CN113166579A - Organic-inorganic nano composite antifouling coating for environment-friendly antifouling paint and preparation method thereof - Google Patents

Organic-inorganic nano composite antifouling coating for environment-friendly antifouling paint and preparation method thereof Download PDF

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CN113166579A
CN113166579A CN201980070592.5A CN201980070592A CN113166579A CN 113166579 A CN113166579 A CN 113166579A CN 201980070592 A CN201980070592 A CN 201980070592A CN 113166579 A CN113166579 A CN 113166579A
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CN113166579B (en
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李春光
刘轶龙
杨名亮
王胜龙
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Xiamen Sunrui Ship Coatings Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

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Abstract

An organic-inorganic nano composite antifouling coating for an environment-friendly antifouling paint and a preparation method thereof, wherein the organic-inorganic nano composite antifouling coating for the environment-friendly antifouling paint comprises the following preparation raw materials: nanoparticles modified with a silane coupling agent, (meth) acrylate, silyl (meth) acrylate, and silyl (meth) acrylate copolymers. The organic-inorganic nano composite antifouling coating for the environment-friendly antifouling paint can be self-renewed on the surface, has strong hydrophobicity, can effectively reduce the accumulation of marine organisms and the adhesion of dirt, is environment-friendly, has excellent antifouling effect and has wide application prospect.

Description

Organic-inorganic nano composite antifouling coating for environment-friendly antifouling paint and preparation method thereof Technical Field
The invention relates to the technical field of antifouling paints, in particular to an organic-inorganic nano composite antifouling coating for an environment-friendly antifouling paint and a preparation method thereof.
Background
Solid bodies in seawater and ships are often subjected to marine biofouling, which accelerates metal corrosion, resulting in slower speeds and increased fuel consumption.
In order to prevent the attachment and growth of marine organisms, antifouling coatings currently on the market on a large scale are still antifouling coatings comprising antifouling agents, in particular cuprous oxide.
EP1476509 discloses a self-polishing antifouling paint which contains inorganic antifouling agents such as copper oxide and copper thiocyanate, and organic antifouling agents such as SeaNine211 and Irgarol1051, and release of the antifouling agents is not friendly to marine environment, and accumulation of the antifouling agents in marine organisms is easily caused.
The invention patent with publication number CN1101841C discloses a silicate antifouling paint, which is used for preventing marine organisms from attaching to the surfaces of ships, marine facilities and the like and simultaneously prolonging the antifouling period of the antifouling paint, but the paint is formed by taking a silicate environment-friendly antifouling agent, organic tin, cuprous oxide, copper sulfate and other components as a composite environment-friendly antifouling agent and adding film-forming resin, a dispersing agent, an anti-settling agent, a proper amount of organic solvent and other components; the antifouling paint disclosed by the invention adopts cuprous oxide and organic tin as environment-friendly antifouling agents, and the environment-friendly antifouling agents can pollute and harm the ocean.
In order to be more environment-friendly, a biofouling release-type coating which does not contain an antifouling agent is developed, and a fouling release-type antifouling paint is disclosed in the patent publication number WO2013107827, which has the advantages of being friendly to marine environment and reducing the consumption of ship fuel to the maximum extent; however, the coating is preferably applied to a ship with the speed of 15 knots, and the surface of the coating cannot be renewed when the ship is slow in running or is static, so that the coating is not ideal in application effect and is easily polluted by dirt.
The invention solves the antifouling problem, prepares the organic-inorganic nano composite coating, does not contain an antifouling agent, can realize surface self-renewal, is environment-friendly and has certain antifouling effect.
Disclosure of Invention
In order to solve the problem that the existing antifouling paint contains an antifouling agent which easily causes marine pollution, the invention provides an organic-inorganic nano composite antifouling coating for an environment-friendly antifouling paint, which comprises the following preparation raw materials: nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (meth) acrylate, (meth) silyl acrylate and (meth) silyl acrylate copolymer.
In this embodiment, the (meth) acrylate includes methacrylate and acrylate; the silyl (meth) acrylate includes silyl methacrylate and silyl acrylate; the silyl (meth) acrylate copolymer includes a silyl methacrylate copolymer and a silyl acrylate copolymer.
