阅读说明：本技术 一种可降解超支化树脂及其制备方法与应用 (degradable hyperbranched resin and preparation method and application thereof ) 是由 张广照 马春风 潘健森 谢庆宜 于 2019-07-18 设计创作，主要内容包括：本发明属于海洋防污材料技术领域,公开了一种可降解超支化树脂及其方法与应用。所述可降解超支化树脂由以下按重量份数计的组分制备而成：环状单体1～100份,乙烯基防污功能单体0～60份,双官能度单体0～60份,乙烯基单体0～70份,引发剂1～20份,链转移剂0.5～10份,有机溶剂50～150份。本发明在聚合过程中引入双官能度单体和链转移剂,将传统直链型高分子防污树脂制备成超支化结构并首次将其应用于海洋防污领域。此外,该树脂还具有超支化聚合物高固含量低黏度的优点且制备方法简单可行,成本较低,适合工业化生产,在海洋防污涂料领域具有很好的发展前景。(The invention belongs to the technical field of marine antifouling materials, and discloses degradable hyperbranched resin and a method and application thereof. The degradable hyperbranched resin is prepared from the following components in parts by weight: 1-100 parts of cyclic monomer, 0-60 parts of vinyl antifouling functional monomer, 0-60 parts of bifunctional monomer, 0-70 parts of vinyl monomer, 1-20 parts of initiator, 0.5-10 parts of chain transfer agent and 50-150 parts of organic solvent. According to the invention, bifunctional monomers and chain transfer agents are introduced in the polymerization process, the traditional straight-chain type polymer antifouling resin is prepared into a hyperbranched structure, and the hyperbranched structure is applied to the field of marine antifouling for the first time. In addition, the resin also has the advantages of high solid content and low viscosity of the hyperbranched polymer, and the preparation method is simple and feasible, has low cost, is suitable for industrial production, and has good development prospect in the field of marine antifouling paint.)

1. the degradable hyperbranched resin is characterized by being prepared from the following components in parts by weight:

2. The degradable hyperbranched resin of claim 1, which is prepared from the following components in parts by weight:

3. The degradable hyperbranched resin of claim 1 or 2, wherein:

The cyclic monomer is at least one of the following compounds (1) to (38): (1) glycolide, (2) lactide, (3) epsilon-caprolactone, (4) 2-methyl-epsilon-caprolactone, (5) 2-chloro-epsilon-caprolactone, (6) gamma-butyrolactone, (7) delta-valerolactone, (8) gamma-valerolactone, (9) ethylene carbonate, (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) gamma-glycidoxypropyltrimethoxysilane, (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-dioxolane, (25)2, 5-dimethylene-1, 3-dioxolane, (26) 2-methylene-5-phenyl-1, 3-dioxan, (27) 2-methylene-4-alkyl-1, 3-dioxan, (28) 2-methylene-1, 3-dioxepane, (29) 2-methylene-5-alkyl-1, 3-dioxepane, (30) 2-methylene-4, 7-dimethyl-1, 3-dioxepane, (31) 2-methylene-1, 3-dioxo-5, 6-benzocycloheptane, (32) 2-methylene-5-phenyl-1, 3-dioxepane, (33) 2-ethylidene-1, 3-dioxepane, (34) 2-methylene-1, 3-dioxo-5-cycloheptene, (35) 2-ethylidene-4-alkyl-1, 3-dioxolane, (36) 2-ethylidene-1, 3-dioxan-e, (37) 2-allylidene-4-phenyl-1, 3-dioxolane and (38) 2-ethylidene-1, 3-dioxo-5, 6-benzocycloheptane;

The structural formulae of the compounds (1) to (38) are as follows:

4. The degradable hyperbranched resin of claim 1 or 2, wherein:

The vinyl antifouling functional monomer is at least one of a vinyl silane ester monomer, a vinyl zinc ester monomer, a vinyl copper ester monomer and a betaine type zwitter-ion precursor;

the bifunctional monomer is a functional monomer with vinyl groups at two ends;

the vinyl monomer is at least one of (methyl) acrylate, hydroxyl-terminated (methyl) acrylate, cyclic hydrocarbon (methyl) acrylate and polyolefin glycol (methyl) acrylate.

