CN107936831B - Hydrophilic modified fouling release type marine antifouling paint and preparation method thereof - Google Patents
Hydrophilic modified fouling release type marine antifouling paint and preparation method thereof Download PDFInfo
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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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
- 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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
Abstract
The invention relates to a hydrophilic modified fouling release type antifouling coating and a preparation method thereof, which comprises the steps of synthesizing a PVP-polyacrylate copolymer or a PVP-OH homopolymer by using an N-vinylpyrrolidone monomer through free radical polymerization or RAFT polymerization method, crosslinking the PVP-polyacrylate copolymer or the PVP-OH homopolymer in a polydimethylsiloxane network, and coating the PDMS network on the surface of a substrate to obtain the hydrophilic modified fouling release type antifouling coating. Compared with a control group, the protein adsorption quantity is reduced by 75.8-83.2%, and the bacterial adhesion quantity is reduced by 96.0-98.7%; the attaching density of the algae is reduced by 93.6 to 97.3 percent; the barnacle adhesive force is reduced by 58.2 to 75.9 percent; the antifouling effect of the hydrophilic modified antifouling coating is greatly improved compared with that of a pure PDMS coating. Therefore, the marine antifouling coating has good practical application value as a marine antifouling coating.
Description
Technical Field
The invention relates to the field of synthesis of antifouling paint, in particular to hydrophilic modified fouling release type antifouling paint and a preparation method thereof.
Background
The development of marine industries and marine facilities such as offshore military, marine transportation, marine culture, offshore drilling platforms and the like faces a great problem, namely marine biofouling. At present, about 4000 to 5000 kinds of discovered marine organisms with fouling adhesion characteristics can adhere to the solid surface in seawater and grow and propagate in large quantities to form a biofouling layer, so that fouling damage accidents are generated on the surfaces of ships, marine engineering and underwater facilities. Such fouling damage may cause many hazards, such as increasing the self weight and the sailing speed of the ship, increasing fuel consumption, and seriously affecting the sailing performance of the ship; blocking the submarine pipeline or the marine culture net; influence the normal use of offshore detection equipment such as acoustic instruments and the like; increase the encumbrance of an offshore oil or gas exploitation platform, accelerate the corrosion speed of the metal under the sea, and the like.
So far, the most effective method for solving the marine biofouling is to paint marine antifouling paint on the surface of facilities in the sea. Most of the traditional marine antifouling paint is added with an antifouling agent, and the antifouling effect is achieved by continuously releasing a toxic biocide underwater. Among them, the most effective is the self-polishing organotin antifouling paint, which brings great profit to the shipping industry since the 60 s of the 20 th century. However, organotin biocides are highly toxic and also cause death or malformation of non-target marine organisms, severely disrupting ecological balance, and thus self-polishing antifouling paints containing organotins have been completely banned by the International Maritime Organization (IMO) since 1/2008. At present, the most used biocides containing copper, zinc and the like are self-polishing antifouling coatings, and although the biocides of copper and zinc type have no great toxicity of organic tin, the biocides also cause potential safety hazards to marine ecological balance and human health. With the enhancement of environmental protection consciousness of people, the marine antifouling paint containing the toxic biocide is bound to gradually exit the historical stage and is replaced by the nontoxic environment-friendly paint.
The low surface energy fouling release type antifouling paint is an ideal environment-friendly marine antifouling paint as an antifouling paint without biocide. The antifouling mechanism is that marine organisms are not easy to attach to the surface of the substrate due to the physical property of the coating with low surface energy, and the attached fouling organisms are easy to wash away by seawater in the running process of the ship or can be removed by simple mechanical cleaning. The low surface energy antifouling paint is generally composed of organic silicon resin, organic fluorine resin or fluorine silicon resin as a base material, and a cross-linking agent, a stabilizing agent, an additive and other auxiliary agents, wherein the organic silicon resin is most widely applied. Although the organic silicon fouling release type coating meets the requirements of no toxicity and environmental protection, the pure organic silicon coating has many problems in practical application, such as poor mechanical properties, low adhesion to ship bodies, easy shedding, limited application to ship surfaces with high navigational speed and the like, and most importantly, the organic silicon fouling release type coating cannot resist the adhesion of fouling mucus and is difficult to wash away. The fouling mucus generally consists of biomolecules such as proteins, and micro marine organisms such as bacteria and diatoms. In order to improve the antifouling performance of the organic silicon fouling release type antifouling paint, hydrophilic or amphiphilic polymer is an effective strategy.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides an organosilicon low-surface-energy antifouling paint containing a hydrophilic polymer, wherein the hydrophilic polymer can effectively prevent or reduce the adhesion and adhesion of protein and bacteria on the surface of a coating, thereby playing a role in resisting fouling mucus in a marine environment and radically inhibiting or reducing the formation of marine biofouling on underwater facilities or ship bodies.