On the basis of the scheme, the nano-particle material further comprises the following raw materials in parts by weight, wherein the (methyl) silyl acrylate copolymer is 4-40 parts, and the nano-particles (P-G-NPs) modified by the Silane Coupling Agent (SCA), the (methyl) acrylate and the (methyl) silyl acrylate are 61-95 parts.
On the basis of the scheme, the nano particles (P-G-NPs) modified by the Silane Coupling Agent (SCA), the (methyl) acrylate and the (methyl) acrylate further comprise the following preparation raw materials: nano particles (G-NPs) modified by Silane Coupling Agent (SCA), methyl (meth) acrylate, initiator and organic solvent B.
On the basis of the scheme, the Silane Coupling Agent (SCA), the (meth) acrylate and the silyl (meth) acrylate modified nanoparticles (P-G-NPs) comprise the following raw materials in parts by weight, 10-30 parts of the Silane Coupling Agent (SCA) modified nanoparticles (G-NPs), 1-20 parts of the (meth) acrylate, 20-40 parts of the silyl (meth) acrylate, 1-5 parts of the initiator and 10-50 parts of the organic solvent B.
On the basis of the scheme, the (meth) acrylate is a composition of any one or more of methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate and isooctyl acrylate;
on the basis of the scheme, the (meth) acrylate is a composition of any one or more of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; the hydroxylated monomer is adopted to help modify the hydrolysis rate of the nano particles, so that the particles are released quickly;
in this embodiment, the (meth) acrylate includes methacrylate and acrylate; the 2-hydroxyethyl (meth) acrylate includes 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate; the 2-hydroxypropyl (meth) acrylate includes 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate; the 2-hydroxybutyl (meth) acrylate includes 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate.
On the basis of the scheme, the structural formula of the silyl (meth) acrylate is as follows:
Figure PCTCN2019123031-APPB-000001
wherein R is H or CH3，R 1、R 2、R 3Is alkyl, cycloalkyl, aryl or aralkyl with 1-20 carbon atoms.
In addition to the above embodiments, the silyl (meth) acrylate is a combination of one or more of trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate.
On the basis of the scheme, the organic solvent B is one or a combination of two of an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent and an ether solvent.
On the basis of the scheme, the aromatic hydrocarbon solvent is any one of toluene and xylene or a combination of the toluene and the xylene.
On the basis of the scheme, the ester solvent is one or a combination of butyl acetate and ethyl acetate.
On the basis of the scheme, the ketone solvent is one or a combination of methyl ethyl ketone, butanone and cyclohexanone.
On the basis of the scheme, the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.
On the basis of the scheme, the initiator is any one or a combination of two of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile.
On the basis of the scheme, further, the nano particles (G-NPs) modified by the Silane Coupling Agent (SCA) comprise the following preparation raw materials: nano particles, a Silane Coupling Agent (SCA) and an organic solvent A.
On the basis of the scheme, the nano particles (G-NPs) modified by the Silane Coupling Agent (SCA) further comprise the following preparation raw materials in parts by weight: 5-25 parts of nano particles, 10-51 parts of Silane Coupling Agent (SCA) and 15-45 parts of organic solvent A.
In addition to the above embodiments, the organic solvent a may be a hydrocarbon solvent or an alcohol solvent, or a combination of both.
In addition to the above scheme, further, the hydrocarbon solvent is any one or a combination of two of toluene, xylene and trimethylbenzene.
On the basis of the scheme, the alcohol solvent is one or a combination of n-butanol, isobutanol and phenethyl alcohol.
On the basis of the scheme, further, the nano particles are one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide or nano aluminum oxide.
On the basis of the scheme, the particle size of the nano particles is 10-40 nm.
On the basis of the scheme, the Silane Coupling Agent (SCA) is one of KBE-1003, KBM503 and KBM 5103.
Further, on the basis of the above scheme, the solid content of the silyl (meth) acrylate copolymer is 55%.
On the basis of the scheme, the viscosity of the (methyl) acrylic acid silyl ester copolymer is 10-15 poise.
On the basis of the scheme, the weight average molecular weight of the (methyl) acrylic acid silyl ester copolymer is 10000-15000.