5. The degradable hyperbranched resin of claim 4, wherein:

In the vinyl antifouling functional monomer, the vinyl silane ester monomer is at least one of acryloxytrimethylsilane, trimethylsilyl methacrylate, acryloxytriethylsilane, triethylsilyl methacrylate, acryloxytriisopropylsilane, triisopropylsilyl methacrylate, acryloxytriphenylsilane, triphenylsilyl methacrylate, acryloxytri-n-butylsilane, tri-n-butylsilyl methacrylate, acryloxytert-butyldimethylsilane, tert-butyldimethylsilyl methacrylate, acryloxybis (trimethylsiloxy) methylsilane, and bis (trimethylsiloxy) methylsilane methacrylate;

The structural general formula of the betaine type zwitter-ion precursor is shown as the following formula:

wherein R1 represents H or CH3, and R2 represents an alkyl group having 1 to 12 carbon atoms, methoxy-terminated polyethylene glycol or an antifouling group.

6. the degradable hyperbranched resin of claim 4, wherein:

The bifunctional monomer is at least one of (methyl) acrylate, metal element-containing (methyl) acrylate, aliphatic polyester with vinyl at two ends, Schiff bases and disulfide bond-containing compounds;

among the vinyl monomers, the vinyl monomer of the (meth) acrylate is at least one of methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate, stearate acrylate, methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate and stearate methacrylate; the (methyl) acrylate containing terminal hydroxyl is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the cyclic hydrocarbon ester of (meth) acrylic acid is at least one of phenyl acrylate, cyclohexyl acrylate, 1-methylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, phenyl methacrylate, cyclohexyl methacrylate, 1-methylcyclohexyl methacrylate, and 4-tert-butylcyclohexyl methacrylate; the (meth) acrylic polyolefin glycol esters are at least one of polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol methacrylate and polypropylene glycol methacrylate.

7. The degradable hyperbranched resin of claim 1 or 2, wherein:

The initiator is at least one of phosphazene, phosphorus nitrile salt, phosphonitrile oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate;

The chain transfer agent is at least one of mercaptan, dithioester, trithioester and 2, 4-diphenyl-4-methyl-1-pentene;

The organic solvent is at least one of hydrocarbon solvent, alcohol solvent, ketone solvent and ester solvent.

8. The degradable hyperbranched resin of claim 7, wherein:

in the chain transfer agent, the mercaptan is at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, thioglycolic acid, isooctyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate and quaternary cyclopentadienyl tetraethanol tetra (3-mercaptopropionate); the dithioester is isopropylphenyl dithiobenzoate, 2-cyanoisopropyl dithiobenzoate, methyl dithiobenzoate, phenethyl dithiobenzoate, benzyl dithiobenzoate, phenethyl dithiophenylacetate, S- (thiobenzoyl) thioacetic acid, S-acetonyl-O-ethyl dithiocarbonate, S-propionyloxy-O-ethyl dithiocarbonate, 2-cyanopropyl-4-cyanodithiobenzoate, 2-cyanopropyl-N-methyl-N- (4-pyridine) aminodithiocarbonate, methyl-2- [ methyl (4-pyridine) dithiocarbonate ] propionate, 4-cyano-4- (thiobenzoyl) pentanoic acid, methyl-2- [ methyl (4-pyridine) dithiocarbonate ] propionate, methyl-2- [ methyl- (4-pyridine) dithiocarbonate, ethyl-2-propionyloxy-4- (thiobenzoyl) pentanoic acid, ethyl-2-propionyloxy-ethyl-, At least one of methyl (phenyl) aminodithioformate, 2-phenylpropyl-2-dithiobenzene, 1-cyano-1-methyl-4-oxo-4- (2-thio-3-thiazolidinyl) butyl ester, bis (thiobenzoyl) disulfide, tetramethylthiuram disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, di-n-butylxanthogen disulfide, and isobutylxanthogen disulfide; the trithiocarbonate is at least one of 2-cyano-2-propyl dodecyl trithiocarbonate, dibenzyl trithiocarbonate, S-cyanomethyl-S-dodecyl trithiocarbonate, 4-cyano-4- (dodecyl sulfanyl thiocarbonyl) thiovaleric acid, bis (carboxymethyl) trithiocarbonate, methyl 2- [ [ (dodecyl mercapto) thiomethyl ] thio ] -2-methylbenzoate, 2- (dodecyl sulfanyl thiocarbonylthio) -2-methylpropionic acid and dimethyl trithiocarbonate;