In order to achieve the aim, the invention designs a hydrophilic modified fouling release type marine antifouling paint; the PVP-polyacrylate copolymer or PVP-OH homopolymer is synthesized by using N-vinylpyrrolidone monomers through free radical polymerization or RAFT polymerization, and is crosslinked in a polydimethylsiloxane network to be coated on the surface of a substrate, so that the hydrophilic modified fouling release type antifouling coating is obtained.
The structure of the polyvinyl pyrrolidone modified polydimethylsiloxane coating is as follows:
in the formula (I), the compound is shown in the specification,
is a hydrophilic side chain polymer A or B; r1Is CH3Or C2H5；
R2Is Polydimethylsiloxane (PDMS) characterized by the structural formula:
wherein the hydrophilic side chain A is polyvinylpyrrolidone-polyacrylic resin (PVP-co-PAR), and the structure is as follows:
in the formula, R3Is H or CH3；R4Is CH3Or C2H5；R5Is C2H5Or C4H9Or C8H17；R6Is CH2Or (CH)2)2Or (CH)2)3(ii) a n is 120 to 160; m is 20-40; p is 20-40; q is 10-20;
the structure of polyvinylpyrrolidone (PVP-SiOH) with a hydrophilic side chain B as a silane coupling agent end capping is as follows:
in the formula, R7Is O or NH; r8Is CH3Or C2H5(ii) a n is 120 to 200.
The concrete description is as follows:
1. the synthesis of the hydrophilic side chain polymer a is as follows:
(1) dissolving 0.5-1 part by weight of initiator in 10-30 parts by weight of organic solvent, and preheating to 65-85 ℃ to obtain a first solution;
(2) dissolving 60-80 parts by weight of N-vinyl pyrrolidone (NVP), 10-30 parts by weight of acrylate soft monomer, 10-30 parts by weight of (methyl) acrylate hard monomer, 5-10 parts by weight of hydroxyalkyl methacrylate monomer and 1.5-3.5 parts by weight of initiator in 20-70 parts by weight of organic solvent to obtain a second solution;
(3) dropwise adding the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dropwise adding speed is controlled to be 0.5-2 ml/s; after the solution is dripped, the reaction is carried out for 2 to 4 hours at the temperature of 65 to 85 ℃, then 0.5 to 2 weight parts of initiator is added, the temperature is raised to 85 to 110 ℃, the reaction is kept unchanged for 6 to 24 hours to obtain a reaction product, then a settling agent with the volume 5 to 10 times of that of the reaction liquid is added to precipitate the polymer, and the polymer A is obtained after centrifugation and vacuum drying.
The initiator in the steps (1), (2) and (3) is selected from 2,2 '-azobisisobutyronitrile, benzoyl peroxide or 2,2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide;
the organic solvent in the step (1) and (2) is selected from mixed solvents of xylene and butyl acetate, and the mass ratio of the mixed solvents is preferably 1: 1;
the soft acrylate monomer in the step (2) is selected from ethyl acrylate, butyl acrylate or n-octyl acrylate; the (meth) acrylate hard monomer is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate or methyl acrylate;
in the step (3), the settling agent is selected from petroleum ether, n-hexane or diethyl ether.
2. The procedure for the synthesis of the hydrophilic side-chain polymer B is as follows:
(1) dissolving 0.5-1.5 parts by weight of initiator in 10-30 parts by weight of organic solvent, adding 30-50 parts by weight of N-vinylpyrrolidone and 2-6 parts by weight of sulfhydryl compound, preheating to 55-85 ℃, keeping the temperature for reacting for 6-12 hours to obtain modified polyvinylpyrrolidone solution, spin-drying the solvent, adding organic solvent with the volume being 1-4 times of the mass of the solid to dissolve the solid, then adding precipitator with the volume being 20-40 times of the volume of the modified polyvinylpyrrolidone solution to precipitate the polymerization reaction product, centrifuging, and vacuum drying to obtain the modified polyvinylpyrrolidone;
(2) dissolving 40-60 parts by weight of the product obtained in the step (1) and 4-6 parts by weight of functional siloxane crosslinking agent in 34-44 parts by weight of organic solvent, preheating to 60-90 ℃, keeping the temperature for reaction for 2-5 hours to obtain a reaction product, adding a settling agent with the volume 5-10 times of that of the reaction liquid to precipitate the polymer, centrifuging and drying in vacuum to obtain the hydrophilic polymer B.
The initiator in the step (1) is selected from 2,2 '-azobisisobutyronitrile, benzoyl peroxide and 2,2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide);
the organic solvent in the step (1) or (2) is selected from dichloromethane or tetrahydrofuran
The mercapto compound in the step (2) is selected from mercaptoethanol or mercaptoethylamine;
the functional siloxane cross-linking agent in the step (2) is selected from (3-isocyano propyl) trimethoxy silane or (3-isocyano propyl) triethoxy silane;
the settling agent in the step (2) is selected from petroleum ether, n-hexane or diethyl ether.