The invention provides a preparation method of an organic-inorganic nano composite antifouling coating for an environment-friendly antifouling paint, which comprises the following steps:
adding a silyl (meth) acrylate copolymer solution into a preparation container, and adding nanoparticles (P-G-NPs) modified by a Silane Coupling Agent (SCA), (meth) acrylate and silyl (meth) acrylate while dispersing, wherein the dispersion rotating speed is preferably 500rpm, and then preferably performing high-speed dispersion, the high-speed dispersion rotating speed is preferably 2000-2500rpm, and the duration of the high-speed dispersion is preferably 15 min;
wherein the preparation vessel is preferably a dispersion tank; the (meth) silyl acrylate copolymer solution is preferably a (meth) silyl acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 10-15 poises, and a weight-average molecular weight of 10000-15000.
On the basis of the scheme, the nano-particles (P-G-NPs) modified by Silane Coupling Agent (SCA), methyl (meth) acrylate and silyl (meth) acrylate further comprise the following preparation steps:
adding an organic solvent B and Silane Coupling Agent (SCA) modified nanoparticles (G-NPs) into a preparation container, heating to 80-115 ℃ in an atmosphere of protective gas, wherein the protective gas is preferably nitrogen, then dripping a mixed solution of (methyl) acrylate, silyl (meth) acrylate and an initiator into the preparation container within 5-10 hours, keeping heating, after dripping is finished, centrifugally washing, and preferably repeatedly carrying out centrifugal washing for 3 times to obtain Silane Coupling Agent (SCA), (meth) acrylate and silyl (meth) acrylate modified nanoparticles (P-G-NPs);
wherein, the preparation container is preferably a four-mouth flask.
On the basis of the above scheme, further, the nanoparticle (G-NPs) modified by the Silane Coupling Agent (SCA) comprises the following preparation steps:
loading an organic solvent A and nanoparticles into a preparation container, carrying out ultrasonic dispersion, wherein the ultrasonic dispersion time is preferably 20min, heating to 40-60 ℃ in the atmosphere of protective gas, wherein the protective gas is preferably nitrogen, then dripping a Silane Coupling Agent (SCA) into the preparation container within 3-6 hours, keeping heating, after dripping, carrying out centrifugal washing, and preferably repeatedly carrying out 3 times of centrifugal washing to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
wherein, the preparation container is preferably a four-mouth flask.
On the basis of the scheme, the nano particle modified by the silane coupling agent further comprises the following preparation raw materials in parts by weight: 5-25 parts of nano particles, 10-51 parts of silane coupling agent and 15-45 parts of organic solvent A.
In addition to the above embodiments, the organic solvent a may be a hydrocarbon solvent or an alcohol solvent, or a combination of both.
In addition to the above scheme, further, the hydrocarbon solvent is any one or a combination of two of toluene, xylene and trimethylbenzene.
On the basis of the scheme, the alcohol solvent is one or a combination of n-butanol, isobutanol and phenethyl alcohol.
On the basis of the scheme, further, the nano particles are one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide or nano aluminum oxide.
On the basis of the scheme, the particle size of the nano particles is 10-40 nm.
On the basis of the scheme, the silane coupling agent is one of KBE-1003, KBM503 and KBM 5103.
Further, on the basis of the above scheme, the solid content of the silyl (meth) acrylate copolymer is 55%.
On the basis of the scheme, the viscosity of the (methyl) acrylic acid silyl ester copolymer is 10-15 poise.
On the basis of the scheme, the weight average molecular weight of the (methyl) acrylic acid silyl ester copolymer is 10000-15000.
On the basis of the scheme, the nano particles modified by the silane coupling agent, the (methyl) acrylate and the (methyl) acrylate further comprise the following raw materials in parts by weight, wherein the nano particles modified by the silane coupling agent comprise 10-30 parts of the (methyl) acrylate, 1-20 parts of the (methyl) acrylate, 20-40 parts of the (methyl) acrylate, 1-5 parts of the initiator and 10-50 parts of the organic solvent B.
On the basis of the scheme, the (meth) acrylate is a composition of any one or more of methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate and isooctyl acrylate.
