AU2020314508A1

AU2020314508A1 - Branch-point-breaking-type hyperbranched resin, preparation method therefor, and use thereof

Info

Publication number: AU2020314508A1
Application number: AU2020314508A
Authority: AU
Inventors: Chunfeng MA; Jiansen PAN; Qingyi XIE; Guangzhao Zhang
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 2019-07-18
Filing date: 2020-07-17
Publication date: 2022-03-10
Anticipated expiration: 2040-07-17
Also published as: CN110511328A; AU2020314508B2; WO2021008604A1; CN110511328B

Abstract

Disclosed are a branch-point-breaking-type hyperbranched resin, a preparation method therefor, and the use thereof. The branch-point-breaking-type hyperbranched resin is prepared mainly from the following components in parts by weight: 0-70 parts of an anti-fouling vinyl functional monomer, 1-60 parts of a difunctional monomer, 0-90 parts of a vinyl monomer, 1-20 parts of an initiator, 0.5-10 parts of a chain transfer agent, and 50-150 parts of an organic solvent. Branch points of the resin can be broken under the attack of seawater, and after breakage, small molecular fragments that are easily absorbed by the environment are formed, so that marine microplastic pollution can be effectively avoided. Moreover, pendant silane ester bonds/zinc ester bonds/copper ester bonds/betaine-type zwitterionic precursors can also be hydrolyzed in seawater, which, in cooperation with the breakage of the branch points, can further increase the hydrolysis rate of a material, achieving rapid polishing, thereby solving the problem of traditional self-polishing materials being dependent on ship speed. Same satisfies static anti-fouling requirements in sea areas where fouling pressure is high.

Description

BRANCH-POINT-BREAKING TYPE HYPERBRANCHED RESIN, PREPARATION METHOD THEREFOR AND USE THEREOF

Technical field The present invention belongs to the technical field of a marine antifouling material, specifically relates to a branch-point-breaking type hyperbranched resin and preparation method therefor and use thereof.

Background Issues of marine biological fouling may cause huge economic losses and hidden safety hazards, and therefore marine antifouling is a subject closely related to major national needs like environment, energy, national defense and so on, and is of great significance. At present, coating a marine antifouling paint is the most economical, the most convenient and commonly used method to solve the problem of marine biological fouling. The mainstream technology of self-polishing resin is represented by polysilyl acrylate, poly(zinc acrylate) and poly(copper acrylate) resins, all of which are side-chain hydrolysis type, and exhibition of whose performances has certain requirements on the ratio of port time to sea time and ship speed. In the stationary phase, it is difficult to achieve the ideal self-polishing !0 effect only by the scouring of sea water. More importantly, this kind of resin has no function and can only rely on the release of an antifouling agent to inhibit and kill fouling organisms. The instability of polishing leads to the antifouling agent being released discontinuously, and therefore the static antifouling effect is not good. Not only that, while it is difficult for the hydrolyzed polymer to break away from the !5 coating surface to increase the swellability of the coating, the main chain cannot be degraded in the sea environment, and its dispersion in the ocean may cause microplastic pollution, which will seriously threaten the safety of the marine ecosystem. The focus of current research is on how to impart multifunctionality to the antifouling resin to enhance its antifouling function, for example, introducing a polyester structure into the polymer backbone to impart degradability, such as patent CN201310314516, a preparation method and an application for a main-chain-breaking type polysilyl acrylate resin; patent CN201710292447, a main chain degradable poly(zinc acrylate) resin prepared by a monomer method and preparation method and application therefor; patent CN201710292938, a main chain degradable poly(copper acrylate) resin and preparation method and application therefor; grafting functional monomers which have antifouling groups with fouling resistance properties or are capable of inducing autogenous zwitterions and so on. However, the implementations of the above technologies are all based on traditional straight-chain type polymer resins, which still cannot well make the hydrolyzed resin break away from the coating surface in time, realize controllable self-polishing, and satisfy the static antifouling requirements in the sea area with great fouling pressure.

Summary In order to overcome defects and shortcomings of the prior art, a primary object of the present invention is to provide a branch-point-breaking type hyperbranched resin. The resin may not only satisfy marine static antifouling !0 requirements, but also avoid causing marine microplastic pollution at the same time. Another object of the present invention is to provide a preparation method for the above-described branch-point-breaking type hyperbranched resin. Yet another object of the present invention is to provide a use for the !5 above-described branch-point-breaking type hyperbranched resin. The branch-point-breaking type hyperbranched resinmay be used for marine antifouling field. The object of the present invention is realized by the following technical solution:

A branch-point-breaking type hyperbranched resin is prepared from the following components in terms of parts by weight: a vinyl antifouling functional monomer 0 to 70 parts, a difunctional monomer 1 to 60 parts, a vinyl monomer 0 to 90 parts, an initiator I to 20 parts, a chain transfer agent 0.5 to 10 parts, and an organic solvent 50 to 150 parts; the vinyl antifouling functional monomer is one of a vinyl silane ester monomer, a vinyl zinc ester monomer, a vinyl copper ester monomer and a precursor of betaine type zwitterion; the vinyl silane ester monomer is at least one of acryloxy trimethyl silane, trimethyl silyl methacrylate, acryloxy triethyl silane, triethyl silyl methacrylate, acryloxy triisopropyl silane, triisopropyl silyl methacrylate, acryloxy triphenyl silane, triphenyl silyl methacrylate, acryloxy tri-n-butyl silane, tri-n-butyl silyl methacrylate, acryloxy t-butyl dimethyl silane, t-butyl dimethyl silyl methacrylate, acryloxy bis(trimethyl siloxanyl) methyl silane and bis(trimethyl siloxanyl) methyl silyl methacrylate; the vinyl zinc ester monomer is prepared by the following method: taking a !0 solvent as a reaction medium, and reacting a zinc-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2), wherein the vinyl zinc ester monomer in a mixed solution of a product has a solid content of 40 to 60%; the vinyl copper ester monomer is prepared by the following method: taking !5 a solvent as a reaction medium, and reacting a copper-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2), wherein the vinyl copper ester monomer in the mixed solution of the product has a solid content of 40 to 60%; a general structual formula of the precursor of betaine type zwitterion is shown as the following formula: 0