3. The preparation process of the hydrophilic modified organic silicon fouling release type antifouling coating comprises the following steps:
(1) weighing 1-8 parts by weight of hydrophilic side chain polymer A or B and 10-30 parts by weight of polydimethylsiloxane, adding the hydrophilic side chain polymer A or B and the polydimethylsiloxane into 20-30 parts by weight of organic solvent, and uniformly stirring to obtain a reaction mixture;
(2) adding 1-4 parts by weight of cross-linking agent into the mixture in the step (1), and uniformly stirring to obtain coating prepolymer
(3) Adding 0.5-1 part by weight of catalyst into the mixture in the step (2), uniformly stirring, quickly and uniformly coating a film on a substrate, and then curing at 40-60 ℃ to obtain a hydrophilic modified antifouling coating;
the polydimethylsiloxane in the step (1) is dihydroxy-terminated polydimethylsiloxane (HO-PDMS-OH);
the organic solvent in the step (1) is a mixed solvent of xylene and butyl acetate, and the mass ratio of the mixed solvent is preferably 1: 1;
the cross-linking agent in the step (2) is selected from methyl triacetoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-aminopropyltriethoxysilane or (3-isocyanopropyl) triethoxysilane;
the catalyst used in the step (3) is selected from dibutyltin dilaurate, dibutyltin diacetate or stannous octoate.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention discloses a preparation method of a hydrophilic modified fouling release type antifouling paint, which aims to solve the fouling problem of marine organisms on the surfaces of ships and marine facilities. The protein adsorption experiment, the bacteria adhesion experiment, the diatom adhesion experiment and the simulation barnacle adhesion experiment prove that the antifouling effect of the hydrophilic modified antifouling coating is greatly improved compared with that of a control group coating. Therefore, the marine antifouling coating has good practical application value as a marine antifouling coating.
1) Protein adsorption experiments prove that the protein adsorption amount of the hydrophilic modified fouling release type antifouling paint provided by the invention is reduced by 75.8% -83.2% compared with that of a control group.
2) The adhesion experiment of escherichia coli proves that the adhesion of bacteria of the hydrophilic modified fouling release type antifouling paint provided by the invention is reduced by 96.0% -98.7% compared with that of bacteria of a control group.
3) The hydrophilic modified fouling release type antifouling paint provided by the invention has the advantage that the bacterial adhesion amount is reduced by 87.5% -97.1% compared with that of a control group through a staphylococcus aureus adhesion experiment.
4) The attachment experiment of the navicular diatom proves that the diatom attachment density of the hydrophilic modified fouling release type antifouling paint provided by the invention is reduced by 93.6% -97.3% compared with that of a control group.
5) The experiment of simulating the barnacle adhesion force proves that the barnacle adhesion force of the hydrophilic modified fouling release type antifouling paint provided by the invention is reduced by 58.2% -75.9% compared with the barnacle adhesion force of a control group.
6) The invention has obtained the open fund project (project number: QNLM2016ORP 0407).
Drawings
Fig. 1 results of Fibrinogen (Fibrinogen) adsorption of a hydrophilically modified fouling release type antifouling paint;
FIG. 2 shows the colony growth of Escherichia coli (Escherichia coli) adhesion experiment of the hydrophilic modified fouling release type antifouling paint;
FIG. 3 Escherichia coli (Escherichia coli) adhesion test bacteria density of the hydrophilically-modified fouling release type antifouling paint;
FIG. 4 shows the colony growth of Staphylococcus aureus (Staphylococcus aureus) adhesion experiment of the hydrophilic modified fouling release type antifouling paint;
FIG. 5 shows the density of Staphylococcus aureus (Staphylococcus aureus) adhered test bacteria of the hydrophilically-modified fouling release type antifouling paint;
FIG. 6 shows the diatom attachment density of navicula (Navicula parva) attachment experiment of the hydrophilically modified fouling release type antifouling paint.
