CN109294431A - A kind of marine antifouling coating - Google Patents
A kind of marine antifouling coating Download PDFInfo
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- CN109294431A CN109294431A CN201811129489.7A CN201811129489A CN109294431A CN 109294431 A CN109294431 A CN 109294431A CN 201811129489 A CN201811129489 A CN 201811129489A CN 109294431 A CN109294431 A CN 109294431A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
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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
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of marine antifouling coatings, belong to marine anti-pollution technical field.The present invention is using hydroxypropyl chitosan, polyvinyl alcohol as raw material interpenetrating networks gel, matrix as pretreatment nylon villus plays its load effect well, reduce the increase of wet quality, that improves nylon fiber uses the time, adhesive composition and other ingredients inside this marine antifouling coating can also play different antifouling effects, form the antifouling active layer of different function effect；The present invention is using polyether polyol as soft segment, 2,4- toluene di-isocyanate(TDI) and 1,4- butanediol is the polyurethane material of hard section, contained silicone segments may make their sample surface enrichments in film forming procedure, it is obviously improved the sea water resistance and stability of coating, the photosynthesis for interfering algae, inhibits the growth of algae pollutant.The present invention solves the problems, such as to commonly use marine antifouling coating water repellent bio adhesiving effect at present bad.
Description
Technical field
The invention belongs to marine anti-pollution technical fields, and in particular to a kind of marine antifouling coating.
Background technique
Wide ocean is survived millions upon millions of kinds of microorganism, sea-plant and marine animal, wherein having attachment characteristic
Marine organisms reach thousands of kinds.These marine organisms can be attached to the surface of solids in seawater and carry out growth and breeding, especially
In oxygen and sun-drenched surface seawater section, these marine organism growths and reproduction speed faster, often in ship, sea
Foreign engineering and the attachment of underwater facility surface, cause ship, ocean engineering and underwater facility surface to generate and are stained malicious event, therefore
Referred to as marine fouling organism.The ship important problem encountered that sails in a mighty ocean is exactly attachment of the marine organisms to hull bottom
And be stained, marine fouling organism is attached to hull bottom, will increase ship resistance, reduces ship's speed, consumes fuel more；It is attached to sea farming
Netting gear will cause blocking mesh, reduce exchange of seawater efficiency, it is even dead to can lead to cultivation fish and shellfish depauperation；It is attached to
On oceanographic instrumentation, instrument signal distortion, performance decline will lead to；It is attached to torpedo, increases weight and ship resistance, causes torpedo
Unbalance failure, to cause heavy losses.Coating antifouling paint is to solve the problems, such as to be stained not only economy but also efficient important channel.Often
Year there is a very big expense to be used in compensation since anti-fouling paint failure causes in deceleration, for coating antirust, antifouling painting again again
Material will also spend a large amount of expense.
In order to reduce the harm of marine organisms attachment, in early days using coating natural minerals and natural resin mixture or manually
It the methods of removes to prevent the attachment of marine fouling organism, but anti-fouling effect is poor, marine biofouling problem is still serious
Influence economic activity.With the development of science and technology developing all kinds of anti-soil technologies prevents marine biofouling, mainly there is coating antifouling
Coating Method, electrolysis antifouling method, mechanical removal method and conductive coat method etc..But even to this day, in many anti-soil technologies
In, coating antifouling paint is still most economical efficient method.Antifouling paint inhibits the effect machine of fouling organism attachment in ocean
System relies primarily on the exudation of toxic biocide in coating system, using the toxicological effect of biocide kill marine fouling organism or
It is inhibited to grow and breeding, wherein being that application effect so far is best, most with the antifouling paint of coating anti-fouling agent containing organotin
Extensive antifouling paint.But the problem that antifouling paint traditional at present is bad there are still water repellent bio adhesiving effect.Therefore it needs
Develop a kind of marine antifouling coating that adhesiving effect is strong.
Summary of the invention
The technical problems to be solved by the invention: bad for common marine antifouling coating water repellent bio adhesiving effect at present
The problem of, a kind of marine antifouling coating is provided.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of marine antifouling coating, including following component: 6 ~ 14 parts of acetone, 3 ~ 7 parts of neopelexes, 2 ~ 5 parts of levellings
Agent, 8 ~ 15 portions of realgars, 4 ~ 8 parts of cinnabar, 1 ~ 4 part of defoaming agent, further includes: 12 ~ 20 parts of compound antisticking components, 25 ~ 40 parts of composite bases
Material.
