CN106977659A - Main chain degradation-type polyacrylic acid zinc resin and its method and application that after a kind of prepared by grafting method - Google Patents

Abstract

The invention belongs to the technical field of marine antifouling materials, and discloses a main chain degradable polyacrylic acid zinc resin prepared by a post-grafting method, a method and an application thereof. Zinc polyacrylate resin is mainly prepared from the following components in parts by weight: 100 parts of acrylate prepolymer, 5-50 parts of zinc-containing compound, 0-50 parts of monocarboxylic acid, and 5-150 parts of organic solvent; The parts by weight of the acrylate prepolymer are based on the total amount of reacted monomers in the acrylate prepolymer. The resin side chain zinc ester bond and the main chain polyester segment of the present invention can be hydrolyzed under the attack of seawater, which solves the dependence of traditional self-polishing materials on the speed, and can make the surface of the coating self-sufficient through hydrolysis and degradation in static seawater. Renewal, effectively control the release of antifouling agent at a constant rate, meeting the antifouling requirements of low-speed ships and offshore oil production platforms and other facilities; it has excellent drag reduction performance. The resin is used in marine antifouling coatings.

Description

A main chain degradable polyacrylic acid zinc resin prepared by a post-grafting method and its method and application

technical field

The invention belongs to the technical field of marine antifouling materials, and relates to a zinc polyacrylate resin for marine antifouling coatings, in particular to a main chain degradable zinc polyacrylate resin prepared by a post-grafting method and its method and application; The resin is used in the preparation of marine antifouling coatings.

Background technique

Marine biofouling refers to the biofouling formed by marine organisms attaching and growing on surfaces immersed in seawater. It causes immeasurable harm to marine aquaculture, transportation and marine engineering, which is directly reflected in huge economic losses. For example: marine biofouling will block the mesh of the breeding box, causing fish to die due to hypoxia and reduce production; increase the ship's weight and navigation resistance, indirectly lead to a decline in maneuverability and combat capability, and increase fuel consumption and greenhouse gas emissions ; Blocking the heat exchange pipes of nuclear power plants greatly reduces the efficiency of cold and heat exchange; it also aggravates the corrosion of steel structures of marine equipment such as oil production platforms. Therefore, solving the problem of marine pollution is of great strategic significance to my country's economy, energy, and military affairs.

Applying marine antifouling coatings is currently the most economical, convenient and commonly used method to solve the problem of marine biofouling, among which self-polishing antifouling coatings are the most widely used. Among the many components of paint, resin plays a decisive role. Parameters such as the structure, molecular weight, and acid value of the resin determine the performance and service life of the coating. Since the International Maritime Organization (IMO) decided to completely ban the production of antifouling coatings containing organotin in 2003, the self-polishing technology has been updated, and now the mainstream self-polishing technology includes polysilyl acrylate resin, zinc polyacrylate resin and polyacrylic acid Three types of copper resin. However, the existing self-polishing technology is mainly of the side chain hydrolysis type, and its performance has certain requirements on the duration and speed of the voyage. In the static stage, it is difficult to achieve the ideal self-polishing effect only by seawater washing, so the static antifouling effect is not good. Not only that, after the side chain is hydrolyzed, the main chain of the polymer breaks away from the surface of the coating and enters the ocean, causing marine microplastic pollution and seriously threatening the marine ecosystem.

Introducing a degradable structure into the main chain of traditional self-polishing resins is expected to prepare a resin for antifouling coatings with high efficiency, long service life and environmental friendliness. Especially for polyacrylic acid zinc resin, its cost is low, its hydrolysis speed is moderate, and the zinc ion generated after the zinc ester bond is hydrolyzed also has a certain anti-algae effect.

Contents of the invention

The purpose of the present invention is to address the deficiencies in the existing self-polishing resin technology for marine antifouling coatings, and to provide a method for preparing a main chain degradable polyacrylate zinc resin with a main chain containing a polyester structure and a side chain containing zinc ester bonds. . The resin can not only meet the static anti-fouling requirements of the ocean, but also solve the problem of marine microplastic pollution. It is a main chain degradable zinc polyacrylate resin.

