CN107936831A - A kind of pollution release type marine antifouling coating of hydrophilic modifying and preparation method thereof - Google Patents

Abstract

The invention relates to a hydrophilic modified fouling-release antifouling coating and a preparation method thereof, wherein a PVP-polyacrylate copolymer or a PVP-OH homopolymer is synthesized by free radical polymerization or RAFT polymerization with N-vinylpyrrolidone monomer Polymer, cross-linked in the polydimethylsiloxane network, coated on the surface of the substrate, obtained a hydrophilic modified fouling release antifouling coating. Compared with the control group, the amount of protein adsorption decreased by 75.8%-83.2%, the amount of bacterial adhesion decreased by 96.0%-98.7%, the density of algae adhesion decreased by 93.6%-97.3%, and the adhesion of barnacles decreased by 58.2%- 75.9%; the antifouling effect of the hydrophilic modified antifouling coating has been greatly improved compared with that of the pure PDMS coating. Therefore, it has good practical application value as a marine antifouling coating.

Description

Hydrophilic modified fouling release marine antifouling coating and preparation method thereof

technical field

The invention relates to the field of synthesis of an antifouling paint, in particular to a hydrophilic modified fouling release type antifouling paint and a preparation method thereof.

Background technique

The development of marine undertakings and marine facilities such as maritime military, marine transportation, marine aquaculture, and offshore drilling platforms has always been facing a major problem-marine biofouling. At present, there are about 4,000 to 5,000 species of marine organisms with fouling adhesion characteristics that have been found. These marine organisms can attach to solid surfaces in seawater and grow and reproduce in large numbers, forming a biofouling layer, thereby causing damage to ships, marine engineering, and water. Fouling and damage accidents occur on the surface of the lower facilities. This kind of fouling damage will cause many hazards, such as increasing the ship's own weight and navigation speed, increasing fuel consumption, and seriously affecting the navigation performance of the ship; blocking submarine pipelines or marine breeding nets; affecting the normal operation of marine detection equipment such as acoustic instruments. Use: increase the burden on offshore oil or natural gas exploration platforms, accelerate the corrosion rate of underwater metals, etc.

So far, the most effective way to solve marine biofouling is to apply marine antifouling paint on the surface of marine facilities. Most of the traditional marine antifouling coatings are added with antifouling agents, which can achieve antifouling effect by continuously releasing toxic biocides underwater. The most effective of these is the organotin self-polishing antifouling paint, which has brought huge profits to the shipping industry since the 1960s. However, organotin biocides are very toxic, and it can also cause death or deformity of non-target marine organisms, seriously destroying the ecological balance. IMO it's completely disabled. At present, self-polishing antifouling coatings containing copper, zinc and other biocides are the most used. Although copper-zinc biocides are not as toxic as organotins, they also pose safety hazards to marine ecological balance and human health. With the enhancement of people's awareness of environmental protection, marine antifouling coatings containing toxic biocides will gradually withdraw from the historical stage and be replaced by non-toxic and environmentally friendly coatings.

Low surface energy fouling release antifouling coatings, as a biocide-free antifouling coating, are ideal environment-friendly marine antifouling coatings. Its anti-fouling mechanism is due to the physical properties of its coating with low surface energy, which makes it difficult for marine organisms to attach to the surface of the substrate, and the attached fouling organisms are easily washed away by seawater during the driving of the ship, or through simple mechanical cleaning. can be removed. Low surface energy antifouling coatings generally use silicone resins, organic fluorine resins or fluorosilicone resins as base materials, together with crosslinking agents, stabilizers, additives and other additives, among which silicone resins are the most widely used. Although silicone fouling release coatings meet the requirements of non-toxic and environmental protection, there are still many problems in the practical application of pure silicone coatings, such as poor mechanical properties, low adhesion to the hull and easy to fall off, and are limited to relatively large The most important thing is that it cannot resist the adhesion of fouling mucus on the surface of ships at high speeds, and it is difficult to wash off. Fouling mucus is generally composed of biomolecules such as proteins, and microscopic marine organisms such as bacteria and diatoms. In order to improve the antifouling performance of silicone fouling release antifouling coatings, it is an effective strategy to make them hydrophilic with hydrophilic or amphiphilic polymers.

Contents of the invention

The technical problem to be solved by the present invention is aimed at the deficiencies of the prior art, and provides a silicone low surface energy antifouling coating containing a hydrophilic polymer. The addition of a hydrophilic polymer can effectively prevent or reduce protein and bacteria Adhesion and adhesion on the surface of the coating, thereby playing a role in resisting fouling mucus in the marine environment, and inhibiting or reducing the formation of marine biofouling in underwater facilities or hulls from the root.