The preparation method of the compound antisticking component, includes the following steps:
(1) in 70 ~ 90 DEG C, 1:20 ~ 40:3 in mass ratio ~ 7:2 takes carboxymethyl chitosan, acetic acid solution, polyvinyl alcohol, acryloyl
Amine is mixed, cooling, and the sodium peroxydisulfate of polyvinyl alcohol quality 3 ~ 6%, 1 ~ 4% glutaraldehyde solution of acetic acid solution volume is added
Mixing, heat preservation, obtains gel, and gel is taken to be cleaned with mixing washing lotion, dry, obtains plural gel；
(2) in 40 ~ 60 DEG C, take plural gel 12 ~ 18:1:2 in mass ratio ~ 5:40 that undecyl acetoxyl group trichlorine silicon is added
Alkane, perfluor trichlorosilane, reagent A are mixed, and are warming up to 80 ~ 100 DEG C, are evaporated in vacuo, and are concentrated under reduced pressure, obtain glue, take glue
7 ~ 12:2 in mass ratio is added pretreatment nylon villus and is mixed, and supersonic oscillations are to get compound antisticking component.
Mixing washing lotion in the step (1): 1:7 ~ 12 take acetone, ethanol solution mixing to wash to get mixing in mass ratio
Liquid.
Reagent A in the step (2): 1:12 ~ 20 take guar gum, acetic acid solution mixing to get reagent A in mass ratio.
Pretreatment nylon villus in the step (2): 1:3 ~ 6:0.1:12 ~ 20 take vinyl trimethoxy in mass ratio
Silane, polylactic acid, silane coupling agent KH-560, PA6 nylon are kneaded in 170 ~ 190 DEG C, and stirring is cooled to 50 ~ 70 DEG C, Static Spinning
Silk, obtains nylon tow, and nylon tow is taken to be cut into villus, collects villus to get pretreatment nylon villus.
The preparation method of the composite base-material, includes the following steps:
S1. 10:3 ~ 6 take 2,4- toluene di-isocyanate(TDI), the mixing of end hydroxy polyether polyalcohol in mass ratio, in 60 ~ 75 DEG C, stir
It mixes, is cooled to 35 ~ 50 DEG C, the 1,4-butanediol mixing of end hydroxy polyether polyol quality 40 ~ 60% is added, is warming up to 68 ~ 80
DEG C, heat preservation is cooled to 55 ~ 65 DEG C, and 15 ~ 25 times of end hydroxy polyether polyol quality of reagent B is added and is mixed, obtains pre-polymerization
Body；
S2. take performed polymer 3:0.1:10 in mass ratio ~ 14 that auxiliary agent, dimethylbenzene mixing is added, prepolymer mass is added in shearing dispersion
The rosin mixing of 2 ~ 5% zinc oxide, the carbon nanotube of prepolymer mass 4 ~ 8%, prepolymer mass 2 ~ 5%, is stored at room temperature, is centrifuged,
Centrifugation object grinding is taken, is discharged to get composite base-material.
Reagent B: 5 ~ 8:2:1 in mass ratio in the step S1 take dimethylbenzene, ethyl acetate, cyclohexanone mixing to get
Reagent B.
Auxiliary agent in the step S2: 4:1 ~ 2 take polyvinylpyrrolidone, microcrystalline wax mixing to get helping in mass ratio
Agent.
The levelling agent: 5:1 ~ 3 take polyacrylic acid, carboxymethyl cellulose mixing to get levelling agent in mass ratio.