Another object of the present invention is to provide a preparation method of the main chain degradable zinc polyacrylate resin.

Another object of the present invention is to provide the application of the main chain degradable zinc polyacrylate resin. The main chain degradable polyacrylic acid zinc resin is used for preparing marine antifouling paint.

The object of the present invention is achieved through the following technical solutions:

A main chain degradable zinc polyacrylate resin is prepared from the following components in parts by weight:

100 parts of the acrylate prepolymer is based on the total amount of monomers (cyclic monomers, vinyl monomers, (meth)acrylic acid) reacted in the acrylate prepolymer.

The zinc-containing compound is one or more of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate. When the zinc-containing compound is zinc oxide and the monocarboxylic acid is not added, deionized water needs to be added in the reaction.

The monocarboxylic acid is acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, itaconic acid, maleic acid, oil One or more of acid, palmitic acid, and abietic acid.

The acrylate prepolymer is mainly prepared from the following components:

50-100 parts by weight of solvent, 5-95 parts by weight of cyclic monomer, 0-95 parts by weight of vinyl monomer, 5-30 parts by weight of (meth)acrylic acid, and 0.01-10 parts by weight of initiator. The (meth)acrylic acid refers to acrylic acid or methacrylic acid.

The solvent is one or more of hydrocarbon solvents, alcohol solvents, ketone solvents, and ester solvents;

The hydrocarbon solvent is more than one of toluene and xylene; the alcohol solvent is more than one of isopropanol, n-butanol, isobutanol, and propylene glycol methyl ether; the ketone solvent is methyl ether One or more of ethyl ethyl ketone, methyl isobutyl ketone, acetone, butanone, and cyclohexanone; the ester solvent is one or more of ethyl acetate and butyl acetate;

The cyclic monomer is one or more of the following 1-38 compounds: (1) glycolide, (2) lactide, (3) ε-caprolactone, (4) 2-methyl- ε-caprolactone, (5) 2-chloro-ε-caprolactone, (6) γ-butyrolactone, (7) δ-valerolactone, (8) γ-valerolactone, (9) carbonic acid Vinyl ester, (10) propylene carbonate, (11) trimethylene cyclocarbonate, (12) 2,2-dimethyltrimethylene cyclocarbonate, (13) 2-methyl-2-oxazoline , (14) 2-ethyl-2-oxazoline, (15) ethylene oxide, (16) propylene oxide, (17) epichlorohydrin, (18) γ-glycidyl ether oxypropyl trimethyl Oxysilane, (19) 2-methylene-1,3-dioxolane, (20) 2-methylene-4-phenyl-1,3-dioxolane, (21) 2-methylene-4-alkyl-1,3-dioxolane, (22)2,4-dimethylene-1,3-dioxolane, (23)2-methylene Base-1,3-dioxo-4,5-benzocyclopentane, (24)2-methylene-1,3-dioxane, (25)2,5-dimethylene- 1,3-dioxane, (26)2-methylene-5-phenyl-1,3-dioxane, (27)2-methylene-4-alkyl-1, 3-Dioxetane, (28) 2-methylene-1,3-dioxetane, (29) 2-methylene-5-alkyl-1,3-dioxetane , (30) 2-methylene-4,7-dimethyl-1,3-dioxetane, (31) 2-methylene-1,3-dioxo-5,6-benzo Cycloheptane, (32) 2-methylene-5-phenyl-1,3-dioxetane, (33) 2-ethylidene-1,3-dioxetane, (34)2 -Methylene-1,3-dioxo-5-cycloheptene, (35)2-ethylidene-4-alkyl-1,3-dioxolane, (36)2-ethylidene-1 ,3-dioxane, (37)2-allylidene-4-phenyl-1,3-dioxolane, (38)2-ethylidene-1,3-dioxo-5, One or more of 6-benzocycloheptane;

The structural formula of the cyclic monomers of compounds 1 to 38 is as follows:

Where m=1-12 means that m is an integer of 1-12.