The organic solvent is at least one of toluene, xylene, isopropanol, n-butanol, isobutanol, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone, cyclohexanone, ethyl acetate and butyl acetate.

9. The method for preparing the degradable hyperbranched resin according to any one of claims 1 to 8, wherein the method comprises the following steps:

In an inert gas or nitrogen atmosphere, an organic solvent is used as a reaction medium, and under the action of an initiator and a chain transfer agent, a vinyl antifouling functional monomer, a bifunctional monomer, a cyclic monomer and a vinyl monomer react at 70-120 ℃ for 8-24 hours to obtain the degradable hyperbranched resin.

10. The use of the degradable hyperbranched resin according to any one of claims 1 to 8 in marine antifouling.

Technical Field

The invention belongs to the technical field of marine antifouling materials, and particularly relates to degradable hyperbranched resin and a preparation method and application thereof.

Background

The marine biofouling problem can cause huge economic loss and potential safety hazard, so marine antifouling is a subject closely related to the national important requirements of environment, energy, national defense and the like, and has important significance. At present, the coating of marine antifouling paint is the most economical, most convenient and commonly used method for solving the fouling problem of marine organisms. The mainstream self-polishing resin technology is represented by polyacrylic silane ester, polyacrylic acid zinc and polyacrylic acid copper resin which are in side chain hydrolysis type, and the performance of the polyacrylic silane ester, the polyacrylic acid zinc and the polyacrylic acid copper resin has certain requirements on the air-stopping ratio and the air speed. In the static stage, the ideal self-polishing effect is difficult to achieve by only the scouring of seawater. More importantly, the resin has no function per se, only depends on the release of the antifouling agent to inhibit and kill fouling organisms, and the unstable polishing causes the antifouling agent not to be released continuously, so that the static antifouling effect is poor. Moreover, the hydrolyzed polymer is difficult to separate from the surface of the coating, so that the swelling property of the coating is increased, and the main chain cannot be degraded in the marine environment, so that the dispersion into the sea causes micro-plastic pollution, thereby seriously threatening the safety of a marine ecosystem.

The focus of the current research is how to make the antifouling resin multifunctional to enhance the antifouling function, for example, introducing a polyester structure into a main chain of a polymer to make the polymer degradable, such as chinese patent publication CN 103396513 a, a preparation method and application of a main chain-broken polyacrylic silane ester resin; chinese patent publication CN 107056990 a, a main chain degradable zinc polyacrylate resin prepared by a monomer method, and a method and application thereof; chinese patent publication CN106986969A, a main chain degradation type polyacrylic acid copper resin and a preparation method and application thereof; grafting an antifouling group having fouling resistance properties or a functional monomer that can induce self-generation of zwitterions, and the like. However, the implementation of the above technologies is based on the traditional straight-chain polymer resin, and the hydrolyzed resin still cannot be separated from the surface of the coating in time, so that controllable self-polishing is realized, and the static antifouling requirement in fouling pressure sea areas is met.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a degradable hyperbranched resin. The resin can meet the static antifouling requirement of the ocean and can avoid causing ocean micro-plastic pollution.

The invention also aims to provide a preparation method of the degradable hyperbranched resin.

the invention further aims to provide application of the degradable hyperbranched resin in the field of marine antifouling.