R1-'Y - N _-, O'.R2 0

wherein, R 1 represents H or CH3, R2 represents one of alkyl having a number of carbon atoms of 1 to 12 (straight chain, branched chain or cyclic), methoxy-terminated polyethylene glycol(n=2 to 24), isothiazolinones, triclosan, paeonol, camptothecin, N-(2,4,6-trichloro phenyl)maleimide, bromopyrrole nitrile, donaxine, capsaicin, hydroxyindoles, R3 COOZn, R4 COOCu or (R) 3 Si, wherein R3 and R4 are both saturated alkyl having a number of carbon atoms of 1 to 12, unsaturated alkyl having a number of carbon atoms of 1 to 12, saturated cycloalkyl having a number of carbon atoms of 1 to 12 or unsaturated cycloalkyl having a number of carbon atoms of 1 to 12, R5 is uniformly or differently selected from alkyl having a number of carbon atoms of I to 8. The branch-point-breaking type hyperbranched resin, in terms of parts by weight, is preferably prepared from the following components: the vinyl antifouling functional monomer 25 to 70 parts, the difunctional monomer 1 to 30 parts, the vinyl monomer 0 to 40 parts, the initiator 3 to 13 parts, the chain transfer agent 2 to 5 parts, and the organic solvent 100 to 110 parts. The zinc-containing compound is preferably at least one of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate and zinc propionate; and the copper-containing compound is preferably at least one of copper oxide, copper hydroxide, copper chloride, copper acetate and copper propionate. The monocarboxylic acid is preferably at least one of formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, oleic acid, palmitic acid and rosin acid. The solvents in the vinyl zinc ester monomer and the vinyl copper ester monomer are preferably at least one of hydrocarbons solvent, alcohols solvent and water; and is more preferably at least one of toluene, xylene, isopropanol, n-butanol, isobutanol and propylene glycol methyl ether.

The difunctional monomer is preferably a functional monomer with vinyl

groups at both terminals; and is more preferably at least one of (meth)acrylates

containing a metallic element, aliphatic polyesters with vinyl groups at both

terminals, schiff bases and compounds containing disulfide bonds. The (meth)acrylates containing a metallic element are preferably at least one of magnesium acrylate, magnesium methacrylate, magnesium acrylate methacrylate, manganese acrylate, manganese methacrylate, manganese acrylate methacrylate, zinc acrylate, zinc methacrylate, zinc acrylate methacrylate, copper acrylate, copper methacrylate, copper acrylate methacrylate, iron acrylate, iron methacrylate, and iron acrylate methacrylate. The aliphatic polyesters with vinyl groups at both terminals are preferably at least one of polyprolylene carbonate with vinyl groups at both terminals, polytrimethylene carbonate with vinyl groups at both terminals, poly(trimethylene carbonate-caprolactone) with vinyl groups at both terminals, poly(caprolactone-glycolide) with vinyl groups at both terminals, poly(caprolactone-lactide) with vinyl groups at both terminals, !0 poly(caprolactone-ethylene glycol) with vinyl groups at both terminals, poly(lactide-glycolide) with vinyl groups at both terminals, poly(lactide-ethylene glycol) with vinyl groups at both terminals, poly 3-hydroxy butyrate with vinyl groups at both terminals, poly(3-hydroxy butyrate-co-3-hydroxy valerate) with vinyl groups at both terminals, polyethylene glycol adipate with vinyl groups at !5 both terminals, polydiethylene glycol adipate with vinyl groups at both terminals, polybutylene glycol adipate with vinyl groups at both terminals, polyhexylene glycol adipate with vinyl groups at both terminals, polybutylene glycol succinate with vinyl groups at both terminals, polyorthoesters with vinyl groups at both terminals, polyanhydrides with vinyl groups at both terminals, polyphosphate with vinyl groups at both terminals, polycaprolactone with vinyl groups at both terminals, polylactide with vinyl groups at both terminals and polyglycolide with vinyl groups at both terminals; and molecular weights of the aliphatic polyesters with vinyl groups at both terminals are all preferably 1x102 to 5x103 g/mol, and are more preferably 3x102 to 2x103 g/mol. The structures of the Schiff bases and compounds containing disulfide bonds are shown as follows:

HN NH HN NH HN Schiffbases M" H

0 14 0 diacrylamide containing oxime diacrylamide containing semicarbazone diacrylamide containing hydrazone structure

compounds containing N N S' N disulfide bonds o H N,N'- bis(acroloyl)cystamine N,N'-diallyl dithiodipropionamide

.