Detailed Description
The present invention will be explained in more detail by the following examples, which are not intended to limit the invention;
example 1
The hydrophilic modified organic silicon fouling release type marine antifouling paint is prepared according to the following steps
(1) Weighing 0.50g of 2,2' -azobisisobutyronitrile, dissolving in a mixed solvent of 5g of dimethylbenzene and 5g of butyl acetate, and preheating to 80 ℃ to obtain an initiator solution;
(2) 6.67g of N-vinylpyrrolidone (NVP), 2.24g of Butyl Acrylate (BA), 1.75g of Methyl Methacrylate (MMA), 0.65g of hydroxyethyl methacrylate (HEMA) and 1g of 2,2' -azobisisobutyronitrile were dissolved in a mixed solvent of 10g of xylene and 10g of butyl acetate to obtain a reactant solution;
(3) slowly dripping the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dripping speed is controlled to be 0.5 ml/s; after the solution is dropwise added, preserving heat for 4 hours, adding 0.5g of 2,2' -azobisisobutyronitrile, heating to 110 ℃, preserving heat for reaction for 12 hours to obtain a reaction product, adding petroleum ether with the volume 10 times that of the reaction solution to precipitate a polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer A;
(4) weighing 0.1g of the hydrophilic side chain polymer A obtained in the step (3), and dissolving the hydrophilic side chain polymer A in a mixed solvent of 1g of dimethylbenzene and 1g of butyl acetate to obtain a uniform mixture;
(5) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (4), and uniformly stirring to obtain a mixture;
(6) 0.2g of methyltriacetoxysilane is weighed and added into the mixture in the step (5), and the mixture is obtained after even stirring;
(7) 0.01g of dibutyltin dilaurate is weighed and added into the mixture in the step (6), and the mixture is stirred uniformly to obtain an antifouling paint prepolymer;
(8) coating the coating prepolymer on a test substrate quickly and uniformly, controlling the thickness to be 100-1000 μm, drying and curing in a 40 ℃ oven to obtain a uniform coating, and soaking the coating in artificial seawater for testing for later use.
Example 2
The hydrophilic modified organic silicon fouling release type marine antifouling paint is prepared according to the following steps
(1) Weighing 0.75g of 2,2' -azobisisobutyronitrile, dissolving in a mixed solvent of 10g of dimethylbenzene and 10g of butyl acetate, and preheating to 85 ℃ to obtain an initiator solution;
(2) 6.0g of N-vinylpyrrolidone (NVP), 3.0g of Butyl Acrylate (BA), 1.0g of Methyl Methacrylate (MMA), 0.5g of hydroxyethyl methacrylate (HEMA), 0.5g of 2,2' -azobisisobutyronitrile were dissolved in a mixed solvent of 10g of xylene and 10g of butyl acetate to obtain a reactant solution;
(3) slowly dripping the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dripping speed is controlled to be 0.5 ml/s; after the solution is dropwise added, preserving heat for 4 hours, adding 0.5g of 2,2' -azobisisobutyronitrile, heating to 110 ℃, preserving heat for reaction for 12 hours to obtain a reaction product, adding petroleum ether with the volume 10 times that of the reaction solution to precipitate a polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer A;
(4) weighing 0.2g of the hydrophilic side chain polymer A obtained in the step (3), and dissolving the hydrophilic side chain polymer A in a mixed solution of 1g of dimethylbenzene and 1g of butyl acetate to obtain a uniform mixture;
(5) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (4), and uniformly stirring to obtain a mixture;
(6) 0.2g of methyltriacetoxysilane is weighed and added into the mixture in the step (5), and the mixture is obtained after even stirring;
(7) 0.01g of dibutyltin dilaurate is weighed and added into the mixture in the step (6), and the mixture is stirred uniformly to obtain an antifouling paint prepolymer;
(8) coating the coating prepolymer on a test substrate quickly and uniformly, controlling the thickness to be 100-1000 μm, drying and curing in a 40 ℃ oven to obtain a uniform coating, and soaking the coating in artificial seawater for testing for later use.
Example 3
The hydrophilic modified organic silicon fouling release type marine antifouling paint is prepared according to the following steps
(1) Weighing 0.50g of 2,2' -azobisisobutyronitrile, dissolving in 15g of xylene and 15g of butyl acetate, and preheating to 80 ℃ to obtain an initiator solution;
(2) dissolving 8.0g of N-vinylpyrrolidone (NVP), 1.0g of Butyl Acrylate (BA), 3.0g of Methyl Methacrylate (MMA), 1.0g of hydroxyethyl methacrylate (HEMA), 1.5g of 2,2' -azobisisobutyronitrile in 35g of a mixed organic solvent of xylene and 35g of butyl acetate to obtain a reactant solution;
(3) slowly dripping the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dripping speed is controlled to be 0.5 ml/s; after the solution is dropwise added, preserving heat for 4 hours, adding 0.5g of 2,2' -azobisisobutyronitrile, heating to 110 ℃, preserving heat for reaction for 12 hours to obtain a reaction product, adding diethyl ether with the volume 10 times that of the reaction solution to precipitate a polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer A;
(4) weighing 0.3g of the hydrophilic side chain polymer A obtained in the step (3), 1g of xylene and 1g of butyl acetate to obtain a uniform mixture;
(5) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (4), and uniformly stirring to obtain a mixture;
(6) 0.2g of methyltriacetoxysilane is weighed and added into the mixture in the step (5), and the mixture is obtained after even stirring;
(7) 0.01g of dibutyltin dilaurate is weighed and added into the mixture in the step (6), and the mixture is stirred uniformly to obtain an antifouling paint prepolymer;
(8) coating the coating prepolymer on a test substrate quickly and uniformly, controlling the thickness to be 100-1000 μm, drying and curing in a 40 ℃ oven to obtain a uniform coating, and soaking the coating in artificial seawater for testing for later use.