In order to achieve the above object, the present invention has designed a kind of fouling release marine antifouling coating of hydrophilic modification; Synthesize PVP-polyacrylate copolymer or PVP with free radical polymerization or RAFT polymerization method with N-vinylpyrrolidone monomer -OH homopolymer, cross-linked in the polydimethylsiloxane network, coated on the surface of the substrate, obtained a hydrophilic modified fouling release antifouling coating.

The polydimethylsiloxane coating modified by polyvinylpyrrolidone has the following structure:

In the formula, Is the hydrophilic side chain polymer A or B; R ₁ is CH ₃ or C ₂ H ₅ ;

R ₂ is polydimethylsiloxane (PDMS), it is characterized in that structural formula is:

Wherein the hydrophilic side chain A is polyvinylpyrrolidone-polyacrylic acid resin (PVP-co-PAR), the structure is:

In the formula, R ₃ is H or CH ₃ ; R ₄ is CH ₃ or C ₂ H ₅ ; R ₅ is C ₂ H ₅ or C ₄ H ₉ or C ₈ H ₁₇ ; R ₆ is CH ₂ or (CH ₂ ) ₂ or (CH ₂ ) ₃ ; n is 120-160; m is 20-40; p is 20-40; q is 10-20;

The hydrophilic side chain B is polyvinylpyrrolidone (PVP-SiOH) terminated by a silane coupling agent. The structure is:

In the formula, R ₇ is O or NH; R ₈ is CH ₃ or C ₂ H ₅ ; n is 120-200.

The specific instructions are as follows:

1. The synthetic process of hydrophilic side chain polymer A is as follows:

(1) 0.5-1 weight part of initiator is dissolved in 10-30 weight part of organic solvent, and preheated to 65°C-85°C to obtain the first solution;

(2) 60-80 parts by weight of N-vinylpyrrolidone (NVP), 10-30 parts by weight of acrylate soft monomer, 10-30 parts by weight of (meth)acrylate hard monomer, 5-10 parts by weight The hydroxyalkyl methacrylate monomer of part, the initiator of 1.5-3.5 part by weight is dissolved in the organic solvent of 20-70 part by weight, obtains the second kind of solution;

(3) Add the solution obtained in step (2) dropwise to the solution obtained in step (1) at a rate of 0.5-2ml/s; after adding the solution, react at 65°C-85°C for 2 -4 hours, then add 0.5-2 parts by weight of initiator, raise the temperature to 85°C-110°C, keep the temperature constant for 6h-24h to obtain the reaction product, then add a settling agent whose volume is 5-10 times that of the reaction solution The polymer was precipitated, centrifuged and vacuum dried to obtain hydrophilic polymer A.

The initiator described in the above steps (1)(2)(3) is selected from 2,2'-azobisisobutyronitrile, benzoyl peroxide or 2,2'-azobis(2-methyl- N-(2-hydroxyethyl)propionamide;

The organic solvent described in the above-mentioned steps (1) (2) is selected from a mixed solvent of xylene and butyl acetate, and the mixed solvent mass ratio is preferably 1:1;

The acrylate soft monomer described in the above step (2) is selected from ethyl acrylate, butyl acrylate or n-octyl acrylate; (meth)acrylate hard monomer is selected from methyl methacrylate, ethyl methacrylate , butyl methacrylate or methyl acrylate;

The settling agent described in the above step (3) is selected from petroleum ether, n-hexane or ether.

2. The synthetic process of hydrophilic side chain polymer B is as follows:

(1) Dissolve 0.5-1.5 parts by weight of initiator in 10-30 parts by weight of organic solvent, add 30-50 parts by weight of N-vinylpyrrolidone and mercapto compound of 2-6 parts by weight, pre- Heat to 55°C-85°C, keep the temperature and react for 6-12 hours to obtain a modified polyvinylpyrrolidone solution, spin dry the solvent, add an organic solvent with a volume of 1-4 times the solid mass to dissolve the solid, and then add a volume of modified polyvinylpyrrolidone Precipitating agent 20-40 times of vinylpyrrolidone solution precipitates the polymerization reaction product, centrifuges, and vacuum-dries to obtain modified polyvinylpyrrolidone;

(2) Dissolving 40-60 parts by weight of the product obtained from (1) and 4-6 parts by weight of a functional silicone crosslinking agent in 34-44 parts by weight of an organic solvent, preheating to 60-90°C, Maintain the temperature and react for 2-5 hours to obtain a reaction product, then add a sedimentation agent whose volume is 5-10 times that of the reaction solution to precipitate the polymer, centrifuge and vacuum-dry to obtain a hydrophilic polymer B.