The vinyl monomer is preferably at least one of (meth)acrylates, (meth)acrylates containing a terminal hydroxyl group, cyclic hydrocarbon (meth)acrylates and polyolefin glycol (meth)acrylates. The vinyl monomer of the (meth)acrylates is preferably at least one of methyl acrylate, ethyl acrylate, 2-methoxy ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methoxy ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate and octadecyl methacrylate. The (meth)acrylates containing a terminal hydroxyl group are preferably at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. The cyclic hydrocarbon (meth)acrylates are preferably at least one of cyclohexyl acrylate, 1-methylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, cyclohexyl methacrylate, 1-methylcyclohexyl methacrylate and 4-t-butyl cyclohexyl methacrylate. The polyolefin glycol (meth)acrylates are preferably at least one of polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol methacrylate and polypropylene glycol methacrylate, and the polyolefin glycol (meth)acrylates all have a degree of polymerization of 1 to 10. The initiator is preferably at least one of phosphonitrile, phosphonitrile salt, phosphonitrile oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide and t-butyl peroxy-2-ethyl hexanoate. The chain transfer agent is preferably at least one of thiol, dithioester, trithioester and methyl styrene dimer (i.e. 2,4-diphenyl-4-methyl-1-pentene). The mercaptan is preferably at least one of n-dodecyl alkyl mercaptan, t-dodecyl alkyl mercaptan, mercapto ethanol, mercapto acetic acid, isooctyl 3-mercapto propionate, 2-ethyl hexyl 3-mercapto propionate and pentaerythritol tetrakis(3-mercapto propionate). The dithioester is preferably at least one of cumenyl benzodithioate, 2-cyano !0 isopropyl benzodithioate, methyl benzodithioate, phenethyl benzodithioate, benzyl benzodithioate, phenylethyl phenylethane dithioate, S-(thiobenzoyl) thioglycolic acid, S-acetonyl-O-ethyl dithiocarbonate, S-vinyl propionate-O-ethyl dithiocarbonate, 2-cyano propyl-4-cyano benzodithioate, 2-cyano propyl-N-methyl-N-(4-pyridine) amino dithiocarbonate, !5 methyl-2-[methyl(4-pyridine)dithiocarbonate]propionate,4-cyano-4-(thiobenzoyl) pentanoic acid, cyanomethyl methyl(phenyl) carbamodithioate, 2-phenyl-2-propyl benzodithioate, 1-cyano-1-methyl-4-oxo-4-(2-thio-3-thiazole alkyl) butyl ester, bis(thiobenzoyl) dithioether, tetramethylthiuram disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, di-n-butyl xanthogen disulfide and diisobutyl xanthogen disulfide. The trithioester is preferably at least one of 2-cyano-2-propyl dodecyl trithiocarbonate, dibenzyl trithiocarbonate, S-cyanomethyl-S-dodecyl trithiocarbonate, 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid, bis(carboxy methyl) trithiocarbonate, methyl 2-[[(dodecyl mercapto)thiomethyl]thio]-2-methyl benzoate, 2-(((dodecylthio)carbonothioyl)thio)-2-methyl propionic acid and dimethyl trithiocarbonate. The organic solvent in the branch-point-breaking type hyperbranched resin ingredients is preferably at least one of hydrocarbons solvent, alcohols solvent, ketones solvent and esters solvent; and is more preferably at least one of tolyene, xylene, iso-propanol, n-butanol, isobutanol, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone, cyclohexanone, ethyl acetate and butyl acetate. The branch-point-breaking type hyperbranched resin of the present invention has a structure which is a hyperbranched random copolymer consisting of a vinyl antifouling functional monomer, a difunctional monomer and a vinyl monomer. When the vinyl antifouling functional monomer is the vinyl silane ester monomer, the product is hyperbranched silicon-based self-polishing resin; when the vinyl !0 antifouling functional monomer is the vinyl zinc ester monomer, the product is hyperbranched zinc-based self-polishing resin; when the vinyl antifouling functional monomer is the vinyl silyl copper ester monomer, the product is hyperbranched copper-based self-polishing resin; when the vinyl antifouling functional monomer is precursor of betaine type zwitterion, the product is !5 hyperbranched self-polishing resin self-generating zwitterion. The hyperbranched silicon-based self-polishing resin has a silicon element content of 1% to 15%, preferably 3% to 8%; the hyperbranched zinc-based self-polishing resin has a zinc element content of 0.5% to 20%, preferably 3% to 10%; the hyperbranched copper-based self-polishing resin has a copper element content of 1% to 20%, preferably 5% to 15%; the hyperbranched silicon/zinc/copper-based self-polishing resin has an acid value of 30 to 350 mg KOH/g, preferably 50 to 250 mg KOH/g. The branch-point-breaking type hyperbranched resin has a number-average molecular weight M,(taking polystyrene as a standard sample, measured by GPC) of 1000 to 10000, preferably 2000 to 6000. A preparation method for the above-described branch-point-breaking type hyperbranched resin includes the following steps: (1) Synthesis of vinyl zinc ester monomer or vinyl copper ester monomer: taking a solvent as a reaction medium, and reacting a zinc-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2) at 50 to 140 °C for 3 to 8 hours, to obtain a vinyl zinc ester monomer; taking a solvent as a reaction medium, and reacting a copper-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2) at 50 to 140 °C for 3 to 8 hours, to obtain a vinyl copper ester monomer; taking a vinyl silane ester monomer, the vinyl zinc ester monomer, the vinyl copper ester monomer or a precursor of betaine type zwitterion as a vinyl !0 antifouling functional monomer; and (2) Synthesis of branch-point-breaking type hyperbranched resin: under inert gas or nitrogen gas atmosphere, under the action of 1 to 20 parts of an initiator and 0.5 to 10 parts of a chain transfer agent, taking 50 to 150 parts by weight of an organic solvent as a reaction medium, and reacting 0 to 70 parts by !5 weight of the vinyl antifouling functional monomer, 1 to 60 parts of a difunctional monomer and 0 to 90 parts of a vinyl monomer at 70 to 120 °C for 8 to 24 hours, to obtain a branch-point-breaking type hyperbranched resin. In the step (1), the synthesis method of the vinyl zinc ester monomer is preferably: at 50 to 140 °C, adding dropwise a mixture of 1 parts by mole of

(meth)acrylic acid and (1 to 1.2) parts by mole of monocarboxylic acid into a mixture of (0.9 to 1.1) parts by mole of zinc-containing compound and solvent within 1 to 4 hours at a uniform velocity, and reacting for 2 to 4 hours upon keeping the temperature, to obtain a vinyl zinc ester monomer, wherein the vinyl zinc ester monomer in a mixed solution of a product has a solid content of 40 to 60%; the zinc-containing compound is changed into a copper-containing compound, and other conditions are the same as synthesis conditions for the vinyl zinc ester monomer, to obtain a vinyl copper ester monomer, wherein the vinyl copper ester monomer in the mixed solution of the product has a solid content of 40 to 60%. In the step (1), the reacting temperature is preferably 75 to 130 °C. In the step (1), the molar ratio of the (meth)acrylic acid, the zinc-containing compound and the monocarboxylic acid is preferably 1:1:1; and the molar ratio of the (meth)acrylic acid, the copper-containing compound and the monocarboxylic acid is preferably 1:1:1. In the step (1), the precursor of betaine type zwitterion is prepared by the following method: subjecting equimolar acrylate containing R 2 group and 2-(methylamino)ethanol to Michael addition reaction at 0 to 50 °C for 6 to 24 h, and thereafter subjecting the resultant as well as equimolar (meth)acrylic chloride !0 to an acylation reaction at 0 to 30 °C for 2 to 9 h, to obtain a precursor of betaine type zwitterion. In the step (2), the synthesis method of the branch-point-breaking type hyperbranched resin is preferably: under inert gas or nitrogen gas atmosphere and at 70 to 120 °C, taking 50 to 150 parts by weight of an organic solvent as a reaction !5 medium, adding dropwise a mixture consisting of 0 to 70 parts by weight of the vinyl antifouling functional monomer, 1 to 60 parts by weight of a difunctional monomer, 0 to 90 parts by weight of a vinyl monomer, 2 to 15 parts by weight of an initiator and 0.5 to 10 parts by weight of a chain transfer agent at a uniform velocity within 4 to 8 hours, then reacting for 0 to 4 hours upon keeping the temperature, adding 0.5 to 2 parts by weight of an initiator at a uniform velocity within 0.5 to 1 hours, and continuing the reaction for 1.5 to 4 hours, to obtain a branch-point-breaking type hyperbranched resin. The above-described branch-point-breaking type hyperbranched resin is used in marine antifouling. The use is preferably to prepare a marine antifouling paint using the above-described branch-point-breaking type hyperbranched resin. Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) The present invention introduces a difunctional monomer and a chain transfer agent during polymerization process, changes a traditional straight chain type high molecular antifouling resin into a hyperbranched structure and uses it in marine antifouling field for the first time. (2) The difunctional monomer used in the present invention each contains chemical bonds which are capable of breaking, and therefore branch points of the prepared hyperbranched resin can likewise break under the attack of seawater, realizing self-renewal of the coating surface. In comparation to a degradable antifouling resin with a main chain containing ester bonds, a fragment formed after branch point breaking of the hyperbranched resin is smaller, and is more easily !0 absorbed by the environment. Moreover, the degree of branching of the material can be enhanced by increasing the content of the difunctional monomer, so that the molecular weight of the fragment is further reduced, marine microplastic pollution can thus be avoided effectively. (3) The branch-point-breaking type hyperbranched resin prepared in the !5 present invention has a side chain with silane ester bonds/zinc ester bonds/copper ester bonds/precursor of betaine type zwitterion, which can be hydrolyzed in seawater, and may further accelerate a hydrolyzation rate of the material in a synergetic effect together with branch point breaking. It can realize rapid polishing even in a static seawater, avoid and inhibit an adhesion of fouling organisms, thereby solve the problem of dependence of a traditional self-polishing material on a navigational speed, and satisfy static antifouling requirements at sea areas with high fouling pressure. (4) Wherein, the hyperbranched silicon-based self-polishing resin has drag reduction function; and zinc/copper ions generated by hydrolyzation of the hyperbranched zinc/copper-based self-polishing resin also have a certain antifouling effect, guaranteeing effective concentrations of active substances on surfaces of ships or marine equipments, and better satisfying antifouling requirement for the facilities like ships with a low navigational speed, offshore oil production platforms and so on. The hyperbranched resin with self-generating zwitterions can release antifouling groups by hydrolyzation action, and the zwitterions generated after hydrolyzation of coating surface impart anti-protein role to the material at the same time, which further enhance antifouling capability of the material, realizing the object of synergetic antifouling with antifouling agent and anti-protein; due to hydrophilic zwitterions are only transformed on the coating surfaces, and therefore defects of the traditional zwitterionic materials, such as great swelling property, poor mechanical property and so on, are overcomed. (5) The present invention regulates glass transition temperature and !0 mechanical property of the material by adding different kinds and different content of a vinyl monomer or a difunctional monomer during polymerization process, and improves solubility of the material in a solvent conventionally used in a marine paint at the same time. (6) The branch-point-breaking type hyperbranched resin provided by the !5 present invention has advantages of high solid content and low viscosity, may reduce an amount of the solvent in the antifouling paint, and thereby reduce VOC; moreover, the preparation method therefor is simple and feasible, low in cost, suitable for industrial production, and has very good development prospect at the marine antifouling paint field.