Example 4
(1) Dissolving 0.5g of azobisisobutyronitrile into 10g of isopropanol, adding 8g N-vinylpyrrolidone and 0.8g of mercaptoethanol, preheating to 65 ℃, preserving heat for 8 hours to obtain a modified polyvinylpyrrolidone solution, spin-drying the solvent, adding 2g of dichloromethane with the volume of solid mass to dissolve the solid, then adding 40g of ether to precipitate the polymerization reaction product, centrifuging, and vacuum-drying to obtain the modified polyvinylpyrrolidone solid;
(2) adding 5g of the product obtained in the step (1) into 0.5g of (3-isocyano propyl) triethoxysilane by weight, dissolving the mixture in 5g of tetrahydrofuran solvent, preheating to 60 ℃, reacting for 2 hours to obtain a reaction product, adding a settling agent with the volume 5-10 times that of the reaction liquid to precipitate the polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer B;
(3) weighing 0.3g of the hydrophilic side chain polymer B obtained in the step (2), 1g of xylene and 1g of butyl acetate to obtain a uniform mixture;
(4) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (3), and uniformly stirring to obtain a mixture;
(5) weighing 0.2g of methyltriacetoxysilane into the mixture in the step (4), and stirring uniformly to obtain a mixture;
(6) 0.01g of dibutyltin dilaurate was weighed out and added to the mixture in (5), and the mixture was stirred uniformly to obtain an antifouling paint prepolymer.
Example 5
The hydrophilic modified organic silicon fouling release type marine antifouling paint is prepared according to the following steps
(1) Weighing 1g of 2,2' -azobisisobutyronitrile, dissolving in a mixed solvent of 15g of xylene and 15g of butyl acetate, and preheating to 85 ℃ to obtain an initiator solution;
(2) dissolving 80g of N-vinylpyrrolidone (NVP), 20g of any ester of acrylic acid (BA), 20g of methyl acrylate (MMA), 11.5g of hydroxyethyl methacrylate (HEMA), 0.75g of 2,2' -azobisisobutyronitrile in 30g of a mixed organic solvent of xylene and 30g of butyl acetate to obtain a reactant solution;
(3) slowly dripping the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dripping speed is controlled to be 0.5 ml/s; after the solution is dropwise added, preserving heat for 4 hours, adding 1g of 2,2' -azobisisobutyronitrile, heating to 110 ℃, preserving heat for reaction for 12 hours to obtain a reaction product, adding n-hexane with the volume 10 times that of the reaction solution to precipitate the polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer A;
(4) weighing 0.1g of the hydrophilic side chain polymer A obtained in the step (3), and dissolving the hydrophilic side chain polymer A in a mixed solution of 1g of dimethylbenzene and 1g of butyl acetate to obtain a uniform mixture;
(5) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (4), and uniformly stirring to obtain a mixture;
(6) 0.2g of methyltriacetoxysilane is weighed and added into the mixture in the step (5), and the mixture is obtained after even stirring;
(7) 0.075g of dibutyltin dilaurate is weighed and added into the mixture in the step (6), and the mixture is stirred uniformly to obtain an antifouling paint prepolymer;
(8) coating the coating prepolymer on a test substrate quickly and uniformly, controlling the thickness to be 100-1000 μm, drying and curing in a 40 ℃ oven to obtain a uniform coating, and soaking the coating in artificial seawater for testing for later use.