The defoaming agent: 3 ~ 6:1 in mass ratio takes dimethyl silicone polymer, silicone emulsion mixing to get defoaming agent.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention is using hydroxypropyl chitosan, polyvinyl alcohol as raw material interpenetrating networks gel, as pretreatment nylon villus
Matrix plays its load effect well, pre-processes nylon villus with systems such as PA6 nylon, polylactic acid, silane coupling agent surface changes
Property, its hydrophobicity is greatly enhanced, the increase of wet quality is reduced, improves the time that uses of nylon fiber, and analog sea lion is not
Stablize tapetum, reduce the adherency of pollutant, be on the one hand due to, the inhibition in small space between villus, nylon villus
Space is far smaller than the volume of minimum fouling organism, and fouling organism can not be approached and be inhaled due to the blocking by copolymer of fiber suede batt
Substrate surface is invested, thus plays the role of antifouling, another aspect, fibre fluff has unstable effect simultaneously, in dynamic condition
Under, fibre fluff is ceaselessly moved with water flow, and fouling organism can not stop, can not be in this completely unstable active-surface
Growth, under the conditions of relative quiescent, even if a small amount of seaweed can be stained with, can also fall off naturally in dynamic, and then provide good
Physics anti-pollution, while good to material compatibilities such as resins, and when portions of nylon villus shedding, this marine antifouling coating
Internal adhesive composition and other ingredients can also play different antifouling effects, form the antifouling active layer of different function effect；
(2) present invention is the polyurethane of hard section using polyether polyol as soft segment, 2,4- toluene di-isocyanate(TDI) and 1,4-butanediol
Material, with the increasing of hard segment content, the hydrogen bond action in polyurethane enhances, and the degree of cross linking increases, and limits segment in polyurethane
Movement effect, improve internal connecting forces, have the characteristic of ontology self-healing at room temperature, polar groups increase segment
Between interaction, the long period of soaking of seawater may make that for the reduction of phase separation degree, contained silicone segments may make them again
The sample surface enrichment in film forming procedure, hence it is evident that improve the sea water resistance and stability of coating, and the carbon nanotube wherein loaded
There is bactericidal effect with zinc oxide, the algal grown in marine fouling organism is influenced vulnerable to photosynthesis, therefore this coating adds face
Expect realgar, cinnabar, there is bactericidal effect, and can further improve the anti-fouling effect of spiked surface, surface can absorb different type
Light, interfere the photosynthesis of algae, inhibit the growth of algae pollutant.
Specific embodiment
Pre-process nylon villus: 1:3 ~ 6:0.1:12 ~ 20 take vinyltrimethoxysilane, polylactic acid, silicon in mass ratio
Alkane coupling agent KH-560, PA6 nylon is mixed in 170 ~ 190 DEG C of kneading machines, is stirred 20 ~ 40min with 120 ~ 200r/min, is cooled to
50 ~ 70 DEG C, electrostatic spinning obtains nylon tow, and nylon tow is taken to be cut into the villus of 1 ~ 4denier partial size, collect villus to get
Pre-process nylon villus.
Mixing washing lotion: the ethanol solution mixing that 1:7 ~ 12 take acetone in mass ratio, volume fraction is 70% is washed to get mixing
Liquid.
Reagent A: the acetic acid solution that 1:12 ~ 20 take guar gum in mass ratio, mass fraction is 8% mixes to get reagent A.
Reagent B: 5 ~ 8:2:1 in mass ratio takes dimethylbenzene, ethyl acetate, cyclohexanone mixing to get reagent B.
Levelling agent: 5:1 ~ 3 take polyacrylic acid, carboxymethyl cellulose mixing to get levelling agent in mass ratio.
Defoaming agent: 3 ~ 6:1 in mass ratio takes dimethyl silicone polymer, silicone emulsion mixing to get defoaming agent.
Auxiliary agent: 4:1 ~ 2 take polyvinylpyrrolidone, microcrystalline wax mixing to get auxiliary agent in mass ratio.
The preparation method of compound antisticking component, includes the following steps:
(1) in 70 ~ 90 DEG C, 1:20 ~ 40:3 in mass ratio ~ 7:2 takes carboxymethyl chitosan, mass fraction is 8% acetic acid solution,
Polyvinyl alcohol, acrylamide mixing naturally cool to 45 ~ 65 DEG C with 450 ~ 700r/min, 40 ~ 60min of magnetic agitation, are added poly-
The glutaraldehyde solution mixing of the sodium peroxydisulfate, 1 ~ 4% concentration 0.01mol/L of acetic acid solution volume of vinyl alcohol quality 3 ~ 6%, is protected
2 ~ 4h of temperature, obtains gel, after taking gel to clean 2 ~ 4 times with mixing washing lotion, moves to 55 ~ 70 DEG C of 1 ~ 3h of oven drying, obtains plural gel；
(2) in 40 ~ 60 DEG C of water-bath, take plural gel 12 ~ 18:1:2 in mass ratio ~ 5:40 that undecyl acetoxyl group trichlorine is added
Silane, perfluor trichlorosilane, reagent A mixing are warming up to 80 ~ 100 DEG C, vacuum is steamed with 800 ~ 1200r/min, 1 ~ 3h of magnetic agitation
Hair, is concentrated under reduced pressure into the 45 ~ 70% of original volume, obtains glue, takes glue 7 ~ 12:2 in mass ratio that pretreatment nylon villus mixing is added
Stirring moves to supersonic oscillations instrument with 50 ~ 65kHz frequency ultrasonic wave and vibrates 14 ~ 20min to get compound antisticking component.
