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

A kind of pollution release type marine antifouling coating of hydrophilic modifying and preparation method thereof Download PDF

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CN107936831A
CN107936831A CN201711241273.5A CN201711241273A CN107936831A CN 107936831 A CN107936831 A CN 107936831A CN 201711241273 A CN201711241273 A CN 201711241273A CN 107936831 A CN107936831 A CN 107936831A
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parts
coating
hydrophilic
solution
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CN107936831B (en
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张雷
赵维强
郭洪爽
李庆斯
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Tianjin University
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Tianjin University
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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
    • 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
    • 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
    • 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
    • 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

Pollution release type antifouling paint the present invention relates to a kind of hydrophilic modifying and preparation method thereof, with the radical polymerization of N vinyl-pyrrolidone monomers or RAFT polymerizations synthesis PVP acrylate copolymers or PVP OH homopolymers, cross-linking is in polydimethylsiloxane network, coated in matrix surface, the pollution release type nonpolluting coating of hydrophilic modifying is obtained.Compared than control group, protein adsorption quantity, which reduces 75.8% 83.2%, bacterial adhesion amount, reduces 96.0% 98.7%；Algae attachment density reduces 93.6% 97.3%；Barnacle adhesive force reduces 58.2% 75.9%；The anti-fouling effect of this hydrophilic modifying nonpolluting coating has than the anti-fouling effect of pure PDMS coatings to be increased substantially.Therefore, it has good actual application value as marine antifouling coating.

Description

A kind of pollution release type marine antifouling coating of hydrophilic modifying and preparation method thereof
Technical field
The present invention relates to a kind of synthesis field of antifouling paint, and in particular to a kind of pollution release type of hydrophilic modifying is antifouling Coating and preparation method thereof.
Background technology
The development of the marine causes such as marine military affairs, marine transportation, mariculture, offshore drilling platform and marine facility is always It is faced with a great problem -- marine biofouling.At present, having for being found is stained the marine organisms of attachment characteristic about 4000~5000 kinds, these marine organisms can adhere to the surface of solids in the seawater and raised growth is bred, and form biology Layer is stained, so that causing ship, ocean engineering and underwater facility surface to produce is stained malicious event.It is this to be stained destruction and make Into many harm, such as increase ship own wt and headway, increase fuel consumption, and seriously affect the navigation on naval vessel Performance；Block submarine pipeline or mariculture netting gear；Influence the normal use of the marine detecting devices such as acoustic instrument；Increase ocean The burden of oil or natural gas extraction platform, accelerates undersea corrosion of metal speed etc..
So far, it is exactly to be applied in marine facility external coating marine anti-pollution to solve marine biofouling most efficient method Material.Majority adds anti-fouling agent in traditional marine antifouling coating, anti-to play by constantly discharging poisonous biocide under water Dirty effect.Wherein effect most preferably organotin self polishing copolymer antifouling paint, brought for shipping business since the 1960s Huge profit.However, organotin biocide toxicity is very strong, it also makes non-targeted property marine organisms lethal or lopsided, seriously The ecological balance is destroyed, therefore, from 1 day January in 2008, self polishing copolymer antifouling paint containing organic tin was by International Maritime Organization (IMO) disable completely.Most commonly used at present is the self polishing copolymer antifouling paint of the biocides such as cupric, zinc, although copper zinc type is killed livestock Agent does not have that the toxicity of organic tin is big, but it also causes security risk to the health of marine ecology balance and the mankind.With people Environmental consciousness enhancing, the marine antifouling coating of toxic biocide will be gradually backed out the arena of history, be applied by non-toxic, environmental friendly Material is substituted.
Low-surface-energy pollution release type antifouling paint is preferable environment-friendly type as a kind of antifouling paint without biocide Marine antifouling coating.Its antifouling mechanism is due to the physical property that its coating has low-surface-energy, makes marine organisms be not easy to adhere to In matrix surface, and the fouling organism adhered to is easily fallen during ship running by seawater scouring, or by simple Mechanical cleaning can just remove.Low surface energy anti-fouling paint generally uses organic siliconresin, and organic fluorine or fluorine silicon resin are as base Material, is equipped with crosslinking agent, stabilizer, additive and other auxiliary agents composition, wherein organic siliconresin is most widely used.It is although organic Silicon pollution release type coating meets the requirement of asepsis environment-protecting, but also there is much ask in practical applications for pure organosilicon coating Topic, such as bad mechanical property, and the adhesive force of hull is relatively low easily comes off, and is restricted for marine surface of the higher speed of a ship or plane etc., Above all it cannot resist the attachment for being stained mucus, and be difficult to wash out.It is stained mucus generally by biomolecule such as albumen, carefully The miniature marine organisms composition such as bacterium, diatom.In order to improve the antifouling property of organosilicon pollution release type antifouling paint, with hydrophilic or It is a kind of effective strategy that amphipathy macromolecule, which carries out it hydrophily,.
The content of the invention
The technical problems to be solved by the invention are in view of the deficiencies of the prior art, there is provided one kind contains hydrophilic polymer Organosilicon low surface energy anti-fouling paint, the addition of hydrophilic polymer effectively can prevent or reduce albumen and bacterium in coating The adhesion and attachment on surface, so that playing the role of resistance in marine environment is stained mucus, suppresses from root or reduce sea The formation of foreign biodeterioration facility or hull under water.
