CN107056990A - Main chain degradation-type polyacrylic acid zinc resin and its method and application prepared by a kind of simplex 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 monomer method, a method and an application thereof. The main chain degradable zinc polyacrylate resin is mainly prepared from the following components in parts by weight: 5-80 parts of vinyl zinc ester functional monomer, 5-95 parts of cyclic monomer, vinyl monomer 0-95 parts, 0.01-10 parts of initiator, 50-100 parts of organic solvent. 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 monomer 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 monomer method and its method and application; the resin 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 provide a main chain degradable polyacrylic acid zinc resin whose main chain contains polyester structure and side chain contains zinc ester bonds, aiming at the deficiencies of the existing self-polishing resin technology for marine antifouling coatings. 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 mainly prepared from the following components in parts by weight:

The vinyl zinc ester functional monomer is prepared from the following components in parts by weight:

The (meth)acrylic acid refers to acrylic acid or methacrylic acid.

The zinc-containing compound is at least one of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate. When the zinc-containing compound is zinc oxide, 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 solvent is more than one of hydrocarbon solvent, alcohol solvent and deionized water; the hydrocarbon solvent is one or more of toluene and xylene; the alcohol solvent is isopropanol, n-butanol , isobutanol, and propylene glycol methyl ether.

The cyclic monomer is one or more of 1 to 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) ethylene carbonate ester, (10) propylene carbonate, (11) trimethylene cyclocarbonate, (12) 2,2-dimethyl trimethylene cyclocarbonate, (13) 2-methyl-2-oxazoline, (14) 2-ethyl-2-oxazoline, (15) ethylene oxide, (16) propylene oxide, (17) epichlorohydrin, (18) γ-glycidyl ether oxypropyl trimethoxy silane, (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 -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-benzocyclo Heptane, (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-5,6 - one or more of benzocycloheptanes;

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 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.

In the main chain degradable zinc polyacrylate resin, the parts by weight of the vinyl zinc ester functional monomer can be based on the total weight of the reaction solution after the preparation of the vinyl zinc ester functional monomer, or can be based on the weight of the vinyl zinc ester functional monomer. The total weight of the reactants (zinc-containing compound, (meth)acrylic acid and monocarboxylic acid) in the body.

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

(1) Synthesis of vinyl zinc ester functional monomer:

Using 50-105 parts by weight of solvent as the reaction medium, react 10-40 parts by weight of zinc-containing compound, 15-30 parts by weight of (meth)acrylic acid and 20-75 parts by weight of monocarboxylic acid at 50-140°C for 3-8 hours , to obtain vinyl zinc ester functional monomer;

(2) Synthesis of zinc polyacrylate resin:

In an inert atmosphere, 50-100 parts by weight of an organic solvent is used as a reaction medium, and under the action of 0.01-10 parts by weight of an initiator, 5-95 parts by weight of a cyclic monomer, 0-95 parts by weight of a vinyl monomer and 5-80 weight parts of vinyl zinc ester functional monomers are reacted, and the reaction condition is to react at 70-120°C for 8-18 hours to obtain polyacrylic acid zinc polymer.

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 main chain degradable zinc polyacrylate resin provided by the invention has a structure of a random copolymer composed of polyester chain segments, vinyl monomers and vinyl zinc ester units, and is prepared by a monomer 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 the copolymerization of cyclic monomers and vinyl zinc ester functional monomers into polyacrylic acid zinc resin, and prepares a main chain degradable self-polishing with polyester segments in the main chain and zinc ester bonds in the side chains Stain-resistant resin. 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 vinyl monomers of different types and different contents in the copolymerization to regulate the glass transition temperature and mechanical properties of the material, while improving the solubility of the material in the common solvents used 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. 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 vinyl zinc ester functional monomer:

Add 81.4g of zinc oxide, 200g of propylene glycol methyl ether and 40g of xylene to the reaction vessel, heat to 65°C, add dropwise a mixture of 72.1g of acrylic acid, 86.1g of methacrylic acid and 10g of deionized water in 3 hours, after the addition is complete, Insulated and reacted for 2 hours to obtain a colorless and transparent vinyl zinc ester functional monomer solution;

