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

Patent metadata

Field	Value
Publication number	US-2020157338-A1
Application number	US-201816605112-A
Country	US
Kind code	A1
Filing date	Mar 29, 2018
Priority date	Apr 14, 2017
Publication date	May 21, 2020
Grant date	—

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

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 Ri 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 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

• C08F226/06

  by a heterocyclic ring containing nitrogen · CPC title

• C08F220/281

  and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate · CPC title

• C08F230/04

  containing a metal · CPC title

• C08G63/688

  containing sulfur · CPC title

• C08F220/14

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