The initiator described in the above step (1) is selected from 2,2'-azobisisobutyronitrile, benzoyl peroxide, 2,2'-azobis(2-methyl-N-(2-hydroxy ethyl) propionamide);

The organic solvent described in the above-mentioned steps (1) (2) is selected from dichloromethane or tetrahydrofuran

The mercapto compound described in the above step (2) is selected from mercaptoethanol or mercaptoethylamine;

The functional siloxane crosslinking agent described in the above step (2) is selected from (3-isocyanopropyl) trimethoxysilane or (3-isocyanopropyl) triethoxysilane;

The settling agent described in the above step (2) is selected from petroleum ether, n-hexane or ether.

3. The preparation process of the hydrophilic modified silicone fouling release antifouling coating is as follows:

(1) Take by weight the hydrophilic side chain polymer A or B of 1-8 and the polydimethylsiloxane of 10-30 by weight, join in the organic solvent that is 20-30 by weight, Stir evenly to obtain a reaction mixture;

(2) Add a crosslinking agent of 1-4 parts by weight to the mixture in (1), stir evenly to obtain a coating prepolymer

(3) Add 0.5-1 parts by weight of catalyst to the mixture in (2), stir evenly, quickly and evenly coat the substrate, and then cure at 40°C-60°C to obtain hydrophilic modified antifouling coating;

The polydimethylsiloxane described in the above step (1) is dihydroxyl-terminated polydimethylsiloxane (HO-PDMS-OH);

The organic solvent described in the above-mentioned steps (1) is a mixed solvent of xylene and butyl acetate, and the mass ratio of the mixed solvent is preferably 1:1;

The crosslinking agent described in the above step (2) is selected from methyltriacetoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane or (3 - isocyanopropyl)triethoxysilane;

The catalyst used in the above step (3) is selected from dibutyltin dilaurate, dibutyltin diacetate or stannous octoate.

The effect of the invention

In order to solve the problem of marine biofouling on the surface of ships and marine facilities, the invention develops a preparation method of a hydrophilic modified fouling release type antifouling coating. Through protein adsorption experiments, bacterial adhesion experiments, diatom adhesion experiments and simulated barnacle adhesion experiments, it is proved that the antifouling effect of the hydrophilic modified antifouling coating has been greatly improved compared with the antifouling effect of the control coating . Therefore, it has good practical application value as a marine antifouling coating.

1) The hydrophilic modified fouling-releasing antifouling coating provided by the present invention has been proved by protein adsorption experiments that its protein adsorption amount is 75.8%-83.2% lower than that of the control group.

2) The hydrophilic modified fouling release type antifouling paint provided by the present invention has been proved by Escherichia coli adhesion experiment that the amount of bacterial adhesion is reduced by 96.0%-98.7% compared with that of the control group.

3) The hydrophilic modified fouling release type antifouling paint provided by the present invention is proved by the Staphylococcus aureus adhesion test that the amount of bacterial adhesion is reduced by 87.5%-97.1% compared with that of the control group.

4) The hydrophilic modified fouling-releasing antifouling coating provided by the present invention has been proved by the attachment experiment of navicula diatoms that its diatom attachment density is reduced by 93.6%-97.3% compared with the diatom attachment density of the control group.

5) The hydrophilic modified fouling-releasing antifouling coating provided by the present invention is proved by simulating barnacle adhesion experiments that its barnacle adhesion is 58.2%-75.9% lower than that of the control group.

6) This invention has been supported by the Open Fund Project of Qingdao National Laboratory of Marine Science and Technology (Project Number: QNLM2016ORP0407).

Description of drawings

Fig. 1 Fibrinogen (Fibrinogen) adsorption result of hydrophilic modified fouling release type antifouling coating;

The escherichia coli (Escherichia coli) adhesion test bacterial colony growth situation of Fig. 2 hydrophilic modification fouling release type antifouling paint;

The Escherichia coli (Escherichia coli) adhesion test bacterium density of the hydrophilic modification fouling release type antifouling coating of Fig. 3;

The colony growth situation of Staphylococcus aureus (Staphylococcus aureus) adhesion experiment of Fig. 4 hydrophilic modification fouling release type antifouling paint;

The bacterial density of the Staphylococcus aureus (Staphylococcus aureus) adhesion test of the hydrophilic modified fouling release type antifouling paint of Fig. 5;

Fig. 6 Navicula parva attachment experiment of hydrophilic modified fouling-release antifouling coating Diatom attachment density.