The vinyl monomers are acrylates, methacrylates, hydroxyl-terminated acrylates, hydroxyl-terminated methacrylates, acrylic cyclic hydrocarbon esters, methacrylic cyclic hydrocarbon esters, acrylic acid Polyolefin glycol esters, one or more of polyolefin glycol methacrylate esters;

Acrylates are methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, More than one of isooctyl acrylate, lauryl acrylate, and stearyl acrylate;

Methacrylates are methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, More than one of isobutyl methacrylate, tert-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and stearate methacrylate;

The hydroxyl-terminated acrylates are more than one of hydroxyethyl acrylate or hydroxypropyl acrylate;

The hydroxyl-terminated methacrylates are more than one of hydroxyethyl methacrylate and hydroxypropyl methacrylate;

Acrylic cyclic hydrocarbon esters are more than one of phenyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, and 4-tert-butylcyclohexyl acrylate;

The cyclic hydrocarbon esters of methacrylate are more than one of phenyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, and 4-tert-butylcyclohexyl methacrylate;

Acrylic polyolefin glycol esters are polyethylene glycol acrylic acid (polymerization degree is preferably 1～10) ester;

Polyolefin glycol methacrylates are polyethylene glycol methacrylates (preferably with a degree of polymerization of 1 to 10).

The initiator is phosphazene, phosphazene salt, phosphazene oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, peroxide-2-ethyl More than one of tert-butyl hexanoate;

In the main chain degradable zinc polyacrylate resin, the components include low-molecular alcohol or low-molecular amine and/or telogen, the low-molecular alcohol or low-molecular amine is compounded with an initiator, and the telogen and initiator The agent is compounded;

The low molecular weight alcohol is one or more of aliphatic or aromatic alcohols containing 1-12 carbon atoms.

The low molecular weight amine is one or more of aliphatic or aromatic amines containing 1-12 carbon atoms.

When the low-molecular alcohol or low-molecular amine is compounded with the initiator, the total weight of the initiator and the low-molecular alcohol or low-molecular amine is 0.01 to 10 parts, and the compounded initiator and the low-molecular alcohol or low-molecular The mass ratio of amines is preferably 1:(0.1-4).

Described telogen is n-dodecyl mercaptan, tertiary dodecyl mercaptan, isooctyl 3-mercapto propionate, ethyl hexyl alcohol 3-mercapto propionate, four (3-mercapto propionate) One or more of quaternetrol ester and α-methylstyrene dimer; preferably more than one of α-methylstyrene dimer and n-dodecyl mercaptan.

When the telogen is compounded with the initiator, the weight part of the telogen is 0.5-5 parts, and the weight-number ratio of the telogen to the initiator is (0.5-5): (0.01-10) .

The components of the main chain degradable polyacrylate zinc resin contain initiators, and the initiators are initiators, compounds of initiators and low-molecular alcohols or low-molecular amines, compounds of telogens and initiators More than one of the things. The parts by weight of the initiator in the initiator are 0.01-10 parts.

The organic solvent is a hydrocarbon solvent, preferably one or more of toluene and xylene.

The preparation method of the main chain degradable polyacrylic acid zinc resin specifically comprises the following steps:

(1) Synthesis of acrylate prepolymer:

In an inert gas atmosphere, 50 to 100 parts by weight of a solvent is used as a reaction medium, and under the action of 0.01 to 10 parts by weight of an initiator, 5 to 95 parts by weight of a cyclic monomer, 0 to 95 parts by weight of a vinyl monomer and 5-30 parts by weight of (meth)acrylic acid are reacted at 70-120°C for 5-18 hours to obtain an acrylate prepolymer;

(2) Synthesis of zinc polyacrylate resin:

Using 50-100 parts by weight of organic solvent as the reaction medium, reacting 100 parts by weight of acrylate prepolymer, 5-50 parts by weight of zinc-containing compound and 0-50 parts by weight of monocarboxylic acid at 70-180°C for 4-10 hours, A zinc polyacrylate resin is obtained.

The zinc element content of the main chain degradable zinc polyacrylate resin is 0.5-20%, preferably 3-10%.