Detailed description of embodiments The present invention will be further described below in detail in conjunction with examples, but embodiments of the present invention are not limited thereto. In examples of the present application, for an adhesion test, reference is made to ISO 2409-2007 "Paints and Varnishes--Cross cut test"; for a hanging panel experiment, reference is made to GB/T 5370-2007 "Method for testing antifouling panels in shallow submergence"; for a drag reduction performance test, reference is made to GB/T 7791-2014 "Test method for performance of reducing frictional resistance of antifouling coatings". In examples of the present application, for an experimental process of testing release rate of a natural antifoulant (5-octyl-2-furanone), reference is made to Ma C, Zhang W, Zhang G, et al. Environmentally friendly anti-fouling coatings based on biodegradable polymer and natural antifoulant [J]. ACS Sustainable Chemistry & Engineering, 2017, 5:6304-6309. In examples of the present application, for an experimental process of anti-protein adsorption test, reference is made to Ma J, Ma C, Zhang G. Degradable Polymer with Protein Resistance in a marine Environment [J]. Langmuir, 2015, 31(23) :6471-6478. In examples of the present application, for a preparation method for S-vinyl !0 propionate-O-ethyl dithiocarbonate, reference is made to Schmitt J, Blanchard N, Poly J. Controlled synthesis of branched poly(vinyl acetate)s by xanthate-mediated RAFT self-condensing vinyl (co)polymerization [J]. Polymer Chemistry, 2011, 2(10):2231. In examples of the present application, S-cyanomethyl-S-dodecyl !5 trithiocarbonate is purchased from Zhengzhou JACS Chem Product co., Ltd.; and 2-ethyl hexyl 3-mercapto propionate is purchased from Bailingwei Technology co., Ltd. In examples of the present application, polyglycolide with vinyl groups at both terminals is prepared by reacting polyglycolide with hydroxyl groups at both terminals and acryloyl chloride in a molar ratio of 1:2 at 0 °C for 12 hours. In examples of the present application, polycaprolactone with vinyl groups at both terminals is prepared by reacting polycaprolactone with hydroxyl groups at both terminals and acryloyl chloride in a molar ratio of is 1:2 at 0 °C for 12 hours. In examples of the present application, poly(caprolactone-lactide) with vinyl groups at both terminals is prepared by reacting poly(caprolactone-lactide) with hydroxyl groups at both terminals and acryloyl chloride in a molar ratio of is 1:2 at 0 °C for 12 hours. In examples of the present application, for a preparation method for diacrylamide containing oxime/semicarbazone/hydrazone structure, reference is made to Sims M B, patel K Y, Bhatta M, et al. Harnessing Imine Diversity To Tune Hyperbranched Polymer Degradation [J]. Macromolecules, 2018, 51:356-363. In examples of the present application, precursors of betaine type zwitterion are all prepared by the following method: subjecting equimolar acrylate containing R2 group and 2-(methylamino)ethanol to Michael addition reaction at 0 °C for 12 h, and thereafter subjecting the resultant as well as equimolar (meth)acrylic chloride to acylation reaction at 0 °C for 6 h, to obtain a precursor of betaine type zwitterion. Example 1 Under a condition of stirring, 50 g xylene and 35 g propylene glycol methyl ether were added into a reacting vessel; the temperature was increased to 90 °C under nitrogen gas atmosphere; a mixture consisting of 50 g bis(trimethyl siloxanyl) methyl silyl methacrylate(purchased from American Momentive Co.), 20 g ethyl acrylate, 30 g polyglycolide with vinyl groups at both terminals having !5 a molecular weight of 500 g/mol, 5 g azobisisobutyronitrile, 2 g diisopropyl xanthogen disulfide and 10 g xylene was added dropwise within 6 hours; after adding dropwise was finished, a mixture of 0.5 g di-t-butyl peroxide and 10 g xylene was continued to be added dropwise within 30 minutes, and then stirring was performed for 1.5 hours, to obtain a hyperbranched silicon-based self-polishing resin. In the present Example, the hyperbranched silicon-based self-polishing resin has a number-average molecular weight Mn of 4.5x10 3 g/mol, a silicon content of 4.6%, and an acid value of 92 mg KOH/g. Paint film thereof has an adhesion of 2 grade, and a drag reducing rate of 3.5%. A varnish was prepared by compounding the hyperbranched silicon-based self-polishing resin with 10 wt% 5-octyl-2-furanone, and a release rate of the 5-octyl-2-furanone in the varnish measured by High Performance Liquid Chromatography was 25 g-cm 2d-. In the South Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 95 points after 7 months. Example 2 Under a condition of stirring, 20 g xylene and 70 g methyl isobutyl ketone were added into a reacting vessel; the temperature was increased to 95 °C under nitrogen gas atmosphere; a mixture consisting of 70 g tri-n-butyl silyl methacrylate(purchased from Bailingwei Technology co., Ltd.), 30 g magnesium acrylate, 2 g azobisisovaleronitrile, 5 g S-(thiobenzoyl) thioglycolic acid, and 10 g methyl isobutyl ketone was added dropwise at a uniform velocity within 8 hours; after adding dropwise was finished, the temperature was kept for 3 hours, then 1 g azobisisobutyronitrile and 10 g xylene were added dropwise at a uniform velocity !0 within 30 minutes, and stirring was performed for 4 hours, to obtain a hyperbranched silicon-based self-polishing resin. In the present Example, the hyperbranched silicon-based self-polishing resin has a number-average molecular weight Mn of 4.5x103 g/mol, a silicon content of 6.9%, and an acid value of 138 mg KOH/g. Paint film thereof has an adhesion of !5 1 grade, and a drag reducing rate of 4.8%. A varnish was prepared by compounding the hyperbranched silicon-based self-polishing resin with 10 wt% 5-octyl-2-furanone, and a release rate of the 5-octyl-2-furanone in the varnish measured by High Performance Liquid Chromatography was 45pg cm 2d-. In the

East Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 97 points after 8 months. Example 3 (1)Synthesis of vinyl zinc ester monomer: 10.4 g zinc oxide, 20 g propylene glycol methyl ether and 7 g xylene were added into a reacting vessel, and heated to 75 °C. A mixture of 9.3 g acrylic acid, 7.7 g acetic acid and 1 g deionized water was added dropwise at a constant rate, controling the dropwise addition within 3 hours; after adding dropwise was finished, reaction was performed upon keeping the temperature for 2 hours, and the solvent was removed by rotary evaporation to obtain a vinyl zinc ester monomer; (2)Synthesis of hyperbranched zinc-based self-polishing resin: Under a condition of stirring, 50 g xylene and 35 g propylene glycol methyl ether were added into a reacting vessel; the temperature was increased to 90 °C under nitrogen gas atmosphere; a mixture consisting of 25 g vinyl zinc ester monomer, 30 g 2-methoxy ethyl methacrylate, 15 g methyl methacrylate, 30 g polycaprolactone with vinyl groups at both terminals having a molecular weight of 500 g/mol, 5 g azobisisobutyronitrile, 2 g methyl-styrene dimer and 10 g xylene was added dropwise at a uniform velocity within 6 hours; after adding !0 dropwise was finished, a mixture of 0.5 g di-t-butyl peroxide and 10 g xylene was continued to be added dropwise at a uniform velocity, controlling the dropwise addition within 30 minutes; and stirring was performed for reacting 1.5 hours, to obtain a hyperbranched zinc-based self-polishing resin. In the present Example, the hyperbranched zinc-based self-polishing resin !5 has a number-average molecular weight Mn of 2.5x10' g/mol, a zinc content of 8.4 %, and an acid value of 143 mg KOH/g. Paint film thereof has an adhesion of 1 grade. A varnish was prepared by compounding the hyperbranched zinc-based self-polishing resin with 10 wt% 5-octyl-2-furanone, and a release rate of

5-octyl-2-furanone in the varnish measured by High Performance Liquid Chromatography was 30 pg-cm 2d-. In the South Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 97 points after 10 months. Example 4 (1)Synthesis of vinyl zinc ester monomer: 6.0 g zinc oxide, 30 g xylene and 6 g iso-propanol were added into a reacting vessel, and heated to 80 °C. A mixture of 5.3 g acrylic acid, 25 g naphthenic acid(acid value 165) was added dropwise at a constant rate, controlling the dropwise addition within 3 hours; after adding dropwise was finished, reaction was performed upon keeping the temperature for 2 hours, and the solvent was removed by rotary evaporation to obtain a vinyl zinc ester monomer; (2)Synthesis of hyperbranched zinc-based self-polishing resin: Under a condition of stirring, 20 g xylene and 70 g methyl isobutyl ketone were added into a reacting vessel; the temperature was increased to 95 °C under nitrogen gas atmosphere; a mixture consisting of 35 g vinyl zinc ester monomer, 20 gmethyl acrylate, 20 g butyl acrylate, 20 g cyclohexyl methacrylate, 5 g poly(caprolactone-lactide) with vinyl groups at both terminals having a molecular weight of 800 g/mol, 2 g azobisisovaleronitrile, 5 g S-cyanomethyl-S-dodecyl !0 trithiocarbonate and 10 g methyl isobutyl ketone was added dropwise at a uniform velocity within 8 hours; after adding dropwise was finished, the temperature was kept for 3 hours, 1 g azobisisobutyronitrile and 10 g xylene were continued to be added dropwise at a uniform velocity, controlling the dropwise additon within 30 minutes; and stirring was performed for reacting 4 hours, to obtain a !5 hyperbranched zinc-based self-polishing resin. In the present Example, the hyperbranched zinc-based self-polishing resin has a number-average molecular weight Mn of 3.Ox103 g/mol, a zinc content of 4.8%, and an acid value of 83 mg KOH/g. Paint film thereof has an adhesion of 1 grade. A varnish was prepared by compounding the hyperbranched zinc-based self-polishing resin with 10 wt% 5-octyl-2-furanone, and a release rate of 5-octyl-2-furanone in the varnish measured by High Performance Liquid 2 Chromatography was 15 pg-cm d-. In the East Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 85 points after 12 months. Example 5 (1)Synthesis of vinyl copper ester monomer: 15.6 g copper hydroxide, 70 g tolyene and 6g isobutanol were added into a reacting vessel, and heated to 90 °C. A mixture of 11.6 g acrylic acid, 48.6 g rosin acid was added dropwise at a uniform velocity within 3 hours; after adding dropwise was finished, reaction was performed upon keeping the temperature for 2 hours, and the solvent was removed by rotary evaporating to obtain a vinyl copper ester monomer; (2) Synthesis of hyperbranched copper-based self-polishing resin: Under a condition of stirring, 50 g xylene and 40 g butyl acetate were added into a reacting vessel; the temperature was increased to 100 °C under nitrogen gas atmosphere; a mixture consisting of 70 g vinyl copper ester monomer, 30 g diacrylamide containing oxime structure, 3 g t-butyl peroxy-2-ethyl hexanoate, 5 !0 g S-vinyl propionate-O-ethyl dithiocarbonate and 10 g butyl acetate was added dropwise at a uniform velocity within 5 hours; after adding dropwise was finished, the temperature was kept for 2 hours, 2 g benzoyl peroxide and 10 g xylene were continued to be added dropwise at a uniform velocity, controlling the dropwise additon within 30 minutes; and stirring was performed for reacting 4 hours, to !5 obtain a hyperbranched copper-based self-polishing resin. In the present Example, the hyperbranched copper-based self-polishing resin has a number-average molecular weight Mn of 1.2x103 g/mol, a copper content of 14.6%, and an acid value of 206 mg KOH/g. Paint film thereof has an adhesion of