In order to achieve the above object, the present invention devises a kind of pollution release type marine antifouling coating of hydrophilic modifying；With The radical polymerization of N- vinyl-pyrrolidone monomers or RAFT polymerizations synthesis PVP- acrylate copolymers or PVP-OH Homopolymer, cross-linking is in polydimethylsiloxane network, coated in matrix surface, obtains the pollution release of hydrophilic modifying Type nonpolluting coating.
The dimethyl silicone polymer coating of polyvinylpyrrolidone modification, structure such as formula：
In formula,For hydrophilic side chain polymer A or B；R1For CH3Or C2H5；
R2For dimethyl silicone polymer (PDMS), it is characterised in that structural formula is：
Wherein hydrophilic side chain A is polyvinylpyrrolidone-polyacrylic resin (PVP-co-PAR), and structure is：
In formula, R3For H or CH3；R4For CH3Or C2H5；R5For C2H5Or C4H9Or C8H17；R6For CH2Or (CH2)2Or (CH2)3； N is 120~160；M is 20~40；P is 20~40；Q is 10~20；
Wherein hydrophilic side chain B is that polyvinylpyrrolidone (PVP-SiOH) structure of silane coupling agent end-blocking is：
In formula, R7For O or NH；R8For CH3Or C2H5；N is 120~200.
It is described as follows：
1st, the building-up process of hydrophilic side chain polymer A is as follows：
(1) initiator of 0.5-1 parts by weight is dissolved in the organic solvent of 10-30 parts by weight, is preheated to 65 DEG C -85 DEG C, Obtain the first solution；
(2) by the N- vinylpyrrolidones (NVP) of 60-80 parts by weight, the acrylate soft monomer of 10-30 parts by weight, 10- (methyl) acrylate hard monomer of 30 parts by weight, the haloalkylacrylates monomer of 5-10 parts by weight, 1.5-3.5 weights The initiator of amount part is dissolved in the organic solvent of 20-70 parts by weight, obtains second of solution；
(3) solution obtained in step (2) is added drop-wise in the solution obtained in step (1), rate of addition control exists 0.5-2ml/s；After dripping solution, when reaction 2-4 is small at 65 DEG C -85 DEG C, the initiator of 0.5-2 parts by weight is added, is risen Temperature keeps temperature-resistant reaction 6h-24h, obtains reaction product to 85 DEG C -110 DEG C, adds volume as 5-10 times of reaction solution Polymer is precipitated out by sedimentation agent, is centrifuged and is dried in vacuo, so as to obtain hydrophilic polymer A.
Initiator described in above-mentioned steps (1) (2) (3) is selected from 2,2 '-azodiisobutyronitrile, benzoyl peroxide or 2, Double (2- methyl-N- (2- ethoxys) propionamides of 2'- azos；
Organic solvent described in above-mentioned steps (1) (2) is selected from the mixed solvent for dimethylbenzene and butyl acetate, mixed solvent Mass ratio is preferably 1:1；
It is just pungent that acrylate soft monomer described in above-mentioned steps (2) is selected from ethyl acrylate, butyl acrylate or acrylic acid Ester；(methyl) acrylate hard monomer is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate or propylene Sour methyl esters；
Sedimentation agent described in above-mentioned steps (3) is selected from petroleum ether, n-hexane or ether.
2nd, the building-up process of hydrophilic side chain polymer B is as follows：
(1) initiator of 0.5-1.5 parts by weight is dissolved in the organic solvent of 10-30 parts by weight, adds 30-50 thereto The N- vinylpyrrolidones of parts by weight and the sulfhydryl compound of 2-6 parts by weight are added thereto, and are preheated to 55 DEG C -85 DEG C, are kept When thermotonus 6-12 is small, modified polyvinyl pyrrolidone solution is obtained, is spin-dried for solvent, adds the 1-4 that volume is solid masses Times organic solvent dissolved solid, then adding volume will polymerization for the precipitating reagent of 20-40 times of modified polyvinyl pyrrolidone solution Reaction product settles out, and centrifuges, and vacuum drying, that is, obtain modified polyvinyl pyrrolidone；
(2) product and 4-6 parts by weight Functional siloxane crosslinking agents obtained 40-60 parts by weight by (1) is dissolved in 34-44 In the organic solvent of parts by weight, 60-90 DEG C is preheated to, when keeping thermotonus 2-5 small, reaction product is obtained, adds volume Polymer is precipitated out for 5-10 times of sedimentation agent of reaction solution, centrifuges and is dried in vacuo, so as to obtain hydrophilic polymer B.
It is double that initiator described in above-mentioned steps (1) is selected from 2,2 '-azodiisobutyronitrile, benzoyl peroxide, 2,2'- azos (2- methyl-N- (2- hydroxyethyls) propionamide)；
Organic solvent is selected from dichloromethane or tetrahydrofuran described in above-mentioned steps (1) (2)
Sulfhydryl compound described in above-mentioned steps (2) is selected from mercaptoethanol or mercaptoethylmaine；
Functional siloxane crosslinking agent described in above-mentioned steps (2) be selected from (3- isocyano groups propyl group) trimethoxy silane or (3- isocyano groups propyl group) triethoxysilane；
Sedimentation agent described in above-mentioned steps (2) is selected from petroleum ether, n-hexane or ether.