(2) Synthesis of zinc polyacrylate resin:

Under the condition of stirring, add 500g of xylene, 100g of propylene glycol methyl ether and 24g of ethyl acrylate to the reaction vessel, raise the temperature to 90°C under a nitrogen atmosphere, add dropwise 44g of 2-methylene-1,3-bis Oxycycloheptane, 44g-2-methoxyethyl methacrylate, 176g methyl methacrylate, 396g ethyl acrylate, 449.6g step (1) vinyl zinc ester functional monomer solution, 22g azobisiso The mixture of butyronitrile and 8g α-methylstyrene dimer is formed. After the dropwise addition is completed, continue to drop the mixture of 8g di-tert-butyl peroxide and 90g xylene in 30 minutes, and stir for another 1.5 hours to obtain the main chain degradation type Zinc polyacrylate resin (colorless or yellowish transparent resin solution).

In this example, the number-average molecular weight M _n of the resin is 2.5×10 ⁴ g/mol, the zinc content is 7.2%, and the acid value is 124 mgKOH/g. The shallow sea hanging board test shows no growth of marine organisms for 14 months.

Example 2

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

(1) Synthesis of vinyl zinc ester functional monomer:

Add 81.4g of zinc oxide, 400g of xylene and 100g of isopropanol to the reaction vessel, heat to 80°C, add dropwise a mixture of 72.1g of acrylic acid and 340g of naphthenic acid (acid number 165) at a constant rate, and drop it in 3 hours , after the dropwise addition was completed, the insulation reaction was carried out for 2 hours to obtain a brown transparent vinyl zinc ester functional monomer solution;

(2) Synthesis of zinc polyacrylate resin:

Under the condition of stirring, add 350g of xylene and 100g of methyl isobutyl ketone into the reaction vessel, raise the temperature to 95°C under a nitrogen atmosphere, and add 100g of caprolactone, 100g of methyl acrylate, and 100g of butyl acrylate dropwise at a constant speed for 4 hours. , 200g cyclohexyl methacrylate, 893.5g step (1) vinyl zinc ester functional monomer solution, 1g methanol and 1mL phosphazene (t-BuP ₄ ) n-hexane solution (0.5g of t-BuP ₄ ) composition After the dropwise addition, keep warm for 2 hours, add 5g of azobisisobutyronitrile and 50g of dimethylbenzene dropwise at a constant speed in 30 minutes, and stir for 4 hours to obtain the main chain degraded polyacrylic acid zinc resin (brown transparent resin solution) .

In this example, the number-average molecular weight _Mn of the resin is 3.0×10 ⁴ g/mol, the zinc content is 6.7%, and the acid value is 115 mgKOH/g. The shallow sea hanging board test has no growth of marine organisms for 12 months.

Example 3

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

(1) Synthesis of vinyl zinc ester functional monomer:

Add 99.4g of zinc hydroxide, 400g of toluene and 74g of isobutanol to the reaction vessel, and heat it to 75°C, dropwise add a mixture of 72.1g of acrylic acid and 302.5g of abietic acid at a constant speed for 3 hours, after the dropwise addition, keep the temperature for 2 hours for reaction , to obtain a yellow transparent vinyl zinc ester functional monomer solution;

(2) Synthesis of zinc polyacrylate resin:

Under the condition of stirring, add 500g of xylene and 400g of butyl acetate into the reaction vessel, raise the temperature to 100°C under a nitrogen atmosphere, and add 150g of lactide, 584g of isooctyl acrylate, and 292g of ethyl methacrylate dropwise at a constant speed for 4 hours. ester, 948g step (1) in the vinyl zinc ester functional monomer solution, the mixture of 0.15g diethylene glycol and 1mL t-BuP ₄ n-hexane solution (0.5g t-BuP ₄ ), after the dropwise addition , insulated for 2 hours, 8g benzoyl peroxide and 100g xylene were added dropwise at a constant speed in 30 minutes, and then stirred for 4 hours to obtain the main chain degradable polyacrylic acid zinc resin (yellow transparent resin solution).