The number average molecular weight Mn of the main chain degradable zinc polyacrylate resin (measured by GPC using polystyrene as a standard sample) is 1000-80000, preferably 1000-50000.

The main chain degradable zinc polyacrylate resin has an acid value of 30-300 mgKOH/g, preferably 50-230 mgKOH/g.

The main chain degradable polyacrylic acid zinc resin is used for preparing marine antifouling paint.

The invention provides a main chain degradable zinc polyacrylate resin, which is a random copolymer composed of polyester chain segments, vinyl monomers and vinyl zinc ester units, and is prepared by a post-grafting method. The present invention introduces a degradable polyester chain segment into the main chain of polyacrylic acid zinc resin, so that the involved materials can be degraded in addition to the side chain zinc ester bond being hydrolyzed under the attack of seawater, and the main chain polyester structure can also degrade. By adjusting the zinc content and the content of the cyclic monomer, the purpose of synergistic hydrolysis and degradation speed is achieved, and the application needs of static antifouling are met. At the same time, with the continuous progress of hydrolysis and degradation, the material can eventually be degraded into small molecules to solve the problem of marine microplastic pollution.

Compared with the prior art, the present invention has the following advantages and outstanding effects:

(1) The present invention introduces a cyclic monomer into polyacrylate zinc resin to prepare a main chain degradable self-polishing antifouling resin whose main chain contains polyester segments and side chains contain zinc ester bonds. In addition to the hydrolysis of the side chain zinc ester bond under the attack of seawater, the obtained resin can also degrade the main chain polyester segment, thereby solving the dependence of traditional self-polishing materials on speed, and can also be hydrolyzed in static seawater. Degradation makes the surface of the coating self-renewal, thereby effectively controlling the release of the antifouling agent at a constant rate, ensuring the maintenance of active substances on the coating surface of ships or marine equipment, and meeting the needs of low-speed ships and offshore oil production platforms and other facilities antifouling requirements;

(2) Since the main and side chains of the material provided by the present invention can be broken under the attack of seawater, it can be uniformly and thoroughly polished, so that the coating surface of the ship can maintain a low roughness during navigation, reduce navigation resistance, and endow the material with excellent performance. Drag reduction performance;

(3) The present invention can also add different types and different contents of vinyl monomers in the copolymerization to regulate the glass transition temperature and mechanical properties of the material, and at the same time improve the solubility of the material in common solvents for marine coatings.

(4) The preparation method provided by the present invention is simple and feasible, has low cost and is suitable for industrial production, and the prepared zinc polyacrylate resin has good development prospects in the field of marine antifouling coatings.

detailed description

The present invention will be described in further detail below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto.

Example 1

A preparation method of main chain degradable polyacrylic acid zinc resin, specifically comprising the following steps:

(1) Synthesis of acrylate prepolymer:

Add 64g of xylene and 16g of n-butanol to the reaction vessel, heat to 90°C under a nitrogen atmosphere, and dropwise add 40g of 4-methylcyclohexyl acrylate, 40g of methyl methacrylate, 10g of 2-chloro – A mixture of ε-caprolactone, 10 g of acrylic acid, 0.1 g of ethanol and 70 μL of t-BuP ₄ in n-hexane (containing 0.04 g of t-BuP ₄ ), after the dropwise addition, keep warm for 2 hours to obtain acrylic acid Ester prepolymers;

(2) Synthesis of zinc polyacrylate resin:

Add 25.2g zinc acetate, 47.2g naphthenic acid (acid value 165) and 100g dimethylbenzene in the acrylate prepolymer of step (1), react in 130 ℃ for 8 hours, obtain polyacrylic acid zinc resin (brown transparent resin solution .)

In this example, the number-average molecular weight M _n of the resin is 1.6×10 ⁴ g/mol, the zinc content is 5.8%, and the acid value is 100 mgKOH/g. The board test in shallow sea shows no growth of marine organisms for 10 months.

