryloyl chloride or acryloy chloride; the structural formula of the R.sub.2-containing acrylate is ##STR00025## where R.sub.2 is the same as R.sub.2 in the structural formula of the betaine type precursor of claim 1; (2) preparation of the anti-fouling resin: under anaerobic conditions, with an organic solvent as a medium, the olefinic reactive monomer, the cycloketene acetal monomer and the betaine type precursor are reacted at 60° C. to 150° C. for 24-48 h under the action of an initiator, and separation is performed to obtain a self-polishing zwitterionic anti-fouling resin.

13. A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 4, characterized in that: the method comprises the following steps: (1) preparation of the betaine type precursor: the R.sub.2-containing acrylate and 2-(methylamino)ethanol are subjected to an addition reaction at 0° C. to 50° C. to obtain an addition product; the addition product is acylated with (meth)acryloyl chloride at 0° C. to 30° C. to obtain a betaine type precursor; wherein the (meth)acryloyl chloride means methacryloyl chloride or acryloyl chloride; the structural formula of the R.sub.2-containing acrylate is ##STR00026## where R.sub.2 is the same as R.sub.2 in the structural formula of the betaine type precursor of claim 1; (2) preparation of the anti-fouling resin: under anaerobic conditions, with an organic solvent as a medium, the olefinic reactive monomer, the cycloketene acetal monomer and the betaine type precursor are reacted at 60° C. to 150° C. for 24-48 h under the action of an initiator, and separation is performed to obtain a self-polishing zwitterionic anti-fouling resin.

14. A method for preventing fouling of a marine structure comprising applying the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 2 to at least one surface of the structure.

15. A method for preventing fouling of a marine structure comprising applying the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 3 to at least one surface of the structure.

16. A method for preventing fouling of a marine structure comprising applying the self-polishing zwitterionic anti-fouling resin having the main chain degradability according to claim 4 to at least one surface of the structure.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The present invention will be further described in detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto.

Example 1

(2) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(3) (1) Preparation of the Betaine Type Precursor:

(4) ethyl acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1 at 30° C. for 6 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 0° C. for 12 h to obtain a betaine type precursor with an ethyl group as the R.sub.2 group; wherein the ratio of ethyl acrylate to acryloyl chloride was 1:1.2;

(5) (2) 20 ml of tetrahydrofuran was added to a polymerization tube, and then 5 g of methyl methacrylate, 5 g of the betaine type precursor with an ethyl group as the R.sub.2 group, 5 g of 2-methylene-1,3-dioxocycloheptane and 0.1 g of azobisisobutyronitrile were added; after oxygen was removed by passing nitrogen for 30 min, the polymerization tube was put into an oil bath at 60° C. and reacted for 24 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with n-hexane, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(6) ##STR00009##

(7) The anti-fouling resin of this example showed no adhesion of marine fouling organisms in a 6-month real sea hanging board test.

Example 2

(8) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(9) (1) Preparation of the Betaine Type Precursor:

(10) N-methylenebenzisothiazolinone acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.5 at 0° C. for 12 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 10° C. for 12 h to obtain a betaine type precursor with N-methylenebenzisothiazolinone as the R.sub.2 group; wherein the molar ratio of N-methylenebenzisothiazolinone acrylate to acryloyl chloride was 1:2;

(11) (2) 20 ml of 1,4-dioxane was added to a polymerization tube, and then 5 g of ethyl acrylate, 2.5 g of the betaine type precursor with N-methylenebenzisothiazolinone as the R.sub.2 group, 2.5 g of 2-methylene-4-methyl-1,3-dioxocyclopentane and 0.1 g of azobisisoheptanenitrile were added; after oxygen was removed by passing nitrogen for 30 min, the polymerization tube was put into an oil bath at 80° C. and reacted for 48 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with n-hexane, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(12) ##STR00010##

(13) The anti-fouling resin of this example could effectively delay the formation of microbial biofilm, and showed effective prevention of adhesion of marine fouling organisms in an 8-month real sea hanging board test.

Example 3

(14) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(15) (1) Preparation of the Betaine Type Precursor:

(16) methylene paeonol acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.2 at 30° C. for 6 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 10° C. for 12 h to obtain a betaine type precursor with methylene paeonol as the R.sub.2 group; wherein the molar ratio of methylene paeonol acrylate to acryloyl chloride was 1:1.1;

(17) (2) 20 ml of N,N-dimethylformamide was added to a polymerization tube, and then 1 g of acrylic acid, 2 g of the betaine type precursor with methylene paeonol as the R.sub.2 group, 1 g of 2-methylene-1,3-dioxo-5,6-benzocycloheptane and 0.2 g of azobisisobutyronitrile were added; after oxygen was removed by freeze pumping for three times, the polymerization tube was put into an oil bath at 70° C. and reacted for 36 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with petroleum ether, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(18) ##STR00011##

(19) The anti-fouling resin of this example had complete resistance to protein adsorption and greatly reduced the adhesion of marine bacteria, showing effective prevention of adhesion of marine fouling organisms in a 12-month real sea hanging board test.