In addition to the above scheme, the (meth) acrylate is any one or more of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
On the basis of the scheme, the structural formula of the silyl (meth) acrylate is as follows:
Figure PCTCN2019123031-APPB-000002
wherein R is H or CH3，R 1、R 2、R 3Is alkyl, cycloalkyl, aryl or aralkyl with 1-20 carbon atoms.
In addition to the above embodiments, the silyl (meth) acrylate is a combination of one or more of trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate.
On the basis of the scheme, the organic solvent B is one or a combination of two of an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent and an ether solvent.
On the basis of the scheme, the aromatic hydrocarbon solvent is any one of toluene and xylene or a combination of the toluene and the xylene.
On the basis of the scheme, the ester solvent is one or a combination of butyl acetate and ethyl acetate.
On the basis of the scheme, the ketone solvent is one or a combination of methyl ethyl ketone, butanone and cyclohexanone.
On the basis of the scheme, the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.
On the basis of the scheme, the initiator is any one or a combination of two of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile.
On the basis of the scheme, the nano-particle material further comprises the following raw materials in parts by weight, 4-40 parts of the (methyl) acrylic acid silyl ester copolymer, and 61-95 parts of nano-particles modified by a silane coupling agent, (methyl) acrylic ester and (methyl) acrylic acid silyl ester.
Compared with the prior art, the organic-inorganic nano composite antifouling coating for the environment-friendly antifouling paint and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:
1. the modified nano particle surface can be hydrolyzed to generate hydrophilicity, is dissolved in seawater, and has a faster dissolving rate than that of the matrix resin SP-Si, so that the surface renewal is facilitated and the attachment of microorganisms is not facilitated.
2. The invention can effectively reduce the accumulation of marine organisms and reduce the adhesion of dirt.
3. Can be self-renewed on the surface, does not contain antifouling agents and is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an organic-inorganic nanocomposite antifouling coating for an environmentally-friendly antifouling paint provided by the invention;
FIG. 2 is a graph showing the hydrolysis rate of an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the following examples and comparative examples:
table 1 examples 1-4 tables of ingredients
Figure PCTCN2019123031-APPB-000003
Table 2 examples 5-8 table of the components
Figure PCTCN2019123031-APPB-000004
Figure PCTCN2019123031-APPB-000005
In example 1, the following starting materials were used:
the NPs adopt nano silicon dioxide with the particle size of 10nm, the Silane Coupling Agent (SCA) adopts KBE503, the organic solvent A adopts dimethylbenzene, the (methyl) silyl acrylate adopts trimethylsilyl acrylate, the (methyl) acrylate adopts methyl methacrylate, the initiator adopts azobisisobutyronitrile, and the organic solvent B adopts butyl acetate; the silyl (meth) acrylate solution SPC employs a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 12 poises, and a weight-average molecular weight of 12000; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 40 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 4 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 80 ℃ under nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 6 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 2, the starting material was prepared as follows:
the NPs adopt nano silicon dioxide with the particle size of 15, the Silane Coupling Agent (SCA) adopts KBE503, the organic solvent A adopts toluene, the (methyl) silyl acrylate adopts triethyl silyl acrylate, the (methyl) acrylate adopts ethyl acrylate, the initiator adopts azobisisobutyronitrile, and the organic solvent B adopts butyl acetate; the silyl (meth) acrylate solution SPC employs a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 12 poises, and a weight-average molecular weight of 12000; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 40 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 3 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 80 ℃ in a nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 6 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 3, the starting material was prepared as follows:
the NPs adopt nano silicon dioxide with the particle size of 20, the Silane Coupling Agent (SCA) adopts KBM5103, the organic solvent A adopts dimethylbenzene, the (methyl) acrylic acid silyl ester adopts triisopropyl silyl methacrylate, the (methyl) acrylic ester adopts 2-hydroxybutyl acrylate, the initiator adopts benzoyl peroxide, and the organic solvent B adopts propylene glycol methyl ether; the silyl (meth) acrylate solution SPC employs a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 10 poises, and a weight-average molecular weight of 10050; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 40 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 5 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 85 ℃ in a nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 6 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 4, the starting material was prepared as follows:
