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

Patent metadata

Field	Value
Publication number	US-11512158-B2
Application number	US-201816605112-A
Country	US
Kind code	B2
Filing date	Mar 29, 2018
Priority date	Apr 14, 2017
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

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.

First claim

The invention claimed is:

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):

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:

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:

where R 1 represents H or CH 3 , and R 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:

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 3 , where R 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 4 , where R 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

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 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 2 -containing acrylate is

where R 2 is the same as R 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 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 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 methacryl

Assignees

• Univ South China Tech

Inventors

• Zhang Guangzhao
• Ma Chunfeng
• Xie Qianni

Classifications

• C09D5/1662

  Synthetic film-forming substance · CPC title

• C08F220/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F220/365

  containing further carboxylic moieties · CPC title

• C09D133/14

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title

• C08G63/688

  containing sulfur · CPC title