1 grade. A varnish was prepared by compounding the hyperbranched copper-based self-polishing resin with 10 wt% 5-octyl-2-furanone, and a release rate of 5-octyl-2-furanone in the varnish measured by High Performance Liquid Chromatography was 40 pg-cm 2d-. In the Yellow Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 90 points after 12 months. Example 6 (1)Synthesis of vinyl copper ester monomer: 10.9 g acetic acidcopper, 30 g tolyene and 5 g n-butanol were added into a reacting vessel, and heated to 130 °C. A mixture of 4.3 g acrylic acid and 17.0 g stearic acid was added dropwise at a constant rate, controlling the dropwise addition within 3 hours; after adding dropwise was finished, reaction was performed upon keeping the temperature for 2 hours, and the solvent was removed by rotary evaporating to obtain a vinyl copper ester monomer; (2)Synthesis of hyperbranched copper-based self-polishing resin: Under a condition of stirring, 70 g propylene glycol methyl ether and 10 g ethyl acetate were added into a reacting vessel; the temperature was increased to 105 °C under nitrogen gas atmosphere; a mixture consisting of 25 g vinyl copper ester monomer, 20 g hydroxypropyl methacrylate, 30 g 4-t-butyl cyclohexyl !0 methacrylate, 25 g diacrylamide containing semicarbazone structure, 12 g di-t-butyl peroxide, 2.5 g 2-ethyl hexyl 3-mercapto propionate and 10 g propylene glycol methyl ether was added dropwise at a uniform velocity within 4 hours; after adding dropwise was finished, the temperature was kept for 2 hours, 1 g t-butyl peroxy-2-ethyl hexanoate and 10 g xylene were continued to be added !5 dropwise at a uniform velocity, controlling the dropwise additon within 30 minutes; and stirring was performed for reacting 2 hours, to obtain a hyperbranched copper-based self-polishing resin. In the present Example, the hyperbranched copper-based self-polishing resin has a number-average molecular weight Mn of 2.6x10 3 g/mol, a copper content of 4.7%, and an acid value of 67 mg KOH/g. Paint film thereof has an adhesion of 1 grade. A varnish was prepared by compounding the hyperbranched copper-based self-polishing resin with 10 wt% 5-octyl-2-furanone, and a release rate of 5-octyl-2-furanone in varnish measured by High Performance Liquid 2 Chromatography was 22 pg-cm d-. In the Bohai Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 88 points after 11 months. Example 7 Under a condition of stirring, 35 g xylene and 50 g methyl isobutyl ketone were added into a reacting vessel; the temperature was increased to 95 °C under nitrogen gas atmosphere; a mixture consisting of 30 g precursor of betaine type zwitterion with R 1 group being methyl and R2 group being ethyl, 50 g methyl methacrylate, 10 g manganese acrylate, 10 g magnesium methacrylate, 9.5 g azobisisobutyronitrile, 1 g dodecyl mercaptan and 15 g xylene was added dropwise at a uniform velocity within 6 hours; after adding dropwise was finished, the temperature was kept for 2 hours; 0.5 g azobisisobutyronitrile and 10 g xylene were added dropwise at a uniform velocity within 30 minutes; and stirring was performed for 4 hours, to obtain a hyperbranched self-polishing resin !0 self-generating zwitterion. In the present Example, the hyperbranched self-polishing resin self-generating zwitterion has a number-average molecular weight Mn of 3.6x10 3 g/mol. Paint film thereof has an adhesion of 1 grade. An adsorption frequency of the resin for 1 mg/mL Fibrinogen measured by Quartz Crystal Microbalance with !5 Dissipation (QCM-D) was 50Hz. In the East Sea area of China, a hanging panel test in shallow sea was carried out, and the fouling evaluation was 85 points after 12 months.

Example 8 Under a condition of stirring, 50 g propylene glycol methyl ether and 45 g butyl acetate were added into a reacting vessel; the temperature was increased to 80 °C under nitrogen gas atmosphere, a mixture consisting of 40 g precursor of betaine type zwitterion with R 1 group being methyl and R2 group being zinc acetate, 10 g precursor of betaine type zwitterion with R1 group being methyl and R2 group being triclosan, 40 g hydroxyethyl methacrylate, 10 g diacrylamide with R group being hydrazone structure, 1 g di-t-butyl peroxide, 5 g dibenzyl trithiocarbonate and 5 g propylene glycol methyl ether was added dropwise at a uniform velocity within 8 hours; after adding dropwise was finished, the temperature was kept for 2 hours; 1 g azobisisobutyronitrile and 10 g xylene was added dropwise at a uniform velocity within 30 minutes; and stirring was performed for 4 hours, to obtain a hyperbranched self-polishing resin self-generatingzwitterion. In the present Example, the hyperbranched self-polishing resin self-generating zwitterion has a number-average molecular weight Mn of 4.3x103 g/mol. Paint film thereof has an adhesion of 1 grade. An adsorption frequency of the resin for 1 mg/mL Fibrinogen measured by Quartz Crystal Microbalance with Dissipation (QCM-D) was 0Hz. In the Yellow Sea area of China, a hanging panel !0 test in shallow sea was carried out, and the fouling evaluation was 90 points after 16 months.

The above-described examples are preferred embodiments of the present invention, but embodiments of the present invention are not limited to the !5 above-described examples, any other changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principle of the present invention, should all be equivalent replacement modes, and are all included in the protection scope of the present invention.