The purpose of the invention is realized by the following technical scheme:

The degradable hyperbranched resin is prepared from the following components in parts by weight:

Preferably, the degradable hyperbranched resin is prepared from the following components in parts by weight:

the cyclic monomer is preferably at least one of the following compounds (1) to (38): (1) glycolide, (2) lactide, (3) epsilon-caprolactone, (4) 2-methyl-epsilon-caprolactone, (5) 2-chloro-epsilon-caprolactone, (6) gamma-butyrolactone, (7) delta-valerolactone, (8) gamma-valerolactone, (9) ethylene carbonate, (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) gamma-glycidoxypropyltrimethoxysilane, (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-dioxolane, (25)2, 5-dimethylene-1, 3-dioxolane, (26) 2-methylene-5-phenyl-1, 3-dioxan, (27) 2-methylene-4-alkyl-1, 3-dioxan, (28) 2-methylene-1, 3-dioxepane, (29) 2-methylene-5-alkyl-1, 3-dioxepane, (30) 2-methylene-4, 7-dimethyl-1, 3-dioxepane, (31) 2-methylene-1, 3-dioxo-5, 6-benzocycloheptane, (32) 2-methylene-5-phenyl-1, 3-dioxepane, (33) 2-ethylidene-1, 3-dioxepane, (34) 2-methylene-1, 3-dioxo-5-cycloheptene, (35) 2-ethylidene-4-alkyl-1, 3-dioxolane, (36) 2-ethylidene-1, 3-dioxan-e, (37) 2-allylidene-4-phenyl-1, 3-dioxolane and (38) 2-ethylidene-1, 3-dioxo-5, 6-benzocycloheptane;

The structural formulae of the compounds (1) to (38) are as follows:

The vinyl antifouling functional monomer is at least one of vinyl silane ester monomer, vinyl zinc ester monomer, vinyl copper ester monomer and betaine type zwitter-ion precursor.

The vinyl silane ester monomer is at least one of acryloxytrimethylsilane, trimethylsilyl methacrylate, acryloxytriethylsilane, triethylsilyl methacrylate, acryloxytriisopropylsilane, triisopropylsilyl methacrylate, acryloxytriphenylsilane, triphenylsilyl methacrylate, acryloxytri-n-butylsilane, tri-n-butylsilyl methacrylate, acryloxytert-butyldimethylsilane, tert-butyldimethylsilyl methacrylate, acryloxybis (trimethylsiloxy) methylsilane, and bis (trimethylsiloxy) methylsilane methacrylate.

the vinyl zinc ester monomer or vinyl copper ester monomer is prepared by the following method: a solvent is used as a reaction medium, and a zinc-containing compound or a copper-containing compound, (methyl) acrylic acid and monocarboxylic acid react for 3-8 hours at 50-140 ℃ according to a molar ratio (0.9-1.1) to 1 (1-1.2). Preferably, a mixture of 1 molar part of (methyl) acrylic acid and (1-1.2) molar part of monocarboxylic acid is uniformly dripped into a mixture of (0.9-1.1) molar part of a zinc-containing compound or a copper-containing compound and a solvent at a temperature of 50-140 ℃ for 2-4 hours at a constant speed. More preferably, the reaction temperature is preferably 75-130 ℃; the molar ratio of the (meth) acrylic acid, the zinc-containing compound or the copper-containing compound and the monocarboxylic acid is 1:1: 1; the molar ratio of the (meth) acrylic acid to the copper-containing compound to the monocarboxylic acid is 1:1: 1. The solid content of the obtained vinyl zinc ester monomer or vinyl copper ester monomer in the product mixed solution is 40-60%;

Wherein the zinc-containing compound is preferably at least one of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate and zinc propionate; 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, iso-octanoic acid, stearic acid, iso-stearic acid, naphthenic acid, itaconic acid, maleic acid, oleic acid, palmitic acid, and abietic acid; the solvent is preferably at least one of a hydrocarbon solvent, an alcohol solvent and water; more preferably at least one of toluene, xylene, isopropanol, n-butanol, isobutanol and propylene glycol methyl ether.

the structural general formula of the betaine type zwitter-ion precursor is shown as the following formula:

wherein R1 represents H or CH3, and R2 represents an alkyl group (linear, branched, or cyclic) having 1 to 12 carbon atoms, a methoxy-terminated polyethylene glycol (n ═ 2 to 24), or an antifouling group.