3rd, the preparation process of hydrophilic modifying organosilicon pollution release type nonpolluting coating is as follows：
(1) the hydrophilic side chain polymer A or B that parts by weight are 1-8 and the polydimethylsiloxanes that parts by weight are 10-30 are weighed Alkane, is added in the organic solvent that parts by weight are 20-30, stirs evenly, obtain reaction mixture；
(2) crosslinking agent that parts by weight are 1-4 is added in the mixture in (1), is stirred evenly, obtains coating prepolymer
(3) catalyst that parts by weight are 0.5-1 is added in the mixture in (2), is stirred evenly, rapidly on substrate Even film, then cures at 40 DEG C -60 DEG C, obtains the nonpolluting coating of hydrophilic modifying；
Dimethyl silicone polymer described in above-mentioned steps (1) is double hydroxy-end capped dimethyl silicone polymer (HO- PDMS-OH)；
Organic solvent described in above-mentioned steps (1) is the mixed solvent of dimethylbenzene and butyl acetate, the quality of mixed solvent Ratio is preferably 1:1；
Crosslinking agent described in above-mentioned steps (2) is selected from methyl triacetoxysilane, γ-(methacryloxypropyl) propyl group three Methoxy silane, gamma-aminopropyl-triethoxy-silane or (3- isocyano groups propyl group) triethoxysilane；
Catalyst used of stating is selected from dibutyl tin laurate, dibutyltin diacetate or octanoic acid Asia in above-mentioned steps (3) Tin.
The effect of invention
The present invention develops a kind of hydrophilic modifying to solve the problems, such as the marine biofouling of ship and marine facility surface The preparation method of pollution release type antifouling paint.Tested by protein adsorption, bacterial adhesion experiment, diatom attachment experiment and simulation Barnacle adhesive force is it is demonstrated experimentally that the anti-fouling effect of this hydrophilic modifying nonpolluting coating has significantly than the anti-fouling effect of control group coating Degree improves.Therefore, it has good actual application value as marine antifouling coating.
1) hydrophilic modifying pollution release type antifouling paint provided by the present invention, by protein adsorption it is demonstrated experimentally that its egg White adsorbance reduces 75.8%-83.2% than the protein adsorption quantity of control group.
2) hydrophilic modifying pollution release type antifouling paint provided by the present invention, by E. coli adhesion it is demonstrated experimentally that Its bacterial adhesion amount reduces 96.0%-98.7% than the bacterial adhesion amount of control group.
3) hydrophilic modifying pollution release type antifouling paint provided by the present invention, passes through staphylococcus aureus adhesion experiment Prove, its bacterial adhesion amount reduces 87.5%-97.1% than the bacterial adhesion amount of control group.
4) hydrophilic modifying pollution release type antifouling paint provided by the present invention, card is tested by the attachment of boat-shaped diatom Bright, the diatom attachment density of its diatom attachment density ratio control group reduces 93.6%-97.3%.
5) hydrophilic modifying pollution release type antifouling paint provided by the present invention, by simulating barnacle adhesive force experiment card Bright, its barnacle adhesive force reduces 58.2%-75.9% than the barnacle adhesive force of control group.
6) present invention has obtained Qingdao Haiyang science and technology National Laboratory open fund project (project number： QNLM2016ORP0407 support).
Brief description of the drawings
Fibrinogen (Fibrinogen) absorption result of Fig. 1 hydrophilic modifying pollution release type antifouling paints；
Escherichia coli (Escherichia coli) adhesion experiment bacterium colony of Fig. 2 hydrophilic modifying pollution release type antifouling paints Growing state；
Escherichia coli (Escherichia coli) adhesion experiment bacterium of Fig. 3 hydrophilic modifying pollution release type antifouling paints Density；
The staphylococcus aureus (Staphylococcus aureus) of Fig. 4 hydrophilic modifying pollution release type antifouling paints Adhesion experiment colony growth situation；
The staphylococcus aureus (Staphylococcus aureus) of Fig. 5 hydrophilic modifying pollution release type antifouling paints Adhesion experiment bacterial density；
Boat-shaped diatom (Naviculaparva) the attachment experiment diatom of Fig. 6 hydrophilic modifying pollution release type antifouling paints is attached Density.
Embodiment
The present invention can be explained in more detail by example below, the invention is not limited in the following examples；
Embodiment 1
The organosilicon pollution release type marine antifouling coating of hydrophilic modifying is prepared according to following steps
(1) the 2 of 0.50g are weighed, 2 '-azodiisobutyronitrile is dissolved in the in the mixed solvent of 5g dimethylbenzene and 5g butyl acetates, 80 DEG C are preheated to, obtains initiator solution；
(2) by the N- vinylpyrrolidones (NVP) of 6.67g, the butyl acrylate (BA) of 2.24g, the metering system of 1.75g Sour methyl esters (MMA), the hydroxyethyl methacrylate (HEMA) of 0.65g and the 2 of 1g, 2 '-azodiisobutyronitrile is dissolved in 10g dimethylbenzene With the in the mixed solvent of 10g butyl acetates, reactant solution is obtained；
(3) solution obtained in step (2) is slowly dropped in the solution obtained in step (1), rate of addition control In 0.5ml/s；After dripping solution, when insulation 4 is small, the 2 of 0.5g is added, 2 '-azodiisobutyronitrile, is warming up to 110 DEG C, protects Temperature reaction 12h, obtains reaction product, adds the petroleum ether that volume is 10 times of reaction solution and is precipitated out polymer, centrifugation is simultaneously Vacuum drying, so as to obtain hydrophilic side chain polymer A；
(4) the hydrophilic side chain polymer A obtained in 0.1g above-mentioned (3) is weighed, 1g dimethylbenzene is dissolved in and 1g butyl acetates mixes In bonding solvent, homogeneous mixture is obtained；
(5) dimethyl silicone polymer for weighing 2g is added in (4) in solution, is stirred evenly, is obtained mixture；
(6) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (5), is stirred evenly, is mixed Thing；
(7) dibutyl tin laurate for weighing 0.01g is added in the mixture in (6), is stirred evenly, is obtained antifouling Coating prepolymer；
(8) by the rapid even application of coating prepolymer on test substrate, thickness control is placed on 40 at 100 μm -1000 μm Dry solidification in DEG C baking oven, obtains uniform coating, coating is immersed in artificial seawater test it is stand-by.