Example 4

(20) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(21) (1) Preparation of the Betaine Type Precursor:

(22) 3-((4-hydroxy-3-methoxybenzyl)amino)-3-oxopropyl acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.3 at 50° C. for 10 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 15° C. for 12 h to obtain a betaine type precursor with N-(4-hydroxy-3-methylene)benzylpropanamide as the R.sub.2 group; wherein the molar ratio of 3-((4-hydroxy-3-methoxybenzyl)amino)-3-oxopropyl acrylate to acryloyl chloride was 1:1.8;

(23) (2) 10 ml of xylene was added to a polymerization tube, and then 1 g of styrene, 1 g of the betaine type precursor with N-(4-hydroxy-3-methylene)benzylpropanamide as the R.sub.2 group, 1 g of 2-methylene-1,3-dioxocyclohexane and 0.02 g of t-butyl hydroperoxide were added; after oxygen was removed by freeze pumping for three times, the polymerization tube was put into an oil bath at 150° C. and reacted for 24 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with ether, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(24) ##STR00012##

(25) The anti-fouling resin of this example showed effective prevention of adhesion of marine fouling organisms in a 12-month real sea hanging board test.

Example 5

(26) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(27) (1) Preparation of the Betaine Type Precursor:

(28) zinc acetate acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.2 at 40° C. for 10 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 5° C. for 10 h to obtain a betaine type precursor with zinc acetate as the R.sub.2 group; wherein the molar ratio of zinc acetate acrylate to acryloyl chloride was 1:1.5;

(29) (2) 20 ml of n-butyl alcohol was added to a polymerization tube, and then 1 g of hydroxyethyl acrylate, 1 g of the betaine type precursor with zinc acetate as the R.sub.2 group, 1 g of 2-methylene-1,3-dioxo-5-cycloheptene and 0.02 g of dibenzoyl peroxide were added; after oxygen was removed by passing nitrogen for 30 min, the polymerization tube was put into an oil bath at 80° C. and reacted for 48 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with n-hexane, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(30) ##STR00013##

(31) The anti-fouling resin of this example showed effective prevention of adhesion of marine fouling organisms in a 14-month real sea hanging board test.

Example 6

(32) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(33) (1) Preparation of the Betaine Type Precursor:

(34) triisopropylsilyl acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1 at 50° C. for 10 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 5° C. for 12 h to obtain a betaine type precursor with triisopropylsilane as the R.sub.2 group; wherein the molar ratio of triisopropylsilyl acrylate to acryloyl chloride was 1:1.5;

(35) (2) 5 ml of acetonitrile was added to a polymerization tube, and then 1.6 g of methyl acrylate, 0.4 g of the betaine type precursor with triisopropylsilane as the R.sub.2 group, 1 g of 2-methylene-5-phenyl-1,3-dioxocycloheptane and 0.02 g of azobisisobutyronitrile were added; after oxygen was removed by passing nitrogen for 30 min, the polymerization tube was put into an oil bath at 70° C. and reacted for 24 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with n-hexane, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(36) ##STR00014##

(37) The anti-fouling resin of this example showed effective prevention of adhesion of marine fouling organisms in a 14-month real sea hanging board test.

Example 7

(38) A preparation method for the self-polishing zwitterionic anti-fouling resin having the main chain degradability comprises the following steps:

(39) (1) Preparation of the Betaine Type Precursor:

(40) copper benzoate acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1 at 0° C. for 10 h to obtain an addition product; the addition product was reacted with acryloyl chloride at 5° C. for 10 h to obtain a betaine type precursor with copper benzoate as the R.sub.2 group; wherein the molar ratio of copper benzoate acrylate to acryloyl chloride was 1:1.5;

(41) (2) 20 ml of xylene was added to a polymerization tube, and then 1 g of 4-vinylpyridine, 0.5 g of the betaine type precursor with copper benzoate as the R.sub.2 group, 2 g of 2-methylene-1,3,6-trioxocyclooctane and 0.02 g of dibenzoyl peroxide were added; after oxygen was removed by passing nitrogen for 30 min, the polymerization tube was put into an oil bath at 80° C. and reacted for 24 h; after the polymerization tube was taken out, the solvent was concentrated, precipitation was performed with n-hexane, and the precipitate was dried in vacuum at 50° C. for 24 h to obtain a product of self-polishing zwitterionic anti-fouling resin; the resulting self-polishing zwitterionic anti-fouling resin has the following structure:

(42) ##STR00015##

(43) The anti-fouling resin of this example showed effective prevention of adhesion of marine fouling organisms in a 10-month real sea hanging board test.