The preparation method of composite base-material, includes the following steps:
S1. 10:3 ~ 6 take 2,4- toluene di-isocyanate(TDI), end hydroxy polyether polyalcohol to mix in reaction kettle in mass ratio, in 60 ~
75 DEG C, with 450 ~ 700r/min, 1 ~ 3h of magnetic agitation, 35 ~ 50 DEG C are cooled to, end hydroxy polyether polyol quality 40 ~ 60% is added
1,4-butanediol mixing, be warming up to 68 ~ 80 DEG C, keep the temperature 1 ~ 3h, be cooled to 55 ~ 65 DEG C, end hydroxy polyether polyalcohol matter is added
The reagent B mixing of 15 ~ 25 times of amount, with 600 ~ 1000r/min, 30 ~ 55min of magnetic agitation, obtains performed polymer；
S2. take performed polymer 3:0.1:10 in mass ratio ~ 14 that auxiliary agent, dimethylbenzene mixing is added, with 3000 ~ 4000r/min shearing point
6 ~ 10min is dissipated, the zinc oxide of prepolymer mass 2 ~ 5%, the carbon nanotube of prepolymer mass 4 ~ 8%, prepolymer mass 2 ~ 5% is added
Rosin mixing, be stored at room temperature 30 ~ 55min, 12 ~ 20min be centrifuged with 5000 ~ 7000/min, take centrifugation object in mortar with 350 ~
550r/min grinds 40 ~ 60min, discharges to get composite base-material.
A kind of marine antifouling coating, according to parts by weight, including following component: 6 ~ 14 parts of acetone, 3 ~ 7 parts of detergent alkylates
Sodium sulfonate, 2 ~ 5 parts of levelling agents, 8 ~ 15 portions of realgars, 4 ~ 8 parts of cinnabar, 1 ~ 4 part of defoaming agent, 12 ~ 20 parts of compound antisticking components, 25 ~ 40
Part composite base-material.
A kind of preparation method of marine antifouling coating, includes the following steps:
(1) according to parts by weight, 6 ~ 14 parts of acetone, 3 ~ 7 parts of neopelexes, 2 ~ 5 parts of levelling agents, 8 ~ 15 parts of heros are taken
Huang, 4 ~ 8 parts of cinnabar, 1 ~ 4 part of defoaming agent, 12 ~ 20 parts of compound antisticking components, 25 ~ 40 parts of composite base-materials；
(2) prior to 30 ~ 45 DEG C, acetone, levelling agent, cinnabar, realgar, defoaming agent, composite base-material is taken to mix in reaction kettle, with 400 ~
After 30 ~ 50min of 600r/min magnetic agitation, 55 ~ 75 DEG C are warming up to, it is mixed that neopelex, compound antisticking component is added
It closes, with 700 ~ 1000r/min magnetic agitation, 1 ~ 3h to get marine antifouling coating.
Pretreatment nylon villus: 1:3:0.1:12 in mass ratio takes vinyltrimethoxysilane, polylactic acid, silane coupled
Agent KH-560, PA6 nylon are mixed in 170 DEG C of kneading machines, are stirred 20min with 120r/min, are cooled to 50 DEG C, electrostatic spinning obtains
Nylon tow takes nylon tow to be cut into the villus of 1denier partial size, collects villus to get pretreatment nylon villus.
Mixing washing lotion: the ethanol solution mixing that 1:7 in mass ratio takes acetone, volume fraction is 70% is to get mixing washing lotion.
Reagent A: the acetic acid solution that 1:12 in mass ratio takes guar gum, mass fraction is 8% mixes to get reagent A.
Reagent B: 5:2:1 in mass ratio takes dimethylbenzene, ethyl acetate, cyclohexanone mixing to get reagent B.
Levelling agent: 5:1 in mass ratio takes polyacrylic acid, carboxymethyl cellulose mixing to get levelling agent.
Defoaming agent: 3:1 in mass ratio takes dimethyl silicone polymer, silicone emulsion mixing to get defoaming agent.
Auxiliary agent: 4:1 in mass ratio takes polyvinylpyrrolidone, microcrystalline wax mixing to get auxiliary agent.