Embodiment 2
The organosilicon pollution release type marine antifouling coating of hydrophilic modifying is prepared according to following steps
(1) the 2,2 '-azodiisobutyronitrile for weighing 0.75g is dissolved in the mixed solvent of 10g dimethylbenzene and 10g butyl acetates In, 85 DEG C are preheated to, obtains initiator solution；
(2) by the N- vinylpyrrolidones (NVP) of 6.0g, the butyl acrylate (BA) of 3.0g, the methacrylic acid of 1.0g Methyl esters (MMA), the hydroxyethyl methacrylate (HEMA) of 0.5g, the 2 of 0.5g, 2 '-azodiisobutyronitrile be dissolved in 10g dimethylbenzene and The in the mixed solvent of 10g butyl acetates, obtains reactant solution；
(3) solution obtained in step (2) is slowly dropped in the solution obtained in step (1), rate of addition control In 0.5ml/s；After dripping solution, when insulation 4 is small, the 2 of 0.5g is added, 2 '-azodiisobutyronitrile, is warming up to 110 DEG C, protects Temperature reaction 12h, obtains reaction product, adds the petroleum ether that volume is 10 times of reaction solution and is precipitated out polymer, centrifugation is simultaneously Vacuum drying, so as to obtain hydrophilic side chain polymer A；
(4) the hydrophilic side chain polymer A obtained in 0.2g above-mentioned (3) is weighed, is dissolved in 1g dimethylbenzene and 1g butyl acetates In mixed solution, homogeneous mixture is obtained；
(5) dimethyl silicone polymer for weighing 2g is added in (4) in solution, is stirred evenly, is obtained mixture；
(6) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (5), is stirred evenly, is mixed Thing；
(7) dibutyl tin laurate for weighing 0.01g is added in the mixture in (6), is stirred evenly, is obtained antifouling Coating prepolymer；
(8) by the rapid even application of coating prepolymer on test substrate, thickness control is placed on 40 at 100 μm -1000 μm Dry solidification in DEG C baking oven, obtains uniform coating, coating is immersed in artificial seawater test it is stand-by.
Embodiment 3
The organosilicon pollution release type marine antifouling coating of hydrophilic modifying is prepared according to following steps
(1) the 2 of 0.50g are weighed, 2 '-azodiisobutyronitrile is dissolved in 15g dimethylbenzene and 15g butyl acetates, is preheated to 80 DEG C, obtain initiator solution；
(2) by the N- vinylpyrrolidones (NVP) of 8.0g, the butyl acrylate (BA) of 1.0g, the methacrylic acid of 3.0g Methyl esters (MMA), the hydroxyethyl methacrylate (HEMA) of 1.0g, the 2 of 1.5g, 2 '-azodiisobutyronitrile be dissolved in 35g dimethylbenzene and In 35g butyl acetate mixed organic solvents, reactant solution is obtained；
(3) solution obtained in step (2) is slowly dropped in the solution obtained in step (1), rate of addition control In 0.5ml/s；After dripping solution, when insulation 4 is small, the 2 of 0.5g is added, 2 '-azodiisobutyronitrile, is warming up to 110 DEG C, protects Temperature reaction 12h, obtains reaction product, adds the ether that volume is 10 times of reaction solution and is precipitated out polymer, centrifuges and true Sky is dry, so as to obtain hydrophilic side chain polymer A；
(4) mixing of hydrophilic side chain polymer A, the 1g dimethylbenzene obtained in 0.3g above-mentioned (3) and 1g butyl acetates is weighed In solution, homogeneous mixture is obtained；
(5) dimethyl silicone polymer for weighing 2g is added in (4) in solution, is stirred evenly, is obtained mixture；
(6) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (5), is stirred evenly, is mixed Thing；
(7) dibutyl tin laurate for weighing 0.01g is added in the mixture in (6), is stirred evenly, is obtained antifouling Coating prepolymer；
(8) by the rapid even application of coating prepolymer on test substrate, thickness control is placed on 40 at 100 μm -1000 μm Dry solidification in DEG C baking oven, obtains uniform coating, coating is immersed in artificial seawater test it is stand-by.