Example 6
The hydrophilic modified organic silicon fouling release type marine antifouling paint is prepared according to the following steps
(1) Weighing 0.75g of 2,2' -azobisisobutyronitrile, dissolving in a mixed solution of 10g of dimethylbenzene and 10g of butyl acetate, and preheating to 70 ℃ to obtain an initiator solution;
(2) dissolving 70g of N-vinylpyrrolidone (NVP), 15g of ethyl methacrylate (BA), 15g of ethyl methacrylate (MMA), 11.5g of hydroxymethyl methacrylate (HMMA) and 3.5g of 2,2' -azobisisobutyronitrile in 70g of a mixed organic solvent of xylene and 70g of butyl acetate to obtain a reactant solution;
(3) slowly dripping the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dripping speed is controlled to be 0.5 ml/s; after the solution is dropwise added, preserving heat for 4 hours, adding 2g of 2,2' -azobisisobutyronitrile, heating to 110 ℃, preserving heat for reaction for 12 hours to obtain a reaction product, adding a settling agent with the volume 10 times that of the reaction solution to precipitate the polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer A;
(4) weighing 0.2g of the hydrophilic side chain polymer A obtained in the step (3), and dissolving the hydrophilic side chain polymer A in a mixed solution of 1g of dimethylbenzene and 1g of butyl acetate to obtain a uniform mixture;
(5) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (4), and uniformly stirring to obtain a mixture;
(6) 0.4g of methyl gamma- (methacryloyloxy) propyl trimethoxy silane is weighed and added into the mixture in the step (5), and the mixture is obtained after even stirring;
(7) 0.1g of dibutyltin diacetate is weighed and added into the mixture in the step (6), and the mixture is uniformly stirred to obtain an antifouling paint prepolymer;
(8) coating the coating prepolymer on a test substrate quickly and uniformly, controlling the thickness to be 100-1000 μm, drying and curing in a 40 ℃ oven to obtain a uniform coating, and soaking the coating in artificial seawater for testing for later use.
Example 7
(1) Dissolving 0.75g of azobisisobutyronitrile into 20g of isopropanol, adding 40g N-vinylpyrrolidone and 4g of mercaptoethanol, preheating to 65 ℃, keeping the temperature for 8 hours to obtain a modified polyvinylpyrrolidone solution, spin-drying the solvent, adding 20g of dichloromethane with the volume of solid mass to dissolve solids, then adding 600g of ether to precipitate a polymerization reaction product, centrifuging, and vacuum-drying to obtain a modified polyvinylpyrrolidone solid;
(2) adding 5g of the product obtained in the step (1) into 0.5g of (3-isocyanopropyl) triethoxysilane to be dissolved in 5g of tetrahydrofuran solvent, preheating to 60 ℃, reacting for 2 hours to obtain a reaction product, adding 50g of n-hexane in volume of reaction liquid to precipitate a polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer B;
(3) weighing 0.1g of the hydrophilic side chain polymer B obtained in the step (2), 1g of xylene and 1g of butyl acetate to obtain a uniform mixture;
(4) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (3), and uniformly stirring to obtain a mixture;
(5) weighing 0.2g of methyltriacetoxysilane into the mixture in the step (4), and stirring uniformly to obtain a mixture;
(6) 0.01g of dibutyltin dilaurate was weighed out and added to the mixture in (5), and the mixture was stirred uniformly to obtain an antifouling paint prepolymer.
Example 8
(1) Dissolving 1.5g of azobisisobutyronitrile into 30g of isopropanol, adding 50g N-vinylpyrrolidone and 6g of mercaptoethanol, preheating to 85 ℃, keeping the temperature for 8 hours to obtain a modified polyvinylpyrrolidone solution, spin-drying the solvent, adding 4g of dichloromethane with the volume of solid mass to dissolve solids, then adding 1200g of diethyl ether to precipitate a polymerization reaction product, centrifuging, and vacuum-drying to obtain a modified polyvinylpyrrolidone solid;
(2) adding 5g of the product obtained in the step (1) into 0.5g of (3-isocyanopropyl) triethoxysilane, dissolving the mixture in 5g of tetrahydrofuran solvent, preheating to 60 ℃, reacting for 2 hours to obtain a reaction product, adding 50g of petroleum ether in volume of reaction liquid to precipitate a polymer, centrifuging and drying in vacuum to obtain a hydrophilic side chain polymer B;
(3) weighing 0.5g of the hydrophilic side chain polymer B obtained in the step (2), 1g of xylene and 1g of butyl acetate to obtain a uniform mixture;
(4) weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into the solution in the step (3), and uniformly stirring to obtain a mixture;
(5) weighing 0.2g of methyltriacetoxysilane into the mixture in the step (4), and stirring uniformly to obtain a mixture;
(6) 0.01g of dibutyltin dilaurate was weighed out and added to the mixture in (5), and the mixture was stirred uniformly to obtain an antifouling paint prepolymer.
Comparative examples
The hydrophilic modified organic silicon fouling release type marine antifouling paint is prepared according to the following steps
(1) Weighing 2g of polydimethylsiloxane, adding the polydimethylsiloxane into 1-2g of dimethylbenzene, and uniformly stirring to obtain a mixture;
(2) weighing 0.17-0.23g of methyltriacetoxysilane into the mixture in the step (1), and stirring uniformly to obtain a mixture;
(3) 0.01-0.05g of dibutyltin dilaurate is weighed and added into the mixture in the step (2), and the mixture is stirred uniformly to obtain an antifouling paint prepolymer;
(4) coating the coating prepolymer on a test substrate quickly and uniformly, controlling the thickness to be 100-1000 μm, drying and curing in a 40 ℃ oven to obtain a uniform coating, and soaking the coating in artificial seawater for testing for later use.