The preparation method of compound antisticking component, includes the following steps:
(1) in 70 DEG C, 1:20:3:2 in mass ratio takes carboxymethyl chitosan, mass fraction is 8% acetic acid solution, polyvinyl alcohol,
Acrylamide mixing naturally cools to 45 DEG C with 450r/min magnetic agitation 40min, and the over cure of polyvinyl alcohol quality 3% is added
Sour sodium, acetic acid solution volume 1% concentration 0.01mol/L glutaraldehyde solution mixing, keep the temperature 2h, obtain gel, take gel with mixed
After closing washing lotion cleaning 2 times, 55 DEG C of oven drying 1h are moved to, plural gel is obtained；
(2) in 40 DEG C of water-bath, take plural gel 12:1:2:40 in mass ratio that undecyl acetoxyl group trichlorosilane, complete is added
Fluorine trichlorosilane, reagent A mixing are warming up to 80 DEG C with 800r/min magnetic agitation 1h, are evaporated in vacuo, are concentrated under reduced pressure into substance
Long-pending 45%, obtains glue, take glue 7:2 in mass ratio be added pretreatment nylon villus be mixed, move to supersonic oscillations instrument with
50kHz frequency ultrasonic wave vibrates 14min to get compound antisticking component.
The preparation method of composite base-material, includes the following steps:
S1. 10:3 in mass ratio takes 2,4- toluene di-isocyanate(TDI), end hydroxy polyether polyalcohol to mix in reaction kettle, in 60 DEG C,
With 450r/min magnetic agitation 1h, 35 DEG C are cooled to, the 1,4-butanediol mixing of end hydroxy polyether polyol quality 40% is added,
68 DEG C are warming up to, 1 ~ 3h is kept the temperature, is cooled to 55 DEG C, 15 times of end hydroxy polyether polyol quality of reagent B mixing is added, with
600r/min magnetic agitation 30min, obtains performed polymer；
S2. it takes performed polymer 3:0.1:10 in mass ratio that auxiliary agent, dimethylbenzene mixing is added, dispersion 6min is sheared with 3000r/min, is added
The rosin mixing for entering the zinc oxide of prepolymer mass 2%, the carbon nanotube of prepolymer mass 4%, prepolymer mass 2%, is stored at room temperature
30min is centrifuged 12min with 5000/min, centrifugation object is taken to grind 40min in mortar with 350r/min, discharges to get composite base
Material.
A kind of marine antifouling coating, according to parts by weight, including following component: 6 parts of acetone, 3 parts of dodecyl benzene sulfonic acid
Sodium, 2 parts of levelling agents, 8 portions of realgars, 4 parts of cinnabar, 1 part of defoaming agent, 12 parts of compound antisticking components, 25 parts of composite base-materials.
A kind of preparation method of marine antifouling coating, includes the following steps:
(1) according to parts by weight, 6 parts of acetone, 3 parts of neopelexes, 2 parts of levelling agents, 8 portions of realgars, 4 parts of cinnabar, 1 are taken
Part defoaming agent, 12 parts of compound antisticking components, 25 parts of composite base-materials；
(2) prior to 30 DEG C, acetone, levelling agent, cinnabar, realgar, defoaming agent, composite base-material is taken to mix in reaction kettle, with 400r/
After min magnetic agitation 30min, 55 DEG C are warming up to, neopelex, the mixing of compound antisticking component is added, with 700r/
1h is to get marine antifouling coating for min magnetic agitation.
Pretreatment nylon villus: 1:5:0.1:18 in mass ratio takes vinyltrimethoxysilane, polylactic acid, silane coupled
Agent KH-560, PA6 nylon are mixed in 180 DEG C of kneading machines, are stirred 30min with 180r/min, are cooled to 60 DEG C, electrostatic spinning obtains
Nylon tow takes nylon tow to be cut into the villus of 3denier partial size, collects villus to get pretreatment nylon villus.
Mixing washing lotion: the ethanol solution mixing that 1:10 in mass ratio takes acetone, volume fraction is 70% is to get mixing washing lotion.
Reagent A: the acetic acid solution that 1:18 in mass ratio takes guar gum, mass fraction is 8% mixes to get reagent A.
Reagent B: 6:2:1 in mass ratio takes dimethylbenzene, ethyl acetate, cyclohexanone mixing to get reagent B.
Levelling agent: 5:2 in mass ratio takes polyacrylic acid, carboxymethyl cellulose mixing to get levelling agent.
Defoaming agent: 5:1 in mass ratio takes dimethyl silicone polymer, silicone emulsion mixing to get defoaming agent.
Auxiliary agent: 4:1.5 in mass ratio takes polyvinylpyrrolidone, microcrystalline wax mixing to get auxiliary agent.