Embodiment 4
(1) 0.5g azodiisobutyronitriles are dissolved in 10g isopropanols, thereto add 8g N- vinylpyrrolidones and The mercaptoethanol of 0.8g is added thereto, and is preheated to 65 DEG C, when insulation 8 is small, is obtained modified polyvinyl pyrrolidone solution, be spin-dried for molten Agent, adds the 2g dichloromethane dissolved solids that volume is solid masses, then adds 40g ether and polymeric reaction product settles out, Centrifugation, vacuum drying, that is, obtain modified polyvinyl pyrrolidone solid；
(2) the product 5g parts by weight that (1) obtains are added to (3- isocyano groups propyl group) triethoxysilane 0.5g and are dissolved in 5g In tetrahydrofuran solvent, 60 DEG C are preheated to, reaction 2 obtains reaction product when small, adds volume as the heavy of 5-10 times of reaction solution Polymer is precipitated out by depressant prescription, is centrifuged and is dried in vacuo, so as to obtain hydrophilic side chain polymer B；
(3) the hydrophilic side chain polymer B obtained in 0.3g above-mentioned (2), the mixing of 1g dimethylbenzene and 1g butyl acetates are weighed In solution, homogeneous mixture is obtained；
(4) dimethyl silicone polymer for weighing 2g is added in (3) in solution, is stirred evenly, is obtained mixture；
(5) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (4), is stirred evenly, is mixed Thing；
(6) dibutyl tin laurate for weighing 0.01g is added in the mixture in (5), is stirred evenly, is obtained antifouling Coating prepolymer.
Embodiment 5
The organosilicon pollution release type marine antifouling coating of hydrophilic modifying is prepared according to following steps
(1) the 2 of 1g are weighed, 2 '-azodiisobutyronitrile is dissolved in the in the mixed solvent of 15g dimethylbenzene and 15g butyl acetates, in advance Heat obtains initiator solution to 85 DEG C；
(2) the N- vinylpyrrolidones (NVP) of 80g, the acrylic acid of 20g are appointed into ester (BA), the methyl acrylate of 20g (MMA), the hydroxyethyl methacrylate (HEMA) of 11.5g, the 2 of 0.75g, 2 '-azodiisobutyronitrile be dissolved in 30g dimethylbenzene and In 30g butyl acetate mixed organic solvents, reactant solution is obtained；
(3) solution obtained in step (2) is slowly dropped in the solution obtained in step (1), rate of addition control In 0.5ml/s；After dripping solution, when insulation 4 is small, the 2 of 1g is added, 2 '-azodiisobutyronitrile, is warming up to 110 DEG C, insulation 12h is reacted, obtains reaction product, the n-hexane that volume is 10 times of reaction solution is added and is precipitated out polymer, centrifuge and true Sky is dry, so as to obtain hydrophilic side chain polymer A；
(4) the hydrophilic side chain polymer A obtained in 0.1g above-mentioned (3) is weighed, is dissolved in 1g dimethylbenzene and 1g butyl acetates In mixed solution, homogeneous mixture is obtained；
(5) dimethyl silicone polymer for weighing 2g is added in (4) in solution, is stirred evenly, is obtained mixture；
(6) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (5), is stirred evenly, is mixed Thing；
(7) dibutyl tin laurate for weighing 0.075g is added in the mixture in (6), is stirred evenly, is prevented Dirty coating prepolymer；
(8) by the rapid even application of coating prepolymer on test substrate, thickness control is placed on 40 at 100 μm -1000 μm Dry solidification in DEG C baking oven, obtains uniform coating, coating is immersed in artificial seawater test it is stand-by.
Embodiment 6
The organosilicon pollution release type marine antifouling coating of hydrophilic modifying is prepared according to following steps
(1) the 2,2 '-azodiisobutyronitrile for weighing 0.75g is dissolved in the mixed solution of 10g dimethylbenzene and 10g butyl acetates In, 70 DEG C are preheated to, obtains initiator solution；
(2) by the N- vinylpyrrolidones (NVP) of 70g, the ethyl methacrylate (BA) of 15g, the methacrylic acid of 15g Ethyl ester (MMA), the hydroxy methyl methacrylate (HMMA) of 11.5g, the 2 of 3.5g, 2 '-azodiisobutyronitrile is dissolved in 70g dimethylbenzene In 70g butyl acetate mixed organic solvents, reactant solution is obtained；
(3) solution obtained in step (2) is slowly dropped in the solution obtained in step (1), rate of addition control In 0.5ml/s；After dripping solution, when insulation 4 is small, the 2 of 2g is added, 2 '-azodiisobutyronitrile, is warming up to 110 DEG C, insulation 12h is reacted, obtains reaction product, the sedimentation agent that volume is 10 times of reaction solution is added and is precipitated out polymer, centrifuge and true Sky is dry, so as to obtain hydrophilic side chain polymer A；
(4) the hydrophilic side chain polymer A obtained in 0.2g above-mentioned (3) is weighed, is dissolved in 1g dimethylbenzene and 1g butyl acetates In mixed solution, homogeneous mixture is obtained；
(5) dimethyl silicone polymer for weighing 2g is added in (4) in solution, is stirred evenly, is obtained mixture；
(6) mixture in methyl γ-(methacryloxypropyl) propyl trimethoxy silicane addition (5) of 0.4g is weighed In, stir evenly, obtain mixture；
(7) dibutyltin diacetate for weighing 0.1g is added in the mixture in (6), is stirred evenly, is obtained antifouling painting Expect prepolymer；
(8) by the rapid even application of coating prepolymer on test substrate, thickness control is placed on 40 at 100 μm -1000 μm Dry solidification in DEG C baking oven, obtains uniform coating, coating is immersed in artificial seawater test it is stand-by.