Example 9
The method for testing the antifouling performance of the hydrophilic modified organic silicon fouling release type marine antifouling coating comprises the following steps:
(1) the antifouling coating protein adsorption test adopts an enzyme-linked immunosorbent assay (ELISA) method;
(2) the adhesion experiment of the bacteria on the antifouling coating adopts a plate method, and the bacteria for the experiment are escherichia coli (Escherichia coli) and Staphylococcus aureus (Staphylococcus aureus);
(3) the antifouling coating diatom adheres to the experiment, the diatom used in the experiment is: navicula diatoms (Naviculaparva);
(4) the simulated barnacle adhesion test uses standard test method ASTM D5618.
And (3) testing results:
(1) the results of ELISA experiments with the hydrophilic modified fouling release antifouling paint are shown in FIG. 1, in which example 1 is a test of pure silicone antifouling paint which is not modified by hydrophilicity as a control group, and other examples are a test group of pure silicone antifouling paint which is modified by hydrophilicity as an experimental group, and the adhesive protein used is Fibrinogen (Fibrinogen). The data in the figure can show that the protein adsorption capacity of the experimental group is reduced by 75.8-83.2% compared with the protein adsorption capacity of the control group, which shows that the protein adsorption resistance of the organic silicon fouling release type antifouling paint is obviously improved after hydrophilic modification.
(2) Results of Escherichia coli (Escherichia coli) experiments on the hydrophilic modified fouling release type antifouling paint are shown in fig. 2 and 3, in which example 1 is a test of a pure silicone antifouling paint which is not hydrophilically modified as a control group, and other examples are experimental groups by using a hydrophilically modified silicone antifouling paint. The data in the figure can show that the bacterial adhesion amount of the experimental group is 1.3-4.0% of that of the control group, which shows that after hydrophilic modification, the anti-escherichia coli adhesion capability of the organic silicon fouling release type antifouling paint is obviously improved.
(3) The results of Staphylococcus aureus (Staphylococcus aureus) experiments of the hydrophilic modified fouling release type antifouling paint are shown in fig. 4 and 5, in which example 1 is a test of a pure silicone antifouling paint which is not hydrophilic modified as a control group, and other examples are silicone antifouling paints modified by hydrophilicity as an experimental group. The data in the figure can show that the bacterial adhesion amount of the experimental group is 2.9% -12.5% of that of the control group, which shows that the anti-staphylococcus aureus adhesion capability of the organic silicon fouling release type antifouling paint is obviously improved after hydrophilic modification.
(4) The experimental results of the attachment experiments of navicula diatoms (Naviculaparva) of the hydrophilically modified fouling release type antifouling paint are shown in fig. 6, in which the control group was a pure silicone antifouling paint which was not hydrophilically modified, and the other examples were experimental groups of hydrophilically modified silicone antifouling paints. The data in the figure can show that the diatom attachment density of the experimental group is 2.7% -6.4% of that of the control group, which shows that the diatom attachment resistance of the organic silicon fouling release type antifouling paint is obviously improved after hydrophilic modification.
(5) The results of experiments on the simulated barnacle adhesion of the hydrophilically modified fouling release antifouling paint are shown in table 1, wherein example 1 is a test of a pure silicone antifouling paint which is not hydrophilically modified as a control group, and other examples are tests of a hydrophilic modified silicone antifouling paint as an experimental group. The data in the figure can show that the simulated barnacle adhesion of the experimental group is 58.2% -75.9% lower than that of the control group, which shows that after hydrophilic modification, the fouling release capacity of the organic silicon fouling release type antifouling paint is obviously improved.
TABLE 1 Experimental results of adhesion of simulated barnacles of hydrophilic modified fouling release antifouling paints
Claims (10)
1. A hydrophilic modified fouling release type marine antifouling paint is characterized in that polyvinylpyrrolidone modified polydimethylsiloxane resin has a structure shown in formula (1):
in the formula (1), the reaction mixture is,
is a hydrophilic side chain polymer A or B; r1Is CH3Or C2H5；
R2Is polydimethylsiloxane having the structure of formula (2):
in the formula (1), the hydrophilic side chain polymer A is polyvinylpyrrolidone-polyacrylic acid resin, and the structure is formula (3):
in the formula (3), R3Is H or CH3；R4Is CH3Or C2H5；R5Is C2H5Or C4H9Or C8H17；R6Is CH2Or (CH)2)2Or (CH)2)3(ii) a n is 120 to 160; m is 20-40; p is 20-40; q is 10-20;
in the formula (1), the structure of the polyvinyl pyrrolidone of which the hydrophilic side chain polymer B is terminated by the silane coupling agent is shown as a formula (4):
in the formula (4), R7Is O or NH; r8Is CH3Or C2H5(ii) a n is 120 to 200.