Claims

Claims 1. A branch-point-breaking type hyperbranched resin, characterized in that, it is prepared from the following components in terms of parts by weight: a vinyl antifouling functional monomer 25 to 70 parts, a difunctional monomer 1 to 60 parts, a vinyl monomer 0 to 90 parts, an initiator I to 20 parts, a chain transfer agent 0.5 to 10 parts, and an organic solvent 50 to 150 parts; the vinyl antifouling functional monomer is one of a vinyl silane ester monomer, a vinyl zinc ester monomer, a vinyl copper ester monomer and a precursor of betaine type zwitterion; the vinyl silane ester monomer is at least one of acryloxy trimethyl silane, trimethyl silyl methacrylate, acryloxy triethyl silane, triethyl silyl methacrylate, acryloxy triisopropyl silane, triisopropyl silyl methacrylate, acryloxy triphenyl silane, triphenyl silyl methacrylate, acryloxy tri-n-butyl silane, tri-n-butyl silyl methacrylate, acryloxy t-butyl dimethyl silane, t-butyl dimethyl silyl methacrylate, acryloxy bis(trimethyl siloxanyl) methyl silane and bis(trimethyl siloxanyl) methyl silyl methacrylate; the vinyl zinc ester monomer is prepared by the following method: taking a solvent as a reaction medium, and reacting a zinc-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2), wherein the vinyl zinc ester monomer in a mixed solution of a product has a solid content of 40 to 60%; the vinyl copper ester monomer is prepared by the following method: taking a solvent as a reaction medium, and reacting a copper-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2), wherein the vinyl copper ester monomer in the mixed solution of the product has a solid content of 40 to 60%; a general structural formula of the precursor of betaine type zwitterion is shown as the following formula: II 0 R1 O N O'..R 2 0 I wherein, R 1 represents H or CH3, R2 represents one of alkyl having a number of carbon atoms of1 to 12, methoxy-terminated polyethylene glycol substituent group, isothiazolinones substituent group, triclosan substituent group, paeonol substituent group, camptothecin substituent group, N-(2,4,6-trichloro phenyl) maleimide substituent group, bromopyrrole nitrile substituent group, donaxine substituent group, capsaicin substituent group, hydroxyindoles substituent group, R3 COOZn, R4 COOCu or (R) 3 Si, wherein R 3 and R4 are both saturated alkyl having a number of carbon atoms of 1 to 12, unsaturated alkyl having a number of carbon atoms of 1 to 12, saturated cycloalkyl having a number of carbon atoms of 1 to 12 or unsaturated cycloalkyl having a number of carbon atoms of 1 to 12, R5 is uniformly or differently selected from alkyl having a number of carbon atoms of 1 to 8, and the methoxy-terminated polyethylene glycol has a degree of polymerization n=2 to 24.
2. The branch-point-breaking type hyperbranched resin according to claim 1, characterized in that, it is prepared from the following components in terms of parts by weight: the vinyl antifouling functional monomer 25 to 70 parts, the difunctional monomer 1 to 30 parts, the vinyl monomer 0 to 40 parts, the initiator 3 to 13 parts, the chain transfer agent 2 to 5 parts, and the organic solvent 100 to 110 parts, the zinc-containing compound is at least one of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate and zinc propionate; and the copper-containing compound is at least one of copper oxide, copper hydroxide, copper chloride, copper acetate and copper propionate; and the monocarboxylic acid is at least one of formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, oleic acid, palmitic acid and rosin acid.
3. The branch-point-breaking type hyperbranched resin according to claims 1 or 2, characterized in that, the difunctional monomer is at least one of (meth)acrylates containing a metallic element, aliphatic polyesters with vinyl groups at both terminals, schiff bases and compounds containing disulfide bonds; and the vinyl monomer is at least one of (meth)acrylates, (meth)acrylates containing a terminal hydroxyl group, cyclic hydrocarbon (meth)acrylates and polyolefin glycol (meth)acrylates.
4. The branch-point-breaking type hyperbranched resin according to claim 3, characterized in that, the (meth)acrylates containing a metallic element are at least one of magnesium acrylate, magnesium methacrylate, magnesium acrylate methacrylate, manganese acrylate, manganese methacrylate, manganese acrylate methacrylate, zinc acrylate, zinc methacrylate, zinc acrylate methacrylate, copper acrylate, copper methacrylate, copper acrylate methacrylate, iron acrylate, iron methacrylate, and iron acrylate methacrylate; the aliphatic polyesters with vinyl groups at both terminals are at least one of polyprolylene carbonate with vinyl groups at both terminals, polytrimethylene carbonate with vinyl groups at both terminals, poly(trimethylene carbonate-caprolactone) with vinyl groups at both terminals, poly(caprolactone-glycolide) with vinyl groups at both terminals, poly(caprolactone-lactide) with vinyl groups at both terminals, poly(caprolactone-ethylene glycol) with vinyl groups at both terminals, poly(lactide-glycolide) with vinyl groups at both terminals, poly(lactide-ethylene glycol) with vinyl groups at both terminals, poly 3-hydroxy butyrate with vinyl groups at both terminals, poly(3-hydroxy butyrate-co-3-hydroxy valerate) with vinyl groups at both terminals, polyethylene glycol adipate with vinyl groups at both terminals, polydiethylene glycol adipate with vinyl groups at both terminals, polybutylene glycol adipate with vinyl groups at both terminals, polyhexylene glycol adipate with vinyl groups at both terminals, polybutylene glycol succinate with vinyl groups at both terminals, polyorthoesters with vinyl groups at both terminals, polyanhydrides with vinyl groups at both terminals, polyphosphate with vinyl groups at both terminals, polycaprolactone with vinyl groups at both terminals, polylactide with vinyl groups at both terminals and polyglycolide with vinyl groups at both terminals; and molecular weights of the aliphatic polyesters with vinyl groups at both terminals are all 1x102 to 5x10' g/mol; the structures of the Schiff bases and compounds containing disulfide bonds are shown as follows:

Schiffbases HN NH NH H NH

-N N -. A N N H

diacrylamide containing oxime diacrylamide containing semicarbazone diacrylamide containing hydrazone structure

compounds containing H' disulfide bonds H NN'- bis(acroloyl)cystamine N,N'-diallyl dithiodipropionamide

the vinyl monomer of the (meth)acrylates is at least one of methyl acrylate, ethyl acrylate, 2-methoxy ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methoxy ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate and octadecyl methacrylate; the (meth)acrylates containing the terminal hydroxyl group is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the cyclic hydrocarbon (meth)acrylates is at least one of cyclohexyl acrylate, 1-methylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, cyclohexyl methacrylate, 1-methylcyclohexyl methacrylate and 4-t-butyl cyclohexyl methacrylate; and the polyolefin glycol (meth)acrylates is at least one of polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol methacrylate and polypropylene glycol methacrylate, and the polyolefin glycol (meth)acrylates all have a degree of polymerization of 1 to 10.
5. The branch-point-breaking type hyperbranched resin according to claim 3, characterized in that, the initiator is at least one of phosphonitrile, phosphonitrile salt, phosphonitrile oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide and t-butyl peroxy-2-ethyl hexanoate; the chain transfer agent is at least one of mercaptan, dithioester, trithioester and methyl-styrene dimer; the mercaptan is at least one of n-dodecyl alkyl mercaptan, t-dodecyl alkyl mercaptan, mercapto ethanol, mercapto acetic acid, isooctyl 3-mercapto propionate, 2-ethyl hexyl 3-mercapto propionate and pentaerythritol tetrakis(3-mercaptopropionate); the dithioester is at least one of cumenyl benzodithioate, 2-cyano isopropyl benzodithioate, methyl benzodithioate, phenethyl benzodithioate, benzyl benzodithioate phenylethyl phenylethane dithioate, S-(thiobenzoyl) thioglycolic acid, S-acetonyl-O-ethyl dithiocarbonate, S-vinyl propionate-O-ethyl dithiocarbonate, 2-cyanopropyl-4-cyano benzodithioate, 2-cyanopropyl-N-methyl-N-(4-pyridine) amino dithiocarbonate, methyl-2-[methyl(4-pyridine) dithiocarbonate] propionate, 4-cyano-4-(thiobenzoyl) pentanoic acid, cyanomethyl methyl(phenyl) carbamodithioate, 2-phenyl-2-propyl benzodithioate,