Embodiment 7
(1) 0.75g azodiisobutyronitriles are dissolved in 20g isopropanols, thereto add 40g N- vinylpyrrolidones with And the mercaptoethanol of 4g is added thereto, 65 DEG C are preheated to, when insulation 8 is small, modified polyvinyl pyrrolidone solution is obtained, is spin-dried for molten Agent, adds the 20g dichloromethane dissolved solids that volume is solid masses, then adds 600g ether and polymeric reaction product sinks Go out, centrifuge, vacuum drying, that is, obtain modified polyvinyl pyrrolidone solid；
(2) the product 5g that (1) obtains is added to (3- isocyano groups propyl group) triethoxysilane 0.5g and is dissolved in 5g tetrahydrochysene furans Mutter in solvent, be preheated to 60 DEG C, reaction 2 obtains reaction product when small, and it is reaction solution 50g n-hexanes by polymer to add volume It is precipitated out, centrifuges and be dried in vacuo, so as to obtains hydrophilic side chain polymer B；
(3) the hydrophilic side chain polymer B obtained in 0.1g above-mentioned (2), the mixing of 1g dimethylbenzene and 1g butyl acetates are weighed In solution, homogeneous mixture is obtained；
(4) dimethyl silicone polymer for weighing 2g is added in (3) in solution, is stirred evenly, is obtained mixture；
(5) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (4), is stirred evenly, is mixed Thing；
(6) dibutyl tin laurate for weighing 0.01g is added in the mixture in (5), is stirred evenly, is obtained antifouling Coating prepolymer.
Embodiment 8
(1) 1.5g azodiisobutyronitriles are dissolved in 30g isopropanols, thereto add 50g N- vinylpyrrolidones and The mercaptoethanol of 6g is added thereto, and is preheated to 85 DEG C, when insulation 8 is small, is obtained modified polyvinyl pyrrolidone solution, be spin-dried for molten Agent, adds the 4g dichloromethane dissolved solids that volume is solid masses, then adds 1200g ether and polymeric reaction product sinks Go out, centrifuge, vacuum drying, that is, obtain modified polyvinyl pyrrolidone solid；
(2) the product 5g that (1) obtains is added to (3- isocyano groups propyl group) triethoxysilane 0.5g and is dissolved in 5g tetrahydrochysene furans Mutter in solvent, be preheated to 60 DEG C, reaction 2 obtains reaction product when small, and it is reaction solution 50g petroleum ethers by polymer to add volume It is precipitated out, centrifuges and be dried in vacuo, so as to obtains hydrophilic side chain polymer B；
(3) the hydrophilic side chain polymer B obtained in 0.5g above-mentioned (2), the mixing of 1g dimethylbenzene and 1g butyl acetates are weighed In solution, homogeneous mixture is obtained；
(4) dimethyl silicone polymer for weighing 2g is added in (3) in solution, is stirred evenly, is obtained mixture；
(5) methyl triacetoxysilane for weighing 0.2g is added in the mixture in (4), is stirred evenly, is mixed Thing；
(6) dibutyl tin laurate for weighing 0.01g is added in the mixture in (5), is stirred evenly, is obtained antifouling Coating prepolymer.
Control group embodiment
The organosilicon pollution release type marine antifouling coating of hydrophilic modifying is prepared according to following steps
(1) dimethyl silicone polymer for weighing 2g is added in 1-2g dimethylbenzene, is stirred evenly, is obtained mixture；
(2) methyl triacetoxysilane for weighing 0.17-0.23g is added in the mixture in (1), is stirred evenly, is obtained To mixture；
(3) dibutyl tin laurate for weighing 0.01-0.05g is added in the mixture in (2), is stirred evenly, is obtained To antifouling paint prepolymer；
(4) by the rapid even application of coating prepolymer on test substrate, thickness control is placed on 40 at 100 μm -1000 μm Dry solidification in DEG C baking oven, obtains uniform coating, coating is immersed in artificial seawater test it is stand-by.
Embodiment 9
The organosilicon pollution release type marine anti-pollution coating antifouling property test method of hydrophilic modifying is as follows：
(1) nonpolluting coating protein adsorption test uses enzyme linked immunosorbent assay (ELISA) (ELISA) method；
(2) nonpolluting coating bacterial adhesion experiment uses flat band method, and it is Escherichia coli (Escherichia to test with bacterium ) and staphylococcus aureus (Staphylococcus aureus) coli；
(3) nonpolluting coating diatom attachment experiment, diatom used in experiment are：Boat-shaped diatom (Naviculaparva)；
(4) simulate the test of barnacle adhesive force and use standard method of test ASTM D5618.
Test result：
(1) the ELISA experimental results of hydrophilic modifying pollution release type antifouling paint are as shown in Figure 1, embodiment 1 is not in figure By the test of the pure organic silicon antifouling paint of hydrophilic modification as a control group, other embodiments are the organosilicons by hydrophilic modifying For antifouling paint as experimental group, attachment proteins used is fibrinogen (Fibrinogen).Reality is can be seen that by data in figure Test the protein adsorption quantity of group reduces 75.8%-83.2% than the protein adsorption quantity of control group, after illustrating hydrophilic modifying, organosilicon The anti-protein adsorption ability of pollution release type antifouling paint significantly improves.