the NPs adopt nano silicon dioxide with the particle size of 15, the Silane Coupling Agent (SCA) adopts KBE-1003, the organic solvent A adopts toluene, the (methyl) acrylic acid silyl ester adopts acrylic acid trimethylsilyl ester, the (methyl) acrylic acid ester adopts 2-hydroxy butyl methacrylate, the initiator adopts azobisisobutyronitrile, and the organic solvent B adopts butyl acetate; the silyl (meth) acrylate solution adopts a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed by a patent US7691938B2, and has the solid content of 55%, the viscosity of 11 poises and the weight-average molecular weight of 11800; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 50 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 4 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 87 ℃ under nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 8 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 5, the following starting materials were used:
the NPs adopt nano zinc oxide with the particle size of 20, the Silane Coupling Agent (SCA) adopts KBE-1003, the organic solvent A adopts dimethylbenzene, the (methyl) silyl acrylate adopts triisopropylsilyl acrylate, the (methyl) acrylate adopts methyl methacrylate, the initiator adopts azobisisobutyronitrile, and the organic solvent B adopts propylene glycol methyl ether; the (meth) silyl acrylate solution SPC is a (meth) silyl acrylate copolymer SP-Si solution prepared by a method disclosed by a patent US7691938B2, and has the solid content of 55%, the viscosity of 14 (10-15) poises and the weight-average molecular weight of 13040; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 48 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 5 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 90 ℃ under nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 7 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 6, the following starting materials were used:
the NPs adopt nano titanium dioxide with the particle size of 30, the Silane Coupling Agent (SCA) adopts KBE-1003, the organic solvent A adopts dimethylbenzene, the (methyl) acrylic acid silyl ester adopts triisopropyl silyl methacrylate, the (methyl) acrylic ester adopts ethyl acrylate, the initiator adopts benzoyl peroxide tert-butyl ester, and the organic solvent B adopts propylene glycol methyl ether; the silyl (meth) acrylate solution SPC adopts a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 13 poises, and a weight-average molecular weight of 12800; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 47 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 4 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 90 ℃ under nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 6 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 7, the following starting materials were used:
the NPs adopt nano titanium dioxide with the particle size of 20, the Silane Coupling Agent (SCA) adopts KBM503, the organic solvent A adopts dimethylbenzene, the (methyl) acrylic acid silyl ester adopts trimethylsilyl methacrylate, the (methyl) acrylic ester adopts 2-hydroxypropyl acrylate, the initiator adopts azobisisobutyronitrile, and the organic solvent B adopts propylene glycol methyl ether; the silyl (meth) acrylate solution SPC employs a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 13 poises, and a weight-average molecular weight of 13500; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 55 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 4 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 110 ℃ in a nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 9 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In example 8, the following starting materials were used:
the NPs adopt nano-alumina with the particle size of 30, the Silane Coupling Agent (SCA) adopts KBM5103, the organic solvent A adopts dimethylbenzene, the (methyl) acrylic acid silyl ester adopts triisopropyl silyl methacrylate, the (methyl) acrylic ester adopts 2-hydroxypropyl acrylate, the initiator adopts azobisisoheptonitrile, and the organic solvent B adopts propylene glycol methyl ether; the silyl (meth) acrylate solution SPC employs a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 15 poises, and a weight-average molecular weight of 14500; and the preparation method comprises the following steps:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 60 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 6 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding an organic solvent B and nanoparticles (G-NPs) modified by Silane Coupling Agent (SCA) into a four-neck flask, heating to 100 ℃ in a nitrogen atmosphere, then dripping a mixed solution of (methyl) acrylate, silyl (methyl) acrylate and an initiator into the four-neck flask within 8 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping to obtain nanoparticles (P-G-NPs) modified by Silane Coupling Agent (SCA), (methyl) acrylate and silyl (methyl) acrylate;