The preparation method of compound antisticking component, includes the following steps:
(1) in 80 DEG C, 1:30:5:2 in mass ratio takes carboxymethyl chitosan, mass fraction is 8% acetic acid solution, polyvinyl alcohol,
Acrylamide mixing naturally cools to 55 DEG C with 600r/min magnetic agitation 50min, and the over cure of polyvinyl alcohol quality 5% is added
Sour sodium, acetic acid solution volume 3% concentration 0.01mol/L glutaraldehyde solution mixing, keep the temperature 3h, obtain gel, take gel with mixed
After closing washing lotion cleaning 3 times, 60 DEG C of oven drying 2h are moved to, plural gel is obtained；
(2) in 50 DEG C of water-bath, take plural gel 16:1:3:40 in mass ratio that undecyl acetoxyl group trichlorosilane, complete is added
Fluorine trichlorosilane, reagent A mixing are warming up to 90 DEG C with 1000r/min magnetic agitation 2h, are evaporated in vacuo, are concentrated under reduced pressure into substance
Long-pending 60%, obtains glue, takes glue 10:2 in mass ratio that pretreatment nylon villus is added and is mixed, moves to supersonic oscillations instrument
With 55kHz frequency ultrasonic wave oscillation 18min to get compound antisticking component.
The preparation method of composite base-material, includes the following steps:
S1. 10:5 in mass ratio takes 2,4- toluene di-isocyanate(TDI), end hydroxy polyether polyalcohol to mix in reaction kettle, in 65 DEG C,
With 600r/min 1 ~ 3h of magnetic agitation, 40 DEG C are cooled to, the 1,4-butanediol that end hydroxy polyether polyol quality 50% is added is mixed
It closes, is warming up to 70 DEG C, keep the temperature 2h, be cooled to 50 DEG C, 20 times of end hydroxy polyether polyol quality of reagent B mixing is added, with
700r/min magnetic agitation 45min, obtains performed polymer；
S2. it takes performed polymer 3:0.1:13 in mass ratio that auxiliary agent, dimethylbenzene mixing is added, dispersion 8min is sheared with 3500r/min, is added
The rosin mixing for entering the zinc oxide of prepolymer mass 4%, the carbon nanotube of prepolymer mass 6%, prepolymer mass 4%, is stored at room temperature
45min is centrifuged 18min with 6000/min, centrifugation object is taken to grind 50min in mortar with 450r/min, discharges to get composite base
Material.
A kind of marine antifouling coating, according to parts by weight, including following component: 12 parts of acetone, 5 parts of dodecyl benzene sulfonic acid
Sodium, 4 parts of levelling agents, 13 portions of realgars, 6 parts of cinnabar, 3 parts of defoaming agents, 18 parts of compound antisticking components, 30 parts of composite base-materials.
A kind of preparation method of marine antifouling coating, includes the following steps:
(1) according to parts by weight, 12 parts of acetone, 5 parts of neopelexes, 4 parts of levelling agents, 13 portions of realgars, 6 parts of Zhu are taken
Sand, 3 parts of defoaming agents, 18 parts of compound antisticking components, 30 parts of composite base-materials；
(2) prior to 35 DEG C, acetone, levelling agent, cinnabar, realgar, defoaming agent, composite base-material is taken to mix in reaction kettle, with 500r/
After min magnetic agitation 40min, 65 DEG C are warming up to, neopelex, the mixing of compound antisticking component is added, with 800r/
2h is to get marine antifouling coating for min magnetic agitation.
Pretreatment nylon villus: 1:6:0.1:20 in mass ratio takes vinyltrimethoxysilane, polylactic acid, silane coupled
Agent KH-560, PA6 nylon are mixed in 190 DEG C of kneading machines, are stirred 40min with 200r/min, are cooled to 70 DEG C, electrostatic spinning obtains
Nylon tow takes nylon tow to be cut into the villus of 4denier partial size, collects villus to get pretreatment nylon villus.
Mixing washing lotion: the ethanol solution mixing that 1:12 in mass ratio takes acetone, volume fraction is 70% is to get mixing washing lotion.
Reagent A: the acetic acid solution that 1:20 in mass ratio takes guar gum, mass fraction is 8% mixes to get reagent A.
Reagent B: 8:2:1 in mass ratio takes dimethylbenzene, ethyl acetate, cyclohexanone mixing to get reagent B.
Levelling agent: 5:3 in mass ratio takes polyacrylic acid, carboxymethyl cellulose mixing to get levelling agent.
Defoaming agent: 6:1 in mass ratio takes dimethyl silicone polymer, silicone emulsion mixing to get defoaming agent.
Auxiliary agent: 4:2 in mass ratio takes polyvinylpyrrolidone, microcrystalline wax mixing to get auxiliary agent.