(2) Escherichia coli (Escherichia coli) experimental result of hydrophilic modifying pollution release type antifouling paint is as schemed Shown in 2 and Fig. 3, in figure embodiment 1 be not by the test of the pure organic silicon antifouling paint of hydrophilic modification as a control group, Qi Tashi It is to be used as experimental group by the organic silicon antifouling paint of hydrophilic modifying to apply example.The bacterium that can be seen that experimental group by data in figure is glued Attached amount is the 1.3%-4.0% of control group bacterial adhesion amount, after illustrating hydrophilic modifying, organosilicon pollution release type antifouling paint Anti- E. coli adhesion ability significantly improves.
(3) staphylococcus aureus (Staphylococcus aureus) of hydrophilic modifying pollution release type antifouling paint As shown in Figure 4 and Figure 5, embodiment 1 is not by the test conduct of the pure organic silicon antifouling paint of hydrophilic modification to experimental result in figure Control group, other embodiments are to be used as experimental group by the organic silicon antifouling paint of hydrophilic modifying.It can be seen that by data in figure The bacterial adhesion amount of experimental group is the 2.9%-12.5% of control group bacterial adhesion amount, and after illustrating hydrophilic modifying, organosilicon is stained The anti-Staphylococcus aureus adhesive capacity of release type antifouling paint significantly improves.
(4) boat-shaped diatom (Naviculaparva) the attachment experiments experiment knot of hydrophilic modifying pollution release type antifouling paint For fruit as shown in fig. 6, control group is not by the pure organic silicon antifouling paint of hydrophilic modification in figure, other embodiments are changed by hydrophilic The organic silicon antifouling paint of property is as experimental group.The diatom attachment density that can be seen that experimental group by data in figure is control group silicon Algae adheres to the 2.7%-6.4% of density, after illustrating hydrophilic modifying, the anti-diatom energy of attachment of organosilicon pollution release type antifouling paint Power ability significantly improves.
(5) the simulation barnacle adhesive force experimental result of hydrophilic modifying pollution release type antifouling paint is as shown in table 1, real in table Apply example 1 be not by the test of the pure organic silicon antifouling paint of hydrophilic modification as a control group, other embodiments are changed by hydrophilic The organic silicon antifouling paint of property is as experimental group.The simulation barnacle adhesive force that can be seen that experimental group by data in figure compares control group Small 58.2%-75.9%, after illustrating hydrophilic modifying, the pollution release ability of organosilicon pollution release type antifouling paint substantially carries It is high.
The simulation barnacle adhesive force experimental result of 1 hydrophilic modifying pollution release type antifouling paint of table

Claims (10)

  1. A kind of 1. pollution release type marine antifouling coating of hydrophilic modifying；It is characterized in that poly- the two of polyvinylpyrrolidone modification Methylsiloxane coating, structure such as formula：
    In formula,For hydrophilic side chain polymer A or B；R1For CH3Or C2H5；
    R2For dimethyl silicone polymer, its structural formula is：
    Wherein hydrophilic side chain polymer A is polyvinylpyrrolidone-polyacrylic resin (PVP-co-PAR), and structure is：
    In formula, R3For H or CH3；R4For CH3Or C2H5；R5For C2H5Or C4H9Or C8H17；R6For CH2Or (CH2)2Or (CH2)3；N is 120~160；M is 20~40；P is 20~40；Q is 10~20；
    Wherein hydrophilic side chain polymer B is that polyvinylpyrrolidone (PVP-SiOH) structure of silane coupling agent end-blocking is：
    In formula, R7For O or NH；R8For CH3Or C2H5；N is 120~200.
  2. 2. coating as claimed in claim 1；It is characterized in that the preparation method of the hydrophilic side chain polymer A includes following step Suddenly：
    (1) initiator of 0.5-1 parts by weight is dissolved in the organic solvent of 10-30 parts by weight, is preheated to 65 DEG C -85 DEG C, obtains The first solution；
    (2) by the N- vinylpyrrolidones of 60-80 parts by weight, the acrylate soft monomer of 10-20 parts by weight, 10-20 parts by weight (methyl) acrylate hard monomer, the haloalkylacrylates monomer of 5-10 parts by weight, 1.5-3.5 parts by weight draw Hair agent is dissolved in the organic solvent of 20-70 parts by weight, obtains second of solution；
    (3) solution obtained in step (2) is added drop-wise in step (1) in obtained solution, rate of addition is controlled in 0.5- 2ml/s；After dripping solution, when reaction 2-4 is small at 65 DEG C -85 DEG C, the initiator of 0.5-2 parts by weight is added, is warming up to 85 DEG C -110 DEG C, temperature-resistant reaction 6h-24h is maintained, obtains reaction product, add the sedimentation that volume is 5-10 times of reaction solution Polymer is precipitated out by agent, is centrifuged and is dried in vacuo, so as to obtain hydrophilic polymer A.