Detailed ways

The present invention can be explained in more detail by the following examples, and the present invention is not limited to the following examples;

Example 1

Follow the steps below to prepare a hydrophilic modified silicone fouling release marine antifouling coating

(1) 0.50 g of 2,2'-azobisisobutyronitrile was dissolved in a mixed solvent of 5 g xylene and 5 g butyl acetate, and preheated to 80° C. 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 was dissolved in a mixed solvent of 10g xylene and 10g butyl acetate to obtain a reactant solution;

(3) The solution obtained in step (2) is slowly added dropwise to the solution obtained in step (1), and the rate of addition is controlled at 0.5ml/s; 2,2'-Azobisisobutyronitrile, heated up to 110°C, kept the temperature for 12 hours to obtain the reaction product, then added petroleum ether 10 times the volume of the reaction solution to precipitate the polymer, centrifuged and dried in vacuum to obtain the hydrophilic Water side chain polymer A;

(4) Weigh 0.1 g of the hydrophilic side chain polymer A obtained in (3) above, dissolve in 1 g of xylene and 1 g of butyl acetate mixed solvent to obtain a homogeneous mixture;

(5) Weigh 2g of polydimethylsiloxane and add it to the solution in (4), stir evenly to obtain a mixture;

(6) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (5), stir evenly to obtain the mixture;

(7) The dibutyltin dilaurate that takes 0.01g joins in the mixture in (6), stirs evenly, obtains antifouling coating prepolymer;

(8) Coat the coating prepolymer quickly and uniformly on the test substrate, control the thickness at 100 μm-1000 μm, dry and solidify in an oven at 40°C to obtain a uniform coating, and soak the coating in artificial seawater for testing. .

Example 2

Follow the steps below to prepare a hydrophilic modified silicone fouling release marine antifouling coating

(1) Weigh 0.75g of 2,2'-azobisisobutyronitrile and dissolve it in a mixed solvent of 10g xylene and 10g butyl acetate, preheat to 85°C 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), 0.5 g of 2,2'-azobisisobutyronitrile was dissolved in a mixed solvent of 10 g xylene and 10 g butyl acetate to obtain a reactant solution;

(3) The solution obtained in step (2) is slowly added dropwise to the solution obtained in step (1), and the rate of addition is controlled at 0.5ml/s; 2,2'-Azobisisobutyronitrile, heated up to 110°C, kept the temperature for 12 hours to obtain the reaction product, then added petroleum ether 10 times the volume of the reaction solution to precipitate the polymer, centrifuged and dried in vacuum to obtain the hydrophilic Water side chain polymer A;

(4) Weigh 0.2g of the hydrophilic side chain polymer A obtained in (3) above, and dissolve it in a mixed solution of 1g xylene and 1g butyl acetate to obtain a homogeneous mixture;

(5) Weigh 2g of polydimethylsiloxane and add it to the solution in (4), stir evenly to obtain a mixture;

(6) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (5), stir evenly to obtain the mixture;

(7) The dibutyltin dilaurate that takes 0.01g joins in the mixture in (6), stirs evenly, obtains antifouling coating prepolymer;

(8) Coat the coating prepolymer quickly and uniformly on the test substrate, control the thickness at 100 μm-1000 μm, dry and solidify in an oven at 40°C to obtain a uniform coating, and soak the coating in artificial seawater for testing. .

Example 3

Follow the steps below to prepare a hydrophilic modified silicone fouling release marine antifouling coating

(1) Weigh 0.50 g of 2,2'-azobisisobutyronitrile and dissolve it in 15 g of xylene and 15 g of butyl acetate, and preheat to 80° C. to obtain an initiator solution;

(2) 8.0g of N-vinylpyrrolidone (NVP), 1.0g of butyl acrylate (BA), 3.0g of methyl methacrylate (MMA), 1.0g of hydroxyethyl methacrylate (HEMA), 1.5 g of 2,2'-azobisisobutyronitrile was dissolved in 35 g of xylene and 35 g of butyl acetate in a mixed organic solvent to obtain a reactant solution;

(3) The solution obtained in step (2) is slowly added dropwise to the solution obtained in step (1), and the rate of addition is controlled at 0.5ml/s; 2,2'-Azobisisobutyronitrile, heat up to 110°C, keep warm for 12 hours to obtain the reaction product, then add ether 10 times the volume of the reaction solution to precipitate the polymer, centrifuge and vacuum dry to obtain a hydrophilic side chain polymer A;

(4) Take by weighing 0.3g of the hydrophilic side chain polymer A obtained in (3) above, in a mixed solution of 1g xylene and 1g butyl acetate, to obtain a homogeneous mixture;

(5) Weigh 2g of polydimethylsiloxane and add it to the solution in (4), stir evenly to obtain a mixture;

(6) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (5), stir evenly to obtain the mixture;

(7) The dibutyltin dilaurate that takes 0.01g joins in the mixture in (6), stirs evenly, obtains antifouling coating prepolymer;

(8) Coat the coating prepolymer quickly and uniformly on the test substrate, control the thickness at 100 μm-1000 μm, dry and solidify in an oven at 40°C to obtain a uniform coating, and soak the coating in artificial seawater for testing. .