The preparation method of compound antisticking component, includes the following steps:
(1) in 90 DEG C, 1:40:7:2 in mass ratio takes carboxymethyl chitosan, mass fraction is 8% acetic acid solution, polyvinyl alcohol,
Acrylamide mixing naturally cools to 65 DEG C with 700r/min magnetic agitation 60min, and the over cure of polyvinyl alcohol quality 6% is added
Sour sodium, acetic acid solution volume 4% concentration 0.01mol/L glutaraldehyde solution mixing, keep the temperature 4h, obtain gel, take gel with mixed
After closing washing lotion cleaning 4 times, 70 DEG C of oven drying 3h are moved to, plural gel is obtained；
(2) in 60 DEG C of water-bath, take plural gel 18:1:5:40 in mass ratio that undecyl acetoxyl group trichlorosilane, complete is added
Fluorine trichlorosilane, reagent A mixing are warming up to 100 DEG C with 1200r/min magnetic agitation 3h, are evaporated in vacuo, are concentrated under reduced pressure into original
The 70% of volume, obtains glue, takes glue 12:2 in mass ratio that pretreatment nylon villus is added and is mixed, moves to supersonic oscillations
Instrument is with 65kHz frequency ultrasonic wave oscillation 20min to get compound antisticking component.
The preparation method of composite base-material, includes the following steps:
S1. 10:6 in mass ratio takes 2,4- toluene di-isocyanate(TDI), end hydroxy polyether polyalcohol to mix in reaction kettle, in 75 DEG C,
With 700r/min magnetic agitation 3h, 50 DEG C are cooled to, the 1,4-butanediol mixing of end hydroxy polyether polyol quality 60% is added,
80 DEG C are warming up to, 3h is kept the temperature, is cooled to 65 DEG C, 25 times of end hydroxy polyether polyol quality of reagent B mixing is added, with 1000r/
Min magnetic agitation 55min, obtains performed polymer；
S2. it takes performed polymer 3:0.1:14 in mass ratio that auxiliary agent, dimethylbenzene mixing is added, dispersion 10min is sheared with 4000r/min,
The rosin mixing of the zinc oxide of prepolymer mass 5%, the carbon nanotube of prepolymer mass 8%, prepolymer mass 5% is added, room temperature is quiet
55min is set, 20min is centrifuged with 7000/min, centrifugation object is taken to grind 60min in mortar with 550r/min, is discharged to get composite base
Material.
A kind of marine antifouling coating, according to parts by weight, including following component: 14 parts of acetone, 7 parts of dodecyl benzene sulfonic acid
Sodium, 5 parts of levelling agents, 15 portions of realgars, 8 parts of cinnabar, 4 parts of defoaming agents, 20 parts of compound antisticking components, 40 parts of composite base-materials.
A kind of preparation method of marine antifouling coating, includes the following steps:
(1) according to parts by weight, 14 parts of acetone, 7 parts of neopelexes, 5 parts of levelling agents, 15 portions of realgars, 8 parts of Zhu are taken
Sand, 4 parts of defoaming agents, 20 parts of compound antisticking components, 40 parts of composite base-materials；
(2) prior to 45 DEG C, acetone, levelling agent, cinnabar, realgar, defoaming agent, composite base-material is taken to mix in reaction kettle, with 600r/
After min magnetic agitation 50min, 75 DEG C are warming up to, neopelex, the mixing of compound antisticking component is added, with 1000r/
3h is to get marine antifouling coating for min magnetic agitation.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking compound antisticking component.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking composite base-material.
Comparative example 3: the marine antifouling coating of Guangzhou company production.
Comparative example and embodiment are tested according to GB/T6822-2007 standard, test result is as shown in table 1.
Table 1
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Barnacle young adhesive rate (%) | 21 | 25 | 23 | 28 | 31 | 55 |
| The inhibiting rate (%) of diatom attachment | 84.7 | 81.1 | 82.5 | 71.4 | 73.6 | 60.1 |
| Drying time (h) | 18 | 20 | 19 | 22 | 23 | 29 |
| Adhesion strength (MPa) | 97 | 95 | 96 | 92 | 93 | 87 |
In summary, marine antifouling coating of the invention is more preferable compared to commercial product effect, is worth promoting.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of marine antifouling coating, according to parts by weight, including following component: 6 ~ 14 parts of acetone, 3 ~ 7 parts of detergent alkylate sulphurs
Sour sodium, 2 ~ 5 parts of levelling agents, 8 ~ 15 portions of realgars, 4 ~ 8 parts of cinnabar, 1 ~ 4 part of defoaming agent, which is characterized in that further include: 12 ~ 20 parts are multiple
Close antisticking component, 25 ~ 40 parts of composite base-materials.