Example 2

A preparation method of main chain degradable polyacrylic acid zinc resin, specifically comprising the following steps:

(1) Synthesis of acrylate prepolymer:

Add 64g of xylene and 16g of propylene glycol methyl ether to the reaction vessel, heat to 95°C under nitrogen atmosphere, and dropwise add 20g of 4-tert-butylcyclohexyl methacrylate, 40g of ethyl acrylate, 25g of 2-methylene Base-1,3-dioxane, 15g of methacrylic acid, 2g of azobisisobutyronitrile and 0.5g of tert-dodecylmercaptan, after the dropwise addition, keep warm for 2 hours to obtain acrylate prepolymer;

(2) Synthesis of polyacrylic acid zinc resin: add 14.2g zinc oxide, 5g deionized water and 30g xylene in the acrylate prepolymer of step (1), in 140 ℃ of reactions 8 hours, obtain polyacrylic acid zinc resin ( colorless transparent resin solution).

In this example, the number-average molecular weight _Mn of the resin is 2.0×10 ⁴ g/mol, the zinc content is 5.1%, and the acid value is 104 mgKOH/g. The shallow sea hanging board test has no marine growth for 12 months.

Example 3

A preparation method of main chain degradable polyacrylic acid zinc resin, specifically comprising the following steps:

(1) Synthesis of acrylate prepolymer:

Add 80g of xylene to the reaction vessel, heat to 100°C under nitrogen atmosphere, dropwise add 10g of polyethylene glycol methacrylate (polymerization degree: 9), 10g of hydroxypropyl methacrylate, 60g of isoacrylate A mixture of octyl esters, 10g 2-methylene-1,3-dioxo-5-cycloheptene, 10g methacrylic acid, 2.5g azobisisovaleronitrile and 0.5g α-methylstyrene dimer , after the dropwise addition was completed, the insulation was kept for 2 hours to obtain an acrylate prepolymer;

(2) Synthesis of zinc polyacrylate resin: add 11.5g zinc hydroxide, 35.2g abietic acid and 80g xylene to the acrylate prepolymer of step (1), and react at 140°C for 8 hours to obtain zinc polyacrylate resin (yellow transparent resin solution).

In this example, the number-average molecular weight _Mn of the resin is 1.1×10 ⁴ g/mol, the zinc content is 5.3%, and the acid value is 91 mgKOH/g. The shallow sea hanging board test has no marine growth for 8 months.

Example 4

A preparation method of main chain degradable polyacrylic acid zinc resin, specifically comprising the following steps:

(1) Synthesis of acrylate prepolymer:

Add 64g propylene glycol methyl ether and 16g butyl acetate to the reaction vessel, heat to 100°C under nitrogen atmosphere, dropwise add 25g polyethylene glycol methacrylate (polymerization degree is 23), 40g ethyl acrylate, A mixture of 30g 2-methylene-1,3-dioxo-5,6-benzocycloheptane, 5g acrylic acid and 4g di-tert-butyl peroxide was added dropwise and kept for 2 hours to obtain acrylate prepolymer;

(2) Synthesis of polyacrylic acid zinc resin: add 9.5g zinc chloride, 4.2g acetic acid and 20g dimethylbenzene in the acrylate prepolymer of step (1), in 120 ℃ of reactions 8 hours, obtain polyacrylic acid zinc resin ( colorless transparent resin solution).

In this example, the number-average molecular weight M _n of the resin is 1.8×10 ⁴ g/mol, the zinc content is 4.2%, and the acid value is 72 mgKOH/g. The shallow sea hanging board test was carried out, and no marine organisms grew for 6 months.

Claims (10)