Example 4

(1) Dissolve 0.5g of azobisisobutyronitrile in 10g of isopropanol, add 8g of N-vinylpyrrolidone and 0.8g of mercaptoethanol into it, preheat to 65°C, and keep it warm for 8 hours to obtain modified polyethylene Pyrrolidone solution, spin to dry the solvent, add 2 g of dichloromethane whose volume is the mass of the solid to dissolve the solid, then add 40 g of ether to precipitate the polymerization product, centrifuge, and dry in vacuum to obtain a modified polyvinyl pyrrolidone solid;

(2) Add 5 g parts by weight of the product obtained in (1) to 0.5 g of (3-isocyanopropyl) triethoxysilane dissolved in 5 g of tetrahydrofuran solvent, preheat to 60 ° C, and react for 2 hours to obtain the reaction product , and then add a sedimentation agent whose volume is 5-10 times that of the reaction solution to precipitate the polymer, centrifuge and vacuum-dry to obtain a hydrophilic side chain polymer B;

(3) Weigh 0.3g of the hydrophilic side chain polymer B obtained in (2) above, in a mixed solution of 1g xylene and 1g butyl acetate to obtain a homogeneous mixture;

(4) Weigh 2g of polydimethylsiloxane and add it to the solution in (3), stir evenly to obtain a mixture;

(5) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (4), stir evenly to obtain the mixture;

(6) Weigh 0.01 g of dibutyltin dilaurate and add it to the mixture in (5), stir evenly to obtain an antifouling coating prepolymer.

Example 5

Follow the steps below to prepare a hydrophilic modified silicone fouling release marine antifouling coating

(1) Weigh 1g of 2,2'-azobisisobutyronitrile and dissolve it in a mixed solvent of 15g xylene and 15g butyl acetate, preheat to 85°C to obtain an initiator solution;

(2) 80g of N-vinylpyrrolidone (NVP), 20g of acrylate (BA), 20g of methyl acrylate (MMA), 11.5g of hydroxyethyl methacrylate (HEMA), 0.75g of 2, 2'-azobisisobutyronitrile was dissolved in 30g xylene and 30g butyl acetate mixed organic solvent to obtain a reactant solution;

(3) The solution obtained in step (2) is slowly added dropwise to the solution obtained in step (1), and the rate of addition is controlled at 0.5ml/s; , 2'-Azobisisobutyronitrile, heated up to 110 ° C, kept the temperature for 12 hours to obtain the reaction product, then added n-hexane whose volume was 10 times that of the reaction solution to precipitate the polymer, centrifuged and dried in vacuum to obtain the hydrophilic Water side chain polymer A;

(4) Weigh 0.1g of the hydrophilic side chain polymer A obtained in (3) above, and dissolve it in a mixed solution of 1g xylene and 1g butyl acetate to obtain a homogeneous mixture;

(5) Weigh 2g of polydimethylsiloxane and add it to the solution in (4), stir evenly to obtain a mixture;

(6) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (5), stir evenly to obtain the mixture;

(7) The dibutyltin dilaurate that takes 0.075g joins in the mixture in (6), stirs evenly, obtains antifouling coating prepolymer;

(8) Coat the coating prepolymer quickly and uniformly on the test substrate, control the thickness at 100 μm-1000 μm, dry and solidify in an oven at 40°C to obtain a uniform coating, and soak the coating in artificial seawater for testing. .

Example 6

Follow the steps below to prepare a hydrophilic modified silicone fouling release marine antifouling coating

(1) Weigh 0.75g of 2,2'-azobisisobutyronitrile and dissolve it in a mixed solution of 10g xylene and 10g butyl acetate, preheat to 70°C to obtain an initiator solution;

(2) 70g of N-vinylpyrrolidone (NVP), 15g of ethyl methacrylate (BA), 15g of ethyl methacrylate (MMA), 11.5g of hydroxymethyl methacrylate (HMMA), 3.5 g of 2,2'-azobisisobutyronitrile was dissolved in 70g xylene and 70g butyl acetate mixed organic solvent to obtain a reactant solution;

(3) The solution obtained in step (2) is slowly added dropwise to the solution obtained in step (1), and the rate of addition is controlled at 0.5ml/s; after the solution has been added dropwise, it is incubated for 4 hours, and then 2g of 2 , 2'-Azobisisobutyronitrile, heat up to 110°C, keep warm for 12 hours to obtain the reaction product, then add a sedimentation agent 10 times the volume of the reaction solution to precipitate the polymer, centrifuge and vacuum dry to obtain a hydrophilic side chain polymer A;