2. a kind of marine antifouling coating according to claim 1, which is characterized in that the preparation side of the compound antisticking component
Method includes the following steps:
(1) in 70 ~ 90 DEG C, 1:20 ~ 40:3 in mass ratio ~ 7:2 takes carboxymethyl chitosan, acetic acid solution, polyvinyl alcohol, acryloyl
Amine is mixed, cooling, and the sodium peroxydisulfate of polyvinyl alcohol quality 3 ~ 6%, 1 ~ 4% glutaraldehyde solution of acetic acid solution volume is added
Mixing, heat preservation, obtains gel, and gel is taken to be cleaned with mixing washing lotion, dry, obtains plural gel；
(2) in 40 ~ 60 DEG C, take plural gel 12 ~ 18:1:2 in mass ratio ~ 5:40 that undecyl acetoxyl group trichlorine silicon is added
Alkane, perfluor trichlorosilane, reagent A are mixed, and are warming up to 80 ~ 100 DEG C, are evaporated in vacuo, and are concentrated under reduced pressure, obtain glue, take glue
7 ~ 12:2 in mass ratio is added pretreatment nylon villus and is mixed, and supersonic oscillations are to get compound antisticking component.
3. a kind of marine antifouling coating according to claim 2, which is characterized in that the mixing washing lotion in the step (1): press
Mass ratio 1:7 ~ 12 take acetone, ethanol solution mixing to get mixing washing lotion.
4. a kind of marine antifouling coating according to claim 2, which is characterized in that the reagent A in the step (2): pressing matter
Amount takes guar gum, acetic acid solution mixing to get reagent A than 1:12 ~ 20.
5. a kind of marine antifouling coating according to claim 2, which is characterized in that the pretreatment nylon in the step (2)
Villus: 1:3 ~ 6:0.1:12 ~ 20 take vinyltrimethoxysilane, polylactic acid, silane coupling agent KH-560, PA6 in mass ratio
Nylon is kneaded in 170 ~ 190 DEG C, and stirring is cooled to 50 ~ 70 DEG C, electrostatic spinning obtains nylon tow, and nylon tow is taken to be cut into suede
Hair collects villus to get pretreatment nylon villus.
6. a kind of marine antifouling coating according to claim 1, which is characterized in that the preparation method of the composite base-material, packet
Include following steps:
S1. 10:3 ~ 6 take 2,4- toluene di-isocyanate(TDI), the mixing of end hydroxy polyether polyalcohol in mass ratio, in 60 ~ 75 DEG C, stir
It mixes, is cooled to 35 ~ 50 DEG C, the 1,4-butanediol mixing of end hydroxy polyether polyol quality 40 ~ 60% is added, is warming up to 68 ~ 80
DEG C, heat preservation is cooled to 55 ~ 65 DEG C, and 15 ~ 25 times of end hydroxy polyether polyol quality of reagent B is added and is mixed, obtains pre-polymerization
Body；
S2. take performed polymer 3:0.1:10 in mass ratio ~ 14 that auxiliary agent, dimethylbenzene mixing is added, prepolymer mass is added in shearing dispersion
The rosin mixing of 2 ~ 5% zinc oxide, the carbon nanotube of prepolymer mass 4 ~ 8%, prepolymer mass 2 ~ 5%, is stored at room temperature, is centrifuged,
Centrifugation object grinding is taken, is discharged to get composite base-material.
7. a kind of marine antifouling coating according to claim 6, which is characterized in that the reagent B in the step S1: pressing quality
Take dimethylbenzene, ethyl acetate, cyclohexanone mixing to get reagent B than 5 ~ 8:2:1.
8. a kind of marine antifouling coating according to claim 6, which is characterized in that the auxiliary agent in the step S2: pressing quality
Take polyvinylpyrrolidone, microcrystalline wax mixing to get auxiliary agent than 4:1 ~ 2.
9. a kind of marine antifouling coating according to claim 1, which is characterized in that the levelling agent: 5:1 ~ 3 take in mass ratio
Polyacrylic acid, carboxymethyl cellulose mixing are to get levelling agent.
10. a kind of marine antifouling coating according to claim 1, which is characterized in that the defoaming agent: 3 ~ 6:1 in mass ratio
Take dimethyl silicone polymer, silicone emulsion mixing to get defoaming agent.
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