step three: adding a (methyl) silyl acrylate copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA), methyl (methyl) acrylate and silyl (methyl) acrylate modified nanoparticles (P-G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In comparative example 1, 75 parts by weight of silyl (meth) acrylate and 25 parts by weight of unmodified Nanoparticles (NPs) were used;
wherein the NPs adopt nano silicon dioxide with the particle size of 20, the silyl (meth) acrylate solution adopts a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed by a patent US7691938B2, the solid content is 55%, the viscosity is 12 poise, and the weight-average molecular weight is 12800; and is obtained by the following preparation method:
adding the (methyl) silyl acrylate copolymer solution into a dispersion tank, adding unmodified Nanoparticles (NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
In comparative example 2, 75 parts by weight of silyl (meth) acrylate and 25 parts by weight of Silane Coupling Agent (SCA) -modified nanoparticles (G-NPs) were used;
wherein the NPs employs nano silica having a particle size of 10, the Silane Coupling Agent (SCA) employs KBE503, the organic solvent a employs xylene, the silyl (meth) acrylate solution employs a silyl (meth) acrylate copolymer SP-Si solution prepared by a method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 12 poise, and a weight-average molecular weight of 12000; and is obtained by the following preparation method:
the method comprises the following steps: loading an organic solvent A and nanoparticles into a four-neck flask, ultrasonically dispersing for 20min, heating to 40 ℃ in a nitrogen atmosphere, then dripping a Silane Coupling Agent (SCA) into the four-neck flask within 4 hours, keeping heating, and repeatedly carrying out centrifugal washing for 3 times after dripping is finished to obtain Silane Coupling Agent (SCA) modified nanoparticles (G-NPs);
step two: adding the (methyl) acrylic acid silyl ester copolymer solution into a dispersion tank, adding Silane Coupling Agent (SCA) modified nanoparticles (G-NPs) at the rotation speed of 500rpm, and then dispersing at high speed for 15min to obtain the nano-particles.
The examples to be tested and the comparative samples were respectively coated on 2.5cm × 6cm glass slides with a coating area of 2.5cm × 6cm, the samples to be tested were placed in a dry 30 ℃ environment, the coating films were completely dried, the dry film thickness was maintained at about 100 μm, the films were placed in flowing artificial seawater (25 ℃) to be tested, and the hydrolysis rate was expressed as a weight loss rate of the copolymer per unit time, wherein:
weight loss rate (100 × (W)0-W dry))/(D*W 0)；
W 0The total weight of the dry film before testing; wdryThe total weight of the dry film is measured after a certain testing time; d is the time of soaking in water.
FIG. 1 is a schematic structural diagram of an organic-inorganic nanocomposite antifouling coating; the modified nano particles can be continuously hydrolyzed from the polished matrix resin and are faster than the matrix resin, so that the surface is not beneficial to the attachment of marine organisms and fouling desorption,
FIG. 2 is a graph of the hydrolysis rate of an organic-inorganic nanocomposite antifouling coating, showing that the coating in the example can stably renew the surface layer.
Table 3 contact angle test results for coatings
Figure PCTCN2019123031-APPB-000006
As can be seen from table 3, the organic-inorganic nanocomposite antifouling coating layer for the environmentally friendly antifouling paint provided by the present invention has more significant strong hydrophobicity than the comparative sample (except comparative example 2).
It can be seen from FIG. 2 that the hydrolysis rate of SP-Si copolymer without nanoparticles is very low and the surface renewal rate is very slow, while the hydrolysis rate of the comparative example with unmodified nanoparticles is too fast and cracks after about 20 days, the rest of the examples have good moderate stable hydrolysis rate.
The test results of the organic-inorganic nano composite antifouling coating are shown in table 4.
TABLE 4 antifouling result of organic and inorganic nano composite antifouling coating (hanging panel 6 months)
Test items Example 1 Example 2 Example 3 Example 4 Comparative example 1 SP-Si
Scoring 88 90 93 95 70 50
Test items Example 5 Example 6 Example 7 Example 8 Comparative example 2 \
Scoring 89 87 94 85 73 \
The detection is carried out according to the national standard GB/T5370 2007 shallow sea immersion test method of antifouling paint sample plate.
As can be seen from Table 4, the organic-inorganic nanocomposite antifouling coating for the environmentally friendly antifouling paint provided by the present invention has a better antifouling effect than the comparative sample.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (50)

  1. An organic-inorganic nano composite antifouling coating for an environment-friendly antifouling paint is characterized by comprising the following preparation raw materials: nanoparticles modified with a silane coupling agent, (meth) acrylate, silyl (meth) acrylate, and silyl (meth) acrylate copolymers.