Preferably, the antifouling group is at least one of an organic antifouling group, a zinc-containing antifouling group, a copper-containing antifouling group, and a silicon-containing antifouling group.

More preferably, the organic antifouling group is one of isothiazolinone, triclosan, paeonol, camptothecin, N- (2,4, 6-trichlorophenyl) maleimide, bromopyrrolecarbonitrile, arundoin, capsaicin or hydroxyindole; the zinc-containing antifouling group is: wherein R3 is a saturated or unsaturated alkyl or cycloalkyl group having 1-12 carbon atoms, "+" represents a connecting site; the copper-containing antifouling group R2 is: wherein R4 is a saturated or unsaturated alkyl or cycloalkyl group having 1-12 carbon atoms, "+" represents a connecting site; the silicon-containing antifouling group R2 is: wherein R5 is an alkyl group having 1 to 8 carbon atoms, and ". times" represents a connecting site.

The preparation method of the betaine type zwitterion precursor comprises the following steps: carrying out Michael addition reaction on equimolar acrylate containing R2 group and 2- (methylamino) ethanol at 0-50 ℃, and carrying out acylation reaction on the acrylate and equimolar (methyl) acryloyl chloride at 0-30 ℃ to obtain a betaine type zwitter-ion precursor;

The bifunctional monomer is preferably a functional monomer with vinyl groups at two ends; more preferably at least one of (meth) acrylates, (meth) acrylates containing a metal element, aliphatic polyesters having vinyl groups at both ends, Schiff bases and disulfide bond-containing compounds.

Wherein the (meth) acrylate is preferably 3- (acryloyloxy) -2-hydroxypropyl acrylate, 3- (acryloyloxy) -2-hydroxypropyl methacrylate, polyethylene glycol diacrylate (polymerization degree n is 1 to 24), polyethylene glycol dimethacrylate (polymerization degree n is 1 to 24), polypropylene glycol diacrylate (polymerization degree n is 1 to 24), polypropylene glycol dimethacrylate (polymerization degree n is 1 to 24), 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol diacrylate, 1-decanediol diacrylate, or a mixture thereof, 1, 10-decanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethoxylated bisphenol A diacrylate (degree of polymerization n is 1 to 24), ethoxylated bisphenol A dimethacrylate (degree of polymerization n is 1 to 24), ethoxylated bisphenol fluorene diacrylate (degree of polymerization n is 1 to 24), ethoxylated bisphenol fluorene dimethacrylate (degree of polymerization n is 1 to 24), tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate and bisphenol A glycerol dimethacrylate. The metal element-containing (meth) acrylate is 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 polyester having vinyl groups at both ends is preferably polypropylene carbonate having vinyl groups at both ends, polytrimethylene carbonate having vinyl groups at both ends, poly (trimethylene carbonate-caprolactone) having vinyl groups at both ends, poly (caprolactone-glycolide) having vinyl groups at both ends, poly (caprolactone-lactide) having vinyl groups at both ends, poly (caprolactone-ethylene glycol) having vinyl groups at both ends, poly (lactide-glycolide) having vinyl groups at both ends, poly (lactide-ethylene glycol) having vinyl groups at both ends, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) having vinyl groups at both ends, polyethylene glycol adipate having vinyl groups at both ends, poly (trimethylene carbonate) having vinyl groups at both ends, poly (caprolactone-lactide) having vinyl groups at both ends, poly (caprolactone, At least one of poly (butylene adipate) with vinyl at two ends, poly (hexanediol adipate) with vinyl at two ends, poly (butylene succinate) with vinyl at two ends, polyorthoester with vinyl at two ends, polyanhydride with vinyl at two ends, polyphosphoester with vinyl at two ends, polycaprolactone with vinyl at two ends, polylactide with vinyl at two ends and polyglycolide with vinyl at two ends; the molecular weight of the aliphatic polyester having vinyl groups at both ends is preferably 1X 102 to 5X 103g/mol, more preferably 3X 102 to 2X 103 g/mol.

the structures of the Schiff bases and the disulfide bond-containing compounds are as follows:

The vinyl monomer is preferably at least one of (meth) acrylates, hydroxyl-terminated (meth) acrylates, cyclic hydrocarbon (meth) acrylates, and polyolefin glycol (meth) acrylates.