In this example, the number-average molecular weight M _n of the resin is 1.2×10 ⁴ g/mol, the zinc content is 4.5%, and the acid value is 77 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 vinyl zinc ester functional monomer:

Add 183.5g of zinc acetate, 114g of toluene and 300g of n-butanol to the reaction vessel, and heat it to 130°C, and dropwise add a mixture of 86.1g of methacrylic acid and 144.2g of isooctanoic acid at a constant speed for 3 hours. Hour, obtain colorless and transparent vinyl zinc ester functional monomer solution;

(2) Synthesis of zinc polyacrylate resin:

Under stirring conditions, add 1800g propylene glycol methyl ether and 400g ethyl acetate to the reaction vessel, raise the temperature to 100°C under a nitrogen atmosphere, and add 1172g 2-methylene-1,3-dioxolane dropwise at a constant speed for 4 hours Alkane, 293g hydroxyethyl methacrylate, 586g phenyl acrylate, 586g tert-butyl methacrylate, 827.8g step (1) vinyl zinc ester functional monomer solution, 88g peroxy-2-ethylhexanoic acid tert-butyl ester and 29g α-methylstyrene dimer, after the dropwise addition, keep warm for 2 hours, add 15g tert-butyl peroxy-2-ethylhexanoate and 300g xylene dropwise at a constant speed in 30 minutes, and then stir for 4 Hours, the main chain degraded polyacrylic acid zinc resin (colorless transparent resin solution) was obtained.

In this example, the number-average molecular weight M _n of the resin is 2.6×10 ⁴ g/mol, the zinc content is 2.3%, and the acid value is 38 mgKOH/g. In a shallow sea hanging board experiment, 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: The vinyl zinc ester functional monomer is prepared from the following components in parts by weight: The (meth)acrylic acid refers to acrylic acid or methacrylic acid. 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; The vinyl monomers are acrylates, methacrylates, hydroxyl-terminated acrylates, hydroxyl-terminated methacrylates, acrylic cyclic hydrocarbon esters, methacrylic cyclic hydrocarbon esters, acrylic acid One or more kinds of polyolefin glycol esters and polyolefin glycol methacrylates. 3. according to the described main chain degradable polyacrylic acid zinc resin of claim 2, 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. 4. 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. 5. The main chain degradable zinc polyacrylate resin according to claim 1, characterized in that: the solvent is at least one of hydrocarbon solvents, alcohol solvents and deionized water. 6. according to the described main chain degradable polyacrylic acid zinc resin of claim 1, it is characterized in that: described organic solvent is more than one in hydrocarbon solvent, alcohol solvent, ketone solvent, ester solvent; The agent is phosphazene, phosphazene salt, phosphazene oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, tert-2-ethylhexanoate peroxide One or more of butyl esters. 7. according to the described main chain degradable polyacrylic acid zinc resin of claim 6, it is characterized in that: described hydrocarbon solvent is more than one in toluene, xylene; Described alcohol solvent is Virahol, n-butyl alcohol , isobutanol, and propylene glycol methyl ether; the ketone solvent is more than one of methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone, and cyclohexanone; the ester The solvent is one or more of ethyl acetate and butyl acetate. 8. The main chain degradable polyacrylic acid zinc resin according to claim 1, characterized in that: in the main chain degradable polyacrylic acid zinc resin, the components also include low-molecular alcohol or low-molecular amine and/or modifier 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 vinyl zinc ester functional monomer: Using 50-105 parts by weight of solvent as the reaction medium, react 10-40 parts by weight of zinc-containing compound, 15-30 parts by weight of (meth)acrylic acid and 20-75 parts by weight of monocarboxylic acid at 50-140°C for 3-8 hours , to obtain vinyl zinc ester functional monomer; (2) Synthesis of zinc acrylate resin: In an inert atmosphere, 50-100 parts by weight of an organic solvent is used as a reaction medium, and under the action of 0.01-10 parts by weight of an initiator, 5-95 parts by weight of a cyclic monomer, 0-95 parts by weight of a vinyl monomer and 5-80 parts by weight of vinyl zinc ester functional monomers are reacted, and the reaction condition is to react at 70-120° C. for 8-18 hours to obtain zinc acrylate polymer. 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.