(4) Weigh 0.2g of the hydrophilic side chain polymer A obtained in (3) above, and dissolve it in a mixed solution of 1g xylene and 1g butyl acetate to obtain a homogeneous mixture;

(5) Weigh 2g of polydimethylsiloxane and add it to the solution in (4), stir evenly to obtain a mixture;

(6) Weigh 0.4 g of methyl γ-(methacryloyloxy)propyltrimethoxysilane into the mixture in (5), stir evenly to obtain the mixture;

(7) The dibutyltin diacetate of 0.1g is weighed and joined in the mixture in (6), stir evenly, obtain antifouling coating prepolymer;

(8) Coat the coating prepolymer quickly and uniformly on the test substrate, control the thickness at 100 μm-1000 μm, dry and solidify in an oven at 40°C to obtain a uniform coating, and soak the coating in artificial seawater for testing. .

Example 7

(1) Dissolve 0.75g of azobisisobutyronitrile in 20g of isopropanol, add 40g of N-vinylpyrrolidone and 4g of mercaptoethanol into it, preheat to 65°C, and keep it warm for 8 hours to obtain modified polyvinylpyrrolidone solution, spin to dry the solvent, add 20 g of dichloromethane with a volume of solid mass to dissolve the solid, then add 600 g of ether to precipitate the polymerization product, centrifuge, and dry in vacuum to obtain a modified polyvinylpyrrolidone solid;

(2) Add 5 g of the product obtained in (1) into 0.5 g of (3-isocyanopropyl) triethoxysilane and dissolve in 5 g of tetrahydrofuran solvent, preheat to 60 ° C, react for 2 hours to obtain the reaction product, and then Add 50 g of n-hexane to the reaction solution to precipitate the polymer, centrifuge and vacuum dry to obtain the hydrophilic side chain polymer B;

(3) Weigh 0.1g of the hydrophilic side chain polymer B obtained in (2) above, in a mixed solution of 1g xylene and 1g butyl acetate to obtain a homogeneous mixture;

(4) Weigh 2g of polydimethylsiloxane and add it to the solution in (3), stir evenly to obtain a mixture;

(5) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (4), stir evenly to obtain the mixture;

(6) Weigh 0.01 g of dibutyltin dilaurate and add it to the mixture in (5), stir evenly to obtain an antifouling coating prepolymer.

Example 8

(1) Dissolve 1.5g of azobisisobutyronitrile in 30g of isopropanol, add 50g of N-vinylpyrrolidone and 6g of mercaptoethanol into it, preheat to 85°C, and keep it warm for 8 hours to obtain modified polyvinylpyrrolidone Solution, spin to dry the solvent, add 4g of dichloromethane with a volume of solid mass to dissolve the solid, then add 1200g of ether to precipitate the polymerization reaction product, centrifuge, and dry in vacuum to obtain the modified polyvinylpyrrolidone solid;

(2) Add 5 g of the product obtained in (1) into 0.5 g of (3-isocyanopropyl) triethoxysilane and dissolve in 5 g of tetrahydrofuran solvent, preheat to 60 ° C, react for 2 hours to obtain the reaction product, and then Add 50 g of petroleum ether to the reaction solution to precipitate the polymer, centrifuge and vacuum-dry to obtain the hydrophilic side chain polymer B;

(3) Weigh 0.5g of the hydrophilic side chain polymer B obtained in (2) above, in a mixed solution of 1g xylene and 1g butyl acetate, to obtain a homogeneous mixture;

(4) Weigh 2g of polydimethylsiloxane and add it to the solution in (3), stir evenly to obtain a mixture;

(5) Weigh 0.2 g of methyltriacetoxysilane and add it to the mixture in (4), stir evenly to obtain the mixture;

(6) Weigh 0.01 g of dibutyltin dilaurate and add it to the mixture in (5), stir evenly to obtain an antifouling coating prepolymer.

Control group example

Follow the steps below to prepare a hydrophilic modified silicone fouling release marine antifouling coating

(1) Weighing 2g of polydimethylsiloxane and adding it to 1-2g xylene, stirring evenly to obtain a mixture;

(2) Weighing 0.17-0.23g of methyltriacetoxysilane into the mixture in (1), stirring evenly to obtain the mixture;

(3) adding 0.01-0.05g of dibutyltin dilaurate into the mixture in (2), stirring evenly, to obtain the antifouling coating prepolymer;

(4) Coat the coating prepolymer quickly and uniformly on the test substrate, control the thickness at 100 μm-1000 μm, dry and solidify in a 40°C oven to obtain a uniform coating, and soak the coating in artificial seawater for testing. .