  2. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 1, comprising 4 to 40 parts by weight of the silyl (meth) acrylate copolymer and 61 to 95 parts by weight of the silane coupling agent, (meth) acrylate, and silyl (meth) acrylate-modified nanoparticles.
  3. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 1 or 2, wherein the silane coupling agent, (meth) acrylate, silyl (meth) acrylate-modified nanoparticles comprise the following preparation raw materials: nano particles modified by a silane coupling agent, (methyl) acrylate, an initiator and an organic solvent B.
  4. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 3, wherein the silane coupling agent, (meth) acrylate, and silyl (meth) acrylate-modified nanoparticles comprise, by weight, 10 to 30 parts of the silane coupling agent-modified nanoparticles, 1 to 20 parts of the (meth) acrylate, 20 to 40 parts of the silyl (meth) acrylate, 1 to 5 parts of the initiator, and 10 to 50 parts of the organic solvent B.
  5. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 3 or 4, wherein: the (methyl) acrylate is one or a combination of methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate and isooctyl acrylate.
  6. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 3 to 5, wherein: the (meth) acrylate is a composition of one or more of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate.
  7. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 3 to 6, wherein the silyl (meth) acrylate has the following structural formula:
    Figure PCTCN2019123031-APPB-100001
    wherein R is H or CH3，R 1、R 2、R 3Is alkyl, cycloalkyl, aryl or aralkyl with 1-20 carbon atoms.
  8. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 3 to 7, wherein the silyl (meth) acrylate is a combination of any one or more of trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate.
  9. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 3 to 8, wherein the organic solvent B is one or a combination of two of an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, and an ether solvent.
  10. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 9, wherein: the aromatic hydrocarbon solvent is one or a combination of toluene and xylene.
  11. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 9, wherein: the ester solvent is one or a combination of butyl acetate and ethyl acetate.
  12. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 9, wherein: the ketone solvent is one or a combination of methyl ethyl ketone, butanone and cyclohexanone.
  13. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 9, wherein: the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.
  14. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 3 to 13, wherein: the initiator is any one or a combination of two of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile.
  15. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 3 to 14, wherein the silane coupling agent-modified nanoparticles comprise the following preparation raw materials: nano particles, a silane coupling agent and an organic solvent A.
  16. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 15, wherein the silane coupling agent modified nanoparticles comprise the following raw materials for preparation in parts by weight: 5-25 parts of nano particles, 10-51 parts of silane coupling agent and 15-45 parts of organic solvent A.
  17. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 15 or 16, wherein: the organic solvent A is one or a combination of a hydrocarbon solvent and an alcohol solvent.
  18. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 17, wherein: the hydrocarbon solvent is any one or a combination of toluene, xylene and trimethylbenzene.
  19. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 17, wherein: the alcohol solvent is one or a combination of n-butanol, isobutanol and phenethyl alcohol.
  20. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 15 to 19, wherein: the nano particles are one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide or nano aluminum oxide.
  21. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 15 to 20, wherein: the particle size of the nanoparticles is 10-40 nm.
  22. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 15 to 21, wherein: the silane coupling agent is one of KBE-1003, KBM503 and KBM 5103.
  23. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 1 to 22, wherein the silyl (meth) acrylate copolymer has a solid content of 55%.
  24. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 1 to 23, wherein the silyl (meth) acrylate copolymer has a viscosity of 10 to 15 poise.
  25. The organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 1 to 24, wherein the silyl (meth) acrylate copolymer has a weight average molecular weight of 10000 to 15000.
  26. A preparation method of an organic-inorganic nano composite antifouling coating for an environment-friendly antifouling paint is characterized by comprising the following steps:
    adding the silyl (meth) acrylate copolymer solution into a preparation container, adding the silane coupling agent, (meth) acrylate and silyl (meth) acrylate modified nanoparticles while dispersing, and dispersing to obtain the product.
  27. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 26, wherein the nanoparticles modified with a silane coupling agent, a (meth) acrylate, a silyl (meth) acrylate comprise the following preparation steps:
    adding an organic solvent B and the nanoparticles modified by the silane coupling agent into a preparation container, heating to 80-115 ℃ in an atmosphere of protective gas, then dripping a mixed solution of (methyl) acrylate, (methyl) silyl acrylate and an initiator into the preparation container within 5-10 hours, keeping heating, and after dripping is finished, centrifugally washing to obtain the nanoparticles modified by the silane coupling agent, (methyl) acrylate and (methyl) silyl acrylate.