2. The coating of claim 1, wherein the hydrophilic side-chain polymer a is prepared by a process comprising the steps of:
(1) dissolving 0.5-1 part by weight of initiator in 10-30 parts by weight of organic solvent, and preheating to 65-85 ℃ to obtain a first solution;
(2) dissolving 60-80 parts by weight of N-vinyl pyrrolidone, 10-20 parts by weight of acrylate soft monomer, 10-20 parts by weight of (methyl) acrylate hard monomer, 5-10 parts by weight of hydroxyalkyl methacrylate monomer and 1.5-3.5 parts by weight of initiator in 20-70 parts by weight of organic solvent to obtain a second solution;
(3) dropwise adding the solution obtained in the step (2) into the solution obtained in the step (1), wherein the dropwise adding speed is controlled to be 0.5-2 mL/s; after the solution is dripped, the reaction is carried out for 2 to 4 hours at the temperature of 65 to 85 ℃, then 0.5 to 2 weight parts of initiator is added, the temperature is raised to 85 to 110 ℃, the reaction is kept unchanged for 6 to 24 hours to obtain a reaction product, then a settling agent with the volume 5 to 10 times of that of the reaction liquid is added to precipitate the polymer, and the polymer is centrifuged and vacuum-dried to obtain the hydrophilic side chain polymer A.
3. The coating according to claim 1, wherein the hydrophilic side-chain polymer B is prepared by a process comprising the steps of:
(1) dissolving 0.5-1.5 parts by weight of initiator in 10-30 parts by weight of organic solvent, adding 30-50 parts by weight of N-vinylpyrrolidone and 2-6 parts by weight of sulfhydryl compound, preheating to 55-85 ℃, keeping the temperature for 6-12 hours to obtain modified polyvinylpyrrolidone solution, spin-drying the solvent, adding 1-4 times of solvent by volume of solid mass to dissolve the solid, then adding 20-40 times of precipitator by volume of modified polyvinylpyrrolidone solution to precipitate polymerization reaction products, centrifuging, and vacuum drying to obtain modified polyvinylpyrrolidone;
(2) dissolving 40-60 parts by weight of the product obtained in the step (1) and 4-6 parts by weight of functional siloxane crosslinking agent in 34-44 parts by weight of organic solvent, preheating to 60-90 ℃, reacting for 2-5 hours to obtain a reaction product, adding a settling agent with the volume 5-10 times of that of the reaction liquid to precipitate the polymer, centrifuging and drying in vacuum to obtain the hydrophilic side chain polymer B.
4. The coating according to claim 2, characterized in that the initiator is selected from 2,2 '-azobisisobutyronitrile, benzoyl peroxide or 2,2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide); the solvent is a mixed solvent of xylene and butyl acetate; the settling agent is selected from petroleum ether, n-hexane or diethyl ether.
5. The coating according to claim 3, characterized in that the initiator is selected from 2,2 '-azobisisobutyronitrile, benzoyl peroxide or 2,2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide); the solvent is selected from dichloromethane or tetrahydrofuran; the settling agent is selected from petroleum ether, n-hexane or diethyl ether.
6. The coating of claim 2, wherein the acrylate soft monomer for preparing the hydrophilic side chain polymer a is selected from the group consisting of ethyl acrylate, butyl acrylate, and n-octyl acrylate; the (meth) acrylate hard monomer is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate or methyl acrylate.
7. The coating according to claim 3, wherein the thiol compound for preparing the hydrophilic side-chain polymer B is selected from mercaptoethanol or mercaptoethylamine.
8. A method of preparing the hydrophilically modified fouling release marine antifouling paint according to claim 1, which comprises the following steps:
(1) weighing 1-8 parts by weight of hydrophilic side chain polymer A or B and 10-30 parts by weight of polydimethylsiloxane, adding the hydrophilic side chain polymer A or B and the polydimethylsiloxane into 20-30 parts by weight of organic solvent, and uniformly stirring to obtain a reaction mixture;
(2) adding 1-4 parts by weight of cross-linking agent into the mixture in the step (1), and uniformly stirring to obtain a coating prepolymer;
(3) adding 0.5-1 weight part of catalyst into the mixture in the step (2), uniformly stirring, uniformly coating a film on a substrate, and curing at 40-60 ℃ to obtain the hydrophilic modified antifouling coating.
9. The method of claim 8, wherein the polydimethylsiloxane is a bishydroxy terminated polydimethylsiloxane; the cross-linking agent is selected from methyl triacetoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-aminopropyl triethoxysilane or (3-isocyanopropyl) triethoxysilane.
10. The process of claim 8 wherein the catalyst is selected from the group consisting of dibutyltin dilaurate, dibutyltin diacetate, and stannous octoate; the organic solvent is a mixed solvent of xylene and butyl acetate.
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