Example 9

The antifouling performance test method of hydrophilic modified silicone fouling release marine antifouling coating is as follows:

(1) Antifouling coating protein adsorption test adopts enzyme-linked immunosorbent assay (ELISA) method;

(2) The antifouling coating bacterial adhesion test adopts the plate method, and the experimental bacteria are Escherichia coli (Escherichiacoli) and Staphylococcus aureus (Staphylococcus aureus);

(3) Antifouling coating diatom attachment experiment, the diatom used in the experiment is: Naviculaparva (Naviculaparva);

(4) The simulated barnacle adhesion test adopts the standard test method ASTM D5618.

Test Results:

(1) The ELISA experimental result of hydrophilic modified fouling release type antifouling paint is as shown in Figure 1, and embodiment 1 in the figure is the test of the pure organic silicon antifouling paint that has not been modified by hydrophilicity as a control group, and other implementations The example is the silicone antifouling coating modified by hydrophilicity as the experimental group, and the adhesion protein used is fibrinogen (Fibrinogen). From the data in the figure, it can be seen that the protein adsorption amount of the experimental group is 75.8%-83.2% lower than that of the control group, indicating that after hydrophilic modification, the anti-protein adsorption ability of the organic silicon fouling release antifouling coating is obvious improve.

(2) Escherichia coli (Escherichia coli) experimental results of hydrophilic modified fouling-release antifouling coatings are shown in Figure 2 and Figure 3, and Example 1 in the figure is a pure silicone antifouling coating that has not been hydrophilically modified The test is used as the control group, and the other examples are as the experimental group through the hydrophilic modified silicone antifouling coating. It can be seen from the data in the figure that the amount of bacterial adhesion in the experimental group is 1.3%-4.0% of that in the control group, indicating that after hydrophilic modification, the anti-E. coli adhesion of silicone fouling release antifouling coatings The ability has improved significantly.

(3) The experimental results of Staphylococcus aureus (Staphylococcus aureus) of hydrophilic modified fouling-release antifouling coatings are shown in Figure 4 and Figure 5, and Example 1 in the figure is a pure silicone antifouling coating that has not been hydrophilically modified. The test of the fouling paint was used as the control group, and other examples were the silicone antifouling paints modified by hydrophilicity as the experimental group. It can be seen from the data in the figure that the amount of bacterial adhesion in the experimental group is 2.9%-12.5% of that in the control group, indicating that after hydrophilic modification, the anti-Staphylococcus aureus of silicone fouling release antifouling coating The adhesion ability is obviously improved.

(4) The experimental results of Naviculaparva adhesion experiment of hydrophilic modified fouling-release antifouling paint are shown in Figure 6. The control group in the figure is a pure silicone antifouling paint that has not been modified by hydrophilicity, and other The example is by hydrophilic modified silicone antifouling paint as the experimental group. It can be seen from the data in the figure that the diatom attachment density of the experimental group is 2.7%-6.4% of the diatom attachment density of the control group, indicating that after hydrophilic modification, the anti-diatom attachment ability of the organic silicon fouling release antifouling coating The ability is significantly improved.

(5) The simulated barnacle adhesion test results of hydrophilic modified fouling release type antifouling coatings are shown in Table 1, and embodiment 1 in the table is the test of pure organic silicon antifouling coatings without hydrophilic modification as a control Group, other examples are the silicone antifouling coatings modified by hydrophilic as the experimental group. It can be seen from the data in the figure that the simulated barnacle adhesion of the experimental group is 58.2%-75.9% smaller than that of the control group, indicating that after hydrophilic modification, the fouling release ability of the organic silicon fouling release antifouling coating is significantly improved.

Table 1 Experimental results of simulated barnacle adhesion of hydrophilic modified fouling release antifouling coatings

Claims (10)