The vinyl monomer of (meth) acrylate is preferably at least one of methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and stearyl methacrylate. The hydroxyl-terminated (meth) acrylate is preferably at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. The cyclic hydrocarbon ester of (meth) acrylic acid is preferably at least one of phenyl acrylate, cyclohexyl acrylate, 1-methylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, phenyl methacrylate, cyclohexyl methacrylate, 1-methylcyclohexyl methacrylate, and 4-t-butylcyclohexyl methacrylate. The (meth) acrylic acid polyolefin glycol esters are preferably at least one of polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol methacrylate and polypropylene glycol methacrylate; the polymerization degree of the (methyl) acrylic polyolefin glycol esters is 1-10.

The initiator is preferably at least one of phosphazene, phosphazene salt, phosphazene oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate.

The chain transfer agent is preferably at least one of a mercaptan, a dithioester, a trithioester, and a methylstyrene dimer (i.e., 2, 4-diphenyl-4-methyl-1-pentene).

Wherein the mercaptan is preferably at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, thioglycolic acid, isooctyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and quaternary cyclopentadienyl tetraol tetrakis (3-mercaptopropionate). The dithioester is preferably isopropylphenyl dithiobenzoate, 2-cyanoisopropyl dithiobenzoate, methyl dithiobenzoate, phenethyl dithiobenzoate, benzyl dithiobenzoate, phenethyl dithiophenylacetate, S- (thiobenzoyl) thioacetic acid, S-acetonyl-O-ethyl dithiocarbonate, S-propionyloxy-O-ethyl dithiocarbonate, 2-cyanopropyl-4-cyanodithiobenzoate, 2-cyanopropyl-N-methyl-N- (4-pyridine) aminodithiocarbonate, methyl-2- [ methyl (4-pyridine) dithiocarbonate ] propionate, 4-cyano-4- (thiobenzoyl) pentanoic acid, methyl-2- [ methyl (4-pyridine) dithiocarbonate ] propionate, methyl-2- [ methyl- (4-pyridine) dithiocarbonate ] propionate, methyl-4- (thiobenzoyl) pentanoic acid, methyl-2-ethyl-propionate, ethyl-propionate, at least one of methyl (phenyl) aminodithioformate, 2-phenylpropyl-2-dithiobenzene, 1-cyano-1-methyl-4-oxo-4- (2-thio-3-thiazolidinyl) butyl ester, bis (thiobenzoyl) disulfide, tetramethylthiuram disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, di-n-butylxanthogen disulfide, and isobutylxanthogen disulfide. The trithioester is preferably at least one of 2-cyano-2-propyldodecyltrithiocarbonate, dibenzyltrithiocarbonate, S-cyanomethyl-S-dodecyltrithiocarbonate, 4-cyano-4- (dodecylsulfanylthiocarbonyl) thiovaleric acid, bis (carboxymethyl) trithiocarbonate, methyl 2- [ [ (dodecylmercapto) thiomethyl ] thio ] -2-methylbenzoate, 2- (dodecylmercaptothiocarbonylthio) -2-methylpropionic acid, and dimethyl trithiocarbonate.

The organic solvent in the degradable hyperbranched resin component is preferably at least one of hydrocarbon solvent, alcohol solvent, ketone solvent and ester solvent; more preferably at least one of toluene, xylene, isopropanol, n-butanol, isobutanol, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate and butyl acetate.

The invention relates to a degradable hyperbranched resin, which structurally is a hyperbranched random copolymer consisting of vinyl antifouling functional monomers, bifunctional monomers, vinyl monomers and polyester chain segments. When the vinyl antifouling functional monomer is a vinyl silane ester monomer, the product is degradable hyperbranched silicon-based self-polishing resin; when the vinyl antifouling functional monomer is a vinyl zinc ester monomer, the product is degradable hyperbranched zinc-based self-polishing resin; when the vinyl antifouling functional monomer is a vinyl silicon copper ester monomer, the product is degradable hyperbranched copper-based self-polishing resin; when the vinyl antifouling functional monomer is a betaine type zwitter-ion precursor, the product is a hyperbranched self-polishing resin capable of degrading self-generated zwitter-ions.