  28. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 27, wherein the silane coupling agent-modified nanoparticles comprise the following preparation steps:
    and (2) loading the organic solvent A and the nanoparticles into a preparation container, carrying out ultrasonic dispersion, heating to 40-60 ℃ in an atmosphere of protective gas, then dripping a silane coupling agent into the preparation container within 3-6 hours, keeping heating, and carrying out centrifugal washing after dripping is finished to obtain the silane coupling agent modified nanoparticles.
  29. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 27 or 28, wherein the silane coupling agent-modified nanoparticles comprise the following preparation raw materials in parts by weight: 5-25 parts of nano particles, 10-51 parts of silane coupling agent and 15-45 parts of organic solvent A.
  30. The method for producing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 28 or 29, wherein: the organic solvent A is one or a combination of a hydrocarbon solvent and an alcohol solvent.
  31. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 30, wherein: the hydrocarbon solvent is any one or a combination of toluene, xylene and trimethylbenzene.
  32. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 30, wherein: the alcohol solvent is one or a combination of n-butanol, isobutanol and phenethyl alcohol.
  33. The method for producing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 28 to 32, wherein: the nano particles are one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide or nano aluminum oxide.
  34. The method for producing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 28 to 33, wherein: the particle size of the nanoparticles is 10-40 nm.
  35. The method for producing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 28 to 34, wherein: the silane coupling agent is one of KBE-1003, KBM503 and KBM 5103.
  36. The method for preparing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 28 to 35, wherein the silyl (meth) acrylate copolymer has a solid content of 55%.
  37. The method for preparing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 28 to 36, wherein the silyl (meth) acrylate copolymer has a viscosity of 10 to 15 poise.
  38. The method for preparing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 28 to 37, wherein the silyl (meth) acrylate copolymer has a weight average molecular weight of 10000 to 15000.
  39. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 26 or 27, wherein the silane coupling agent, (meth) acrylate, and silyl (meth) acrylate-modified nanoparticles comprise, by weight, 10 to 30 parts of the silane coupling agent-modified nanoparticles, 1 to 20 parts of the (meth) acrylate, 20 to 40 parts of the silyl (meth) acrylate, 1 to 5 parts of the initiator, and 10 to 50 parts of the organic solvent B.
  40. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 27, wherein: the (methyl) acrylate is one or a combination of methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate and isooctyl acrylate.
  41. The method for producing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 27 to 40, wherein: the (methyl) acrylate is one or a combination of 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate and 2-hydroxybutyl (methyl) acrylate.
  42. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 27 to 41, wherein the silyl (meth) acrylate has the following structural formula:
    Figure PCTCN2019123031-APPB-100002
    wherein R is H or CH3，R 1、R 2、R 3Is alkyl, cycloalkyl, aryl or aralkyl with 1-20 carbon atoms.
  43. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to any one of claims 27 to 42, wherein the silyl (meth) acrylate is a combination of any one or more of trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate.
  44. The method for preparing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 27 to 43, wherein the organic solvent B is one or a combination of two of an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, and an ether solvent.
  45. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 44, wherein: the aromatic hydrocarbon solvent is one or a combination of toluene and xylene.
  46. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 44, wherein: the ester solvent is one or a combination of butyl acetate and ethyl acetate.
  47. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 44, wherein: the ketone solvent is one or a combination of methyl ethyl ketone, butanone and cyclohexanone.
  48. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 44, wherein: the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.
  49. The method for producing an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling paint according to any one of claims 27 to 40, wherein: the initiator is any one or a combination of two of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile.
  50. The method for preparing an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling paint according to claim 26, wherein the organic-inorganic nanocomposite antifouling coating comprises the following raw materials, by weight, 4 to 40 parts of the silyl (meth) acrylate copolymer and 61 to 95 parts of the silane coupling agent, (meth) acrylate, and silyl (meth) acrylate-modified nanoparticles.
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