1. A main chain degradable polyacrylic acid zinc resin is characterized in that: it is mainly prepared from the following components in parts by weight: 100 parts of the acrylate prepolymer are based on the total amount of monomers reacted in the acrylate prepolymer; The acrylate prepolymer is mainly prepared from the following components: 50-100 parts by weight solvent, 5-95 parts by weight cyclic monomer, 0-95 parts by weight vinyl monomer, 5-30 parts by weight (meth)acrylic acid, 0.01-10 parts by weight initiator; Base) acrylic means acrylic or methacrylic. 2. main chain degradable polyacrylic acid zinc resin according to claim 1, is characterized in that: The cyclic monomer is one or more of the following 1-38 structures: Where m=1-12 means that m is an integer of 1-12. 3. according to the described main chain degradable zinc polyacrylate resin of claim 2, it is characterized in that: described vinyl monomer is acrylates, methacrylates, the acrylates of terminal hydroxyl, the methyl of terminal hydroxyl Acrylic esters, cyclic hydrocarbon acrylates, cyclic hydrocarbon methacrylates, polyolefin glycol acrylates, and polyolefin glycol methacrylates. 4. according to the described main chain degradable zinc polyacrylate resin of claim 3, it is characterized in that: acrylates are methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate One or more of ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, stearate acrylate; Methacrylates are methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, More than one of isobutyl methacrylate, tert-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and stearate methacrylate; The hydroxyl-terminated acrylates are more than one of hydroxyethyl acrylate or hydroxypropyl acrylate; The hydroxyl-terminated methacrylates are more than one of hydroxyethyl methacrylate and hydroxypropyl methacrylate; Acrylic cyclic hydrocarbon esters are more than one of phenyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, and 4-tert-butylcyclohexyl acrylate; The cyclic hydrocarbon esters of methacrylate are more than one of phenyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, and 4-tert-butylcyclohexyl methacrylate; Acrylic polyolefin glycol esters are polyethylene glycol acrylates; The polyolefin glycol methacrylate is polyethylene glycol methacrylate. 5. The main chain degradable polyacrylic acid zinc resin according to claim 1, characterized in that: the zinc-containing compound is more than one of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate; The monocarboxylic acid is acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, itaconic acid, maleic acid, oil One or more of acid, palmitic acid, and abietic acid. 6. main chain degradable zinc polyacrylic acid resin according to claim 1, is characterized in that: described solvent is more than one of hydrocarbon solvent, alcoholic solvent and deionized water; Described initiator is phosphazene, phosphorus Nitrile salt, phosphazene oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate above. 7. The main chain degradable zinc polyacrylate resin according to claim 1, characterized in that: the organic solvent is a hydrocarbon solvent. 8. The main chain degradable zinc polyacrylate resin according to claim 1, characterized in that: in the main chain degradable zinc polyacrylate resin, the components also include low-molecular alcohols or low-molecular amines and/or modifiers Compounding agent, compounding of low molecular alcohol or low molecular amine and initiator, compounding of telogen and initiator; The low molecular weight alcohol is one or more of aliphatic or aromatic alcohols containing 1 to 12 carbon atoms; The low-molecular-weight amine is one or more of aliphatic or aromatic amines containing 1 to 12 carbon atoms; Described telogen is n-dodecyl mercaptan, tertiary dodecyl mercaptan, isooctyl 3-mercapto propionate, ethyl hexyl alcohol 3-mercapto propionate, four (3-mercapto propionate) One or more of quaternetritol ester and α-methylstyrene dimer. 9. According to the preparation method of the main chain degradable polyacrylic acid zinc resin according to any one of claims 1 to 8, it is characterized in that: it specifically comprises the following steps: (1) Synthesis of acrylate prepolymer: In an inert gas atmosphere, 50 to 100 parts by weight of a solvent is used as a reaction medium, and under the action of 0.01 to 10 parts by weight of an initiator, 5 to 95 parts by weight of a cyclic monomer, 0 to 95 parts by weight of a vinyl monomer and 5-30 parts by weight of (meth)acrylic acid are reacted at 70-120°C for 5-18 hours to obtain an acrylate prepolymer; (2) Synthesis of zinc polyacrylate resin: Using 50-100 parts by weight of organic solvent as the reaction medium, reacting 100 parts by weight of acrylate prepolymer, 5-50 parts by weight of zinc-containing compound and 0-50 parts by weight of monocarboxylic acid at 70-180°C for 4-10 hours, A zinc polyacrylate resin is obtained. 10. The application of the main chain degradable zinc polyacrylate resin according to any one of claims 1 to 8, characterized in that: the main chain degradable zinc polyacrylate resin is used for preparing marine antifouling coatings.