  3. 3. coating as claimed in claim 1；It is characterized in that the preparation method of the hydrophilic side chain polymer B includes following step Suddenly：
    (1) initiator of 0.5-1.5 parts by weight is dissolved in the organic solvent of 10-30 parts by weight, adds 30-50 weight thereto The N- vinylpyrrolidones of part and the sulfhydryl compound of 2-6 parts by weight are added thereto, and are preheated to 55 DEG C -85 DEG C, keep the temperature 6-12 Hour, modified polyvinyl pyrrolidone solution is obtained, solvent is spin-dried for, volume is added and is dissolved for 1-4 times of solvent of solid masses Solid, then adds volume and polymeric reaction product settles out for the precipitating reagent of 20-40 times of modified polyvinyl pyrrolidone solution, from The heart, vacuum drying, that is, obtain modified polyvinyl pyrrolidone；
    (2) product and 4-6 parts by weight Functional siloxane crosslinking agents obtained 40-60 parts by weight by (1) is dissolved in 34-44 weight In the organic solvent of part, 60-90 DEG C is preheated to, reaction 2-5 obtains reaction product when small, and it is 5-10 times of reaction solution to add volume Sedimentation agent polymer is precipitated out, centrifuge and be dried in vacuo, so as to obtain hydrophilic polymer.
  4. 4. coating according to claim 2；It is characterized in that the initiator is selected from 2,2 '-azodiisobutyronitrile, peroxidating Benzoyl or 2,2'- azos are double (2- methyl-N- (2- hydroxyethyls) propionamide)；The solvent is dimethylbenzene and butyl acetate Mixed solvent；The sedimentation agent is selected from petroleum ether, n-hexane or ether.
  5. 5. coating according to claim 3；It is characterized in that the initiator is selected from 2,2 '-azodiisobutyronitrile, peroxidating Benzoyl or 2,2'- azos are double (2- methyl-N- (2- hydroxyethyls) propionamide)；The solvent is selected from dichloromethane or tetrahydrochysene furan Mutter；The sedimentation agent is selected from petroleum ether, n-hexane or ether.
  6. 6. coating according to claim 2；Selected it is characterized in that preparing acrylate soft monomer described in hydrophilic side chain polymer A From ethyl acrylate, butyl acrylate or n-octyl；(methyl) acrylate hard monomer be selected from methyl methacrylate, Ethyl methacrylate, butyl methacrylate or methyl acrylate.
  7. 7. coating according to claim 3；It is characterized in that the sulfhydryl compound prepared described in hydrophilic side chain polymer B is selected from Mercaptoethanol or mercaptoethylmaine.
  8. 8. the pollution release type marine antifouling coating preparation method of the hydrophilic modifying described in claim 1, it is characterised in that including Following steps：
    (1) the hydrophilic side chain polymer A or B that parts by weight are 1-8 and the dimethyl silicone polymer that parts by weight are 10-30 are weighed, is added Enter in the organic solvent for being 20-30 to parts by weight, stir evenly, obtain reaction mixture；
    (2) crosslinking agent that parts by weight are 1-4 is added in the mixture in (1), is stirred evenly, obtains coating prepolymer；
    (3) catalyst that parts by weight are 0.5-1 is added in the mixture in (2), is stirred evenly, the uniform coating on substrate, Then cure at 40 DEG C -60 DEG C, obtain the nonpolluting coating of hydrophilic modifying.
  9. 9. according to the method described in claim 8, it is characterized in that, the dimethyl silicone polymer is double hydroxy-end capped poly- two Methylsiloxane；The crosslinking agent is selected from methyl triacetoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicon Alkane, gamma-aminopropyl-triethoxy-silane or (3- isocyano groups propyl group) triethoxysilane.
  10. 10. according to the method described in claim 8, it is characterized in that, the catalyst is selected from dibutyl tin laurate, two vinegar Sour dibutyl tin or stannous octoate；The organic solvent is dimethylbenzene and the mixed solvent of butyl acetate.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114349897A (en) * 2021-12-07 2022-04-15 吉林大学 Preparation method and novel antifouling application of bionic hydrophilic magnetic-control high-length-diameter ratio cilia

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53108126A (en) * 1977-03-03 1978-09-20 Toa Paint Co Ltd Foullproof paint for waterline
US4745140A (en) * 1987-03-13 1988-05-17 Chesebrough-Pond's Inc. Aqueous adhesive composition containing N-vinyl lactam resin, tackifier, and ethylene/vinyl acetate emulsion stabilizer
CN101531865A (en) * 2009-04-03 2009-09-16 中国船舶重工集团公司第七二五研究所 Method for preparing pollution-proof surface material suitably applied in marine environment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53108126A (en) * 1977-03-03 1978-09-20 Toa Paint Co Ltd Foullproof paint for waterline
US4745140A (en) * 1987-03-13 1988-05-17 Chesebrough-Pond's Inc. Aqueous adhesive composition containing N-vinyl lactam resin, tackifier, and ethylene/vinyl acetate emulsion stabilizer
CN101531865A (en) * 2009-04-03 2009-09-16 中国船舶重工集团公司第七二五研究所 Method for preparing pollution-proof surface material suitably applied in marine environment

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114349897A (en) * 2021-12-07 2022-04-15 吉林大学 Preparation method and novel antifouling application of bionic hydrophilic magnetic-control high-length-diameter ratio cilia
CN114349897B (en) * 2021-12-07 2022-12-09 吉林大学 Preparation method and novel antifouling application of bionic hydrophilic magnetic-control high-length-diameter ratio cilia

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