1-cyano-1-methyl-4-oxo-4-(2-thio-3-thiazole alkyl) butyl ester, bis(thiobenzoyl) dithioether, tetramethylthiuram disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, di-n-butyl xanthogen disulfide and diisobutyl xanthogen disulfide; and the trithioester is at least one of 2-cyano-2-propyl dodecyl trithiocarbonate, dibenzyl trithiocarbonate, S-cyanomethyl-S-dodecyl trithiocarbonate, 4-cyano-4-(dodecylsulfanylthiocarbonyl) sulfanylpentanoic acid, bis(carboxy methyl) trithiocarbonate, methyl 2-[[(dodecyl mercapto)thiomethyl]thio]-2-methyl benzoate, 2-(((dodecylthio)carbonothioyl)thio)-2-methyl propionic acid and dimethyl trithiocarbonate.
6. The branch-point-breaking type hyperbranched resin according to claim 3, characterized in that, the organic solvent in the branch-point-breaking type hyperbranched resin ingredients is at least one of hydrocarbons solvent, alcohols solvent, ketones solvent and esters solvent; and the solvents in the vinyl zinc ester monomer and the vinyl copper ester monomer are both at least one of hydrocarbons solvent, alcohols solvent and water.
7. The branch-point-breaking type hyperbranched resin according to claim 6, characterized in that, the organic solvent in the branch-point-breaking type hyperbranched resin ingredients is at least one of tolyene, xylene, iso-propanol, n-butanol, isobutanol, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone, cyclohexanone, ethyl acetate and butyl acetate; and the solvents in the vinyl zinc ester monomer and the vinyl copper ester monomer are both at least one of toluene, xylene, isopropanol, n-butanol, isobutanol and propylene glycol methyl ether.
8. The branch-point-breaking type hyperbranched resin according to claim 2, characterized in that, when the vinyl antifouling functional monomer is the vinyl silane ester monomer, the branch-point-breaking type hyperbranched resin has a silicon element content of 1% to 15%; when the vinyl antifouling functional monomer is the vinyl zinc ester monomer, the branch-point-breaking type hyperbranched resin has a zinc element content of 0.5% to 20%; and when the vinyl antifouling functional monomer is the vinyl silyl copper ester monomer, the branch-point-breaking type hyperbranched resin has a copper element content of 1% to 20%; and the branch-point-breaking type hyperbranched resin has an acid value of 30 to 350 mg KOH/g, and a number-average molecular weightM of 1000 to 10000.
9. The preparation method for the branch-point-breaking type hyperbranched resin claims 1, characterized in that, it includes the following steps: (1) Synthesis of vinyl zinc ester monomer or vinyl copper ester monomer: taking a solvent as a reaction medium, and reacting a zinc-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2) at 50 to 140 °C for 3 to 8 hours, to obtain a vinyl zinc ester monomer; taking a solvent as a reaction medium, and reacting a copper-containing compound, (meth)acrylic acid and a monocarboxylic acid in a molar ratio of (0.9 to 1.1):1:(1 to 1.2) at 50 to 140 °C for 3 to 8 hours, to obtain a vinyl copper ester monomer; and taking a vinyl silane ester monomer, the vinyl zinc ester monomer, the vinyl copper ester monomer or a precursor of betaine type zwitterion as a vinyl antifouling functional monomer; and (2) Synthesis of branch-point-breaking type hyperbranched resin: under inert gas or nitrogen gas atmosphere, under the action of 1 to 20 parts of an initiator and 0.5 to 10 parts of a chain transfer agent, taking 50 to 150 parts by weight of an organic solvent as a reaction medium, and reacting 25 to 70 parts by weight of the vinyl antifouling functional monomer, 1 to 60 parts of a difunctional monomer and 0 to 90 parts of a vinyl monomer at 70 to 120 °C for 8 to 24 hours, to obtain a branch-point-breaking type hyperbranched resin.
10. The preparation method for the branch-point-breaking type hyperbranched resin according to claim 9, characterized in that, the synthesis method of the vinyl zinc ester monomer in the step (1) is: adding dropwise a mixture of 1 parts by mole of (meth)acrylic acid and 1 to 1.2 parts by mole of monocarboxylic acid into a mixture of 0.9 to 1.1 parts by mole of zinc-containing compound and solvent at a uniform velocity at 50 to 140 °C within 1 to 4 hours, and reacting the same for 2 to 4 hours upon keeping the temperature, to obtain a vinyl zinc ester monomer, wherein the vinyl zinc ester monomer in a mixed solution of a product has a solid content of 40 to 60%; changing the zinc-containing compound into a copper-containing compound, and other conditions are the same as the synthesis conditions for the vinyl zinc ester monomer, to obtain a vinyl copper ester monomer, wherein the vinyl copper ester monomer in the mixed solution of the product has a solid content of 40 to %; the precursor of betaine type zwitterion in the step (1) is prepared by the following method: subjecting equimolar acrylate containing R2 group and 2-(methylamino) ethanol to Michael addition reaction at 0 to 50 °C for 6 to 24 h, and thereafter subjecting the resultant as well as equimolar (meth)acrylic chloride to acylation reaction at 0 to 30 °C for 2 to 9 h, to obtain the precursor of betaine type zwitterion; and the synthesis method of the branch-point-breaking type hyperbranched resin in the step (2) is: under inert gas or nitrogen gas atmosphere and at 70 to 120 °C, taking 50 to 150 parts by weight of an organic solvent as a reaction medium, adding dropwise a mixture consisting of 0 to 70 parts by weight of the vinyl antifouling functional monomer, 1 to 60 parts by weight of a difunctional monomer, 0 to 90 parts by weight of a vinyl monomer, 2 to 15 parts by weight of an initiator and 0.5 to 10 parts by weight of a chain transfer agent at a uniform velocity within 4 to 8 hours, then reacting the same for 0 to 4 hours upon keeping the temperature, further adding 0.5 to 2 parts by weight of an initiator at a uniform velocity within 0.5 to 1 hours, and continuing the reaction for 1.5 to 4 hours, to obtain the branch-point-breaking type hyperbranched resin, wherein a sum of the time of adding dropwise the mixture at a uniform velocity, the time of reaction performed upon keeping the temperature, the time of adding the initiator at a uniform velocity and the time of continuing the reaction is 8 to 24 hours.
11. A use of the branch-point-breaking type hyperbranched resin according to any one of claims 1 to 8 in marine antifouling.