1. A hydrophilic modified fouling release type marine antifouling coating; It is characterized in that polydimethylsiloxane coating modified by polyvinylpyrrolidone, and its structure is as follows: In the formula, Is the hydrophilic side chain polymer A or B; R ₁ is CH ₃ or C ₂ H ₅ ; R ₂ is polydimethylsiloxane, its structural formula is: Wherein the hydrophilic side chain polymer A is polyvinylpyrrolidone-polyacrylic acid resin (PVP-co-PAR), the structure is: In the formula, R ₃ is H or CH ₃ ; R ₄ is CH ₃ or C ₂ H ₅ ; R ₅ is C ₂ H ₅ or C ₄ H ₉ or C ₈ H ₁₇ ; R ₆ is CH ₂ or (CH ₂ ) ₂ or (CH ₂ ) ₃ ; n is 120-160; m is 20-40; p is 20-40; q is 10-20; Wherein the hydrophilic side chain polymer B is a silane coupling agent-terminated polyvinylpyrrolidone (PVP-SiOH) structure as follows: In the formula, R ₇ is O or NH; R ₈ is CH ₃ or C ₂ H ₅ ; n is 120-200. 2. coating as claimed in claim 1; It is characterized in that the preparation method of described hydrophilic side chain polymer A comprises the following steps: (1) 0.5-1 weight part of initiator is dissolved in 10-30 weight part of organic solvent, and preheated to 65°C-85°C to obtain the first solution; (2) 60-80 parts by weight of N-vinylpyrrolidone, 10-20 parts by weight of acrylate soft monomer, 10-20 parts by weight of (meth)acrylate hard monomer, 5-10 parts by weight of formaldehyde Hydroxyalkyl acrylate monomer, the initiator of 1.5-3.5 weight parts is dissolved in the organic solvent of 20-70 weight parts, obtains the second kind of solution; (3) Add the solution obtained in step (2) dropwise to the solution obtained in step (1) at a rate of 0.5-2ml/s; after adding the solution, react at 65°C-85°C After 2-4 hours, add 0.5-2 parts by weight of initiator, raise the temperature to 85°C-110°C, keep the temperature constant for 6h-24h to obtain the reaction product, and then add a sedimentation agent whose volume is 5-10 times that of the reaction solution The polymer was precipitated, centrifuged and vacuum dried to obtain hydrophilic polymer A. 3. coating as claimed in claim 1; It is characterized in that the preparation method of described hydrophilic side chain polymer B comprises the following steps: (1) Dissolve 0.5-1.5 parts by weight of initiator in 10-30 parts by weight of organic solvent, add 30-50 parts by weight of N-vinylpyrrolidone and mercapto compound of 2-6 parts by weight, pre- Heat to 55°C-85°C, keep it warm for 6-12 hours to obtain a modified polyvinylpyrrolidone solution, spin the solvent dry, add a solvent with a volume of 1-4 times the solid mass to dissolve the solid, and then add a volume of modified polyvinylpyrrolidone 20-40 times of the precipitant in the solution precipitates the polymerization reaction product, centrifuges, and vacuum-dries to obtain the modified polyvinylpyrrolidone; (2) Dissolving 40-60 parts by weight of the product obtained from (1) and 4-6 parts by weight of a functional silicone crosslinking agent in 34-44 parts by weight of an organic solvent, preheating to 60-90°C, React for 2-5 hours to obtain a reaction product, then add a sedimentation agent whose volume is 5-10 times that of the reaction solution to precipitate the polymer, centrifuge and dry in vacuum to obtain a hydrophilic polymer. 4. coating according to claim 2; It is characterized in that described initiator is selected from 2,2'-azobisisobutyronitrile, benzoyl peroxide or 2,2'-azobis(2-methyl Base-N-(2-hydroxyethyl) propionamide); The solvent is a mixed solvent of xylene and butyl acetate; The settling agent is selected from petroleum ether, normal hexane or ether. 5. coating according to claim 3; It is characterized in that described initiator is selected from 2,2'-azobisisobutyronitrile, benzoyl peroxide or 2,2'-azobis(2-methyl Base-N-(2-hydroxyethyl) propionamide); The solvent is selected from dichloromethane or tetrahydrofuran; The settling agent is selected from petroleum ether, n-hexane or ether. 6. coating according to claim 2; It is characterized in that the acrylate soft monomer of preparing hydrophilic side chain polymer A is selected from ethyl acrylate, butyl acrylate or n-octyl acrylate; (meth)acrylate The hard monomer is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate or methyl acrylate. 7. coating according to claim 3; It is characterized in that the mercapto compound described in preparing hydrophilic side chain polymer B is selected from mercaptoethanol or mercaptoethylamine. 8. the preparation method of the fouling release type marine antifouling paint of hydrophilic modification according to claim 1, is characterized in that comprising the following steps: (1) Take by weight the hydrophilic side chain polymer A or B of 1-8 and the polydimethylsiloxane of 10-30 by weight, join in the organic solvent that is 20-30 by weight, Stir evenly to obtain a reaction mixture; (2) Adding a crosslinking agent of 1-4 parts by weight into the mixture in (1), stirring evenly to obtain a coating prepolymer; (3) Add 0.5-1 parts by weight of catalyst to the mixture in (2), stir evenly, evenly coat the film on the substrate, and then cure at 40°C-60°C to obtain a hydrophilic modified antifouling coating Floor. 9. The method according to claim 8, wherein the polydimethylsiloxane is a dihydroxy-terminated polydimethylsiloxane; the crosslinking agent is selected from the group consisting of methyltriacetoxy Silane, γ-(methacryloxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane or (3-isocyanopropyl)triethoxysilane. 10. The method according to claim 8, wherein the catalyst is selected from dibutyltin dilaurate, dibutyltin diacetate or stannous octoate; the organic solvent is a mixed solvent of xylene and butyl acetate.