CN108948837A - A kind of marine antifouling coating - Google Patents
A kind of marine antifouling coating Download PDFInfo
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- CN108948837A CN108948837A CN201810727174.6A CN201810727174A CN108948837A CN 108948837 A CN108948837 A CN 108948837A CN 201810727174 A CN201810727174 A CN 201810727174A CN 108948837 A CN108948837 A CN 108948837A
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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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- 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 coating technology application field.The present invention is using methyl methacrylate, the own ester of acrylic acid hexyl and dodecylacrylate monomer as primary raw material, it introduces methyl methacrylate and improves the hardness of basement membrane, adhesive force, water resistance, improve the hydrophobic performance of coating, using L-Aspartic acid and catalyst phosphoric acid as raw material, gamma-aminopropyl-triethoxy-silane is modified it, has preferable hydrophily；Tetradecy lamine, n,N-dimethylacetamide form the surface-active substance with amidine group under the catalytic action of phosphorus oxychloride, can improve the surface nature of coating, be unfavorable for biological attachment, extend the antifouling time.It is raw material using graphene oxide, sodium hydroxide, chloroacetic acid, 4, N-(2,4,6- trichlorophenyls is added) maleimide, capsaicine kill marine microorganism, reduce the pollution of microorganism.The present invention solves the problems, such as that the antifouling phase for current antifouling paint imitates that short, impact resistance is insufficient, anti-fouling effect is poor.
Description
Technical field
The invention belongs to coating technology application fields, and in particular to a kind of marine antifouling coating.
Background technique
The ship important problem encountered that sails in a mighty ocean is exactly marine organisms to the attachment of hull bottom and is stained.Marime fouling
Biological attachment will increase ship resistance, reduce ship's speed, consume fuel more in hull bottom；It is attached to sea farming netting gear, will cause blocking
Mesh reduces exchange of seawater efficiency, and it is even dead to can lead to cultivation fish and shellfish depauperation；It is attached on oceanographic instrumentation, can lead
Cause instrument signal distortion, performance decline；It is attached to torpedo, increases weight and ship resistance, so that the unbalance failure of torpedo, to make
At heavy losses.Therefore the marine antifouling coating for developing high-efficiency environment friendly, is an important issue.Marine antifouling coating is a kind of
Sapecial coating, its main function are to have an effect with marine organisms by the gradually exudation of anti-fouling agent in paint film, kill or drive
Marine organisms are walked, to prevent marine organisms attachment on the surface of the material, prevent marine organisms to oceans such as ship, harbour, harbours
Engineering is stained, and the vital movement of most of marine organisms is related with variation of ambient temperature, and environment temperature increases, and marine organisms are raw
Life activity is vigorous, and biological attachment ability enhancing on the surface of the material, environment temperature decline, marine organisms vital movement is rare,
The biological attachment reduced capability of material surface.The antifouling paint of the prior art is generally mainly anti-by base-material, environmental protection currently on the market
The compositions such as dirty agent, auxiliary material, pigments and fillers and organic solvent are constituted, and are gradually released in seawater to press down by environment-friendly antifouling agent
The attachment and growth of system and prevention biology on the ocean structures such as ship, to achieve the purpose that antifouling.Antifouling paint is discharging
Initial stage, there are violent release phenomenons causes the release of antifouling paint uncontrolled, short with the amount quick release far more than effective concentration
Failure in time.Cuprous oxide and organic tin environment-friendly antifouling agent are most common sea environment-friendly antifouling agent, organotin ring
Protect anti-fouling agent to prevent marine fouling organism have spectrum, will not be by the shadow of pollutant sulfide and sulfate in waters
It rings and loses antifouling activity, and dosage only has 1/10th of cuprous oxide, but since organotin environment-friendly antifouling agent is to ocean
Ecological environment has very big harm, is limited by various environmental regulations and disabling, International Maritime Organization passed through in 2001
Resolution: on January 1st, 2008, Organotin antifouling paints are disabled on all ships in the whole world.What National Bureau of Oceanography of China formulated
" China Ocean Agenda 21 " also clearly proposes to develop pollution-free marine anticorrosion anti-soil technology.
Summary of the invention
The technical problems to be solved by the invention: for current antifouling paint the antifouling phase effect it is short, impact resistance is insufficient, anti-
The problem of dirty effect difference, provides a kind of marine antifouling coating.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of marine antifouling coating, according to parts by weight include following component, 10 ~ 15 parts of polyvinyl alcohol, 2 ~ 4 parts of zinc stearates,
80 ~ 100 parts of water further include 50 ~ 70 parts of hydrophobic coatings, 30 ~ 40 parts of hydrophilic additives, 8 ~ 12 parts of surface reactive materials, 15 ~ 20 parts
Antifouling activity agent；
The preparation method of the hydrophobic coating, includes the following steps:
(1) it takes dimethylbenzene 1 ~ 3:1 in mass ratio ~ 4 that butyl acetate is added to be stirred, obtains mixed liquor, according to the mass fraction, take 6 ~
10 parts of methyl methacrylates, the own ester of 5 ~ 10 parts of acrylic acid hexyls, 5 ~ 9 parts of dodecylacrylates, 90 ~ 120 portions of mixed liquors,
It is stirred 40 ~ 50min, then instills 1 ~ 3 times of methyl methacrylate quality of acrylic acid, obtains mixture；
(2) it takes mixture 70 ~ 80:1 in mass ratio ~ 3 that benzoyl peroxide is added, is warming up to 110 ~ 120 DEG C of heat preservations, must stir mixed
Object is closed, takes stirring mixture 5 ~ 8:3 in mass ratio ~ 6 that polyethylene is added, then be warming up to 140 ~ 160 DEG C and be stirred, is cooled to room
Temperature obtains cooled material, adjusts pH to 7.5 ~ 8 with ammonium hydroxide, takes cooled material 10 ~ 20:1 in mass ratio