The content of silicon element in the degradable hyperbranched silicon-based self-polishing resin is 1-15%, preferably 3-8%; the content of zinc element in the degradable hyperbranched zinc-based self-polishing resin is 0.5-20%, preferably 3-10%; the content of copper element in the degradable hyperbranched copper-based self-polishing resin is 1-20%, preferably 5-15%; the acid value of the degradable hyperbranched silicon/zinc/copper-based self-polishing resin is 30-350 mgKOH/g, preferably 50-250 mgKOH/g.

the number average molecular weight Mn (measured by GPC with polystyrene as standard sample) of the degradable hyperbranched resin is 1000-10000, preferably 2000-6000.

the preparation method of the degradable hyperbranched resin comprises the following steps:

In an inert gas or nitrogen atmosphere, an organic solvent is used as a reaction medium, and under the action of an initiator and a chain transfer agent, a vinyl antifouling functional monomer, a bifunctional monomer, a cyclic monomer and a vinyl monomer react at 70-120 ℃ for 8-24 hours to obtain the degradable hyperbranched resin.

when the vinyl antifouling functional monomer is a vinyl silane ester monomer, obtaining the hyperbranched silicon-based self-polishing resin; when the monomer is vinyl zinc ester/copper ester monomer, the degradable hyperbranched zinc/copper-based self-polishing resin is obtained; when the precursor is betaine type zwitter ion, the hyperbranched self-polishing resin capable of degrading the self-generated zwitter ion is obtained.

the synthetic method of the degradable hyperbranched silicon-based self-polishing resin is preferably as follows: under the atmosphere of inert gas or nitrogen and at the temperature of 70-120 ℃, taking an organic solvent as a reaction medium, dropwise adding a mixture consisting of a vinyl silane ester monomer, a bifunctional monomer, a cyclic monomer, a vinyl monomer, an initiator and a chain transfer agent at a constant speed within 4-8 hours, then carrying out heat preservation reaction for 0-4 hours, then adding the initiator at a constant speed within 0.5-1 hour, and continuing the reaction for 1.5-4 hours to obtain the degradable hyperbranched silicon-based self-polishing resin;

When the vinyl antifouling functional monomer is a vinyl silane ester monomer, obtaining the hyperbranched silicon-based self-polishing resin; when the monomer is vinyl zinc ester/copper ester monomer, the degradable hyperbranched zinc/copper-based self-polishing resin is obtained; when the precursor is betaine type zwitter ion, the hyperbranched self-polishing resin capable of degrading the self-generated zwitter ion is obtained.

the degradable hyperbranched resin is applied to marine antifouling.

the application is preferably to prepare the marine antifouling paint by using the degradable hyperbranched resin.

compared with the prior art, the invention has the following advantages and beneficial effects:

(1) According to the invention, bifunctional monomers and chain transfer agents are introduced in the polymerization process, the traditional straight-chain type polymer antifouling resin is prepared into a hyperbranched structure, and the hyperbranched structure is applied to the field of marine antifouling for the first time.

(2) the bifunctional monomer adopted by the invention contains a chemical bond which can be broken, so that the branch point of the prepared hyperbranched resin can be broken under the attack of seawater. The polyester chain segment is also degraded at the same time, the product of the degraded degradable hyperbranched resin has smaller molecular weight than the degradable antifouling resin with the main chain containing ester bonds under the synergistic effect of the polyester chain segment and the polyester chain segment, and is easier to be absorbed by the environment, and the molecular weight of fragments can be further reduced by increasing the content of the annular monomer and the bifunctional monomer, so that the marine micro-plastic pollution is effectively avoided.

(3) The side chain silane ester bond/zinc ester bond/copper ester bond/betaine type zwitter-ion precursor of the degradable hyperbranched resin prepared by the invention can be hydrolyzed in seawater, and can be cooperated with three parts of branch point fracture and polyester chain segment degradation to further accelerate the hydrolytic degradation rate of the material, and can also realize rapid polishing in static seawater, so that the adhesion of fouling organisms is avoided or inhibited, thereby solving the problem of the dependence of the traditional self-polishing material on the navigational speed, and meeting the static antifouling requirement of fouling pressure sea areas.

(4) the degradable hyperbranched silicon-based self-polishing resin has a drag reduction function; the zinc/copper ions generated by hydrolyzing the degradable hyperbranched zinc/copper-based self-polishing resin also have a certain anti-fouling effect, so that the effective concentration of active substances on the surface of ships or marine equipment is ensured, and the anti-fouling requirements of facilities such as low-speed ships and offshore oil production platforms are well met. The hyperbranched resin capable of degrading the authigenic zwitterions can release an antifouling group through hydrolysis, and meanwhile, the zwitterions generated on the surface of the coating after hydrolysis endow the material with an anti-protein effect, so that the antifouling capacity of the material is further enhanced, and the purpose of synergistic antifouling of an antifouling agent and an anti-protein is realized; only the surface of the coating is converted into hydrophilic zwitterions, so that the defects of high swelling property, poor mechanical property and the like of the traditional zwitterion material are overcome.

(5) In the polymerization process, different types and different contents of vinyl monomers or bifunctional monomers are added to regulate and control the glass transition temperature and the mechanical property of the material, and the solubility of the material in a common solvent for marine coatings is improved.

(6) the degradable hyperbranched resin provided by the invention has the advantages of high solid content and low viscosity, and the dosage of a solvent in the antifouling paint can be reduced, so that VOC (volatile organic compounds) is reduced; and the preparation method is simple and feasible, has lower cost, is suitable for industrial production, and has good development prospect in the field of marine antifouling paint.

Detailed Description

the present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

The adhesion test described in the examples of the present application is referred to ISO 2409-2007 test for color paint and varnish-grid test; the hanging plate experiment refers to GB/T5370 & 2007 shallow sea immersion test method of antifouling paint sample plate; the resistance reduction performance test refers to GB/T7791-2014 antifouling paint resistance reduction performance test method. In the examples of the present application, the experimental procedures for testing the release rate of the natural antifouling agent (5-octyl-2-furanone) are described in Ma C, Zhang W, Zhang G, et al, environmental friendly inorganic coating based on biodegradable polymer and natural antifouling [ J ]. ACS, stable Chemistry & Engineering,2017,5: 6304-. For the experimental procedures of the anti-Protein adsorption test in the examples of this application, reference is made to Ma J, Ma C, Zhang G.degradable Polymer with Protein Resistance in a sodium Environment [ J ]. Langmuir,2015,31(23): 6471-.

in the examples of the present application, the preparation of S-vinyl propionate-O-ethyl dithiocarbonate is described in Schmitt J, Blancard 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 the examples of the present application, S-cyanomethyl-S-dodecyl trithiocarbonate was purchased from Zhengzhou Jex chemical products, Ltd; 3-mercaptopropionic acid-2-ethylhexyl ester was purchased from Bailingwei science and technology Co.

the polyglycolide with vinyl groups at two ends in the examples of the application is obtained by reacting the polyglycolide with hydroxyl groups at two ends with acryloyl chloride according to the molar ratio of 1:2 at 0 ℃ for 12 hours.

in the embodiment of the application, the polycaprolactone with vinyl groups at two ends is obtained by reacting the polycaprolactone with hydroxyl groups at two ends with acryloyl chloride according to the molar ratio of 1:2 at 0 ℃ for 12 hours.

in the examples of the application, poly (caprolactone-lactide) with vinyl groups at both ends was obtained by reacting poly (caprolactone-lactide) with hydroxyl groups at both ends with acryloyl chloride at a molar ratio of 1:2 at 0 ℃ for 12 hours.

In the embodiment of the application, the preparation method of the bisacrylamide containing oxime/semicarbazone/hydrazone structure refers To Sims M B, Patel K Y, Bhatta M, et al, Harnesing Imine university To tube superabsorbent Polymer Degradation [ J ]. Macromolecules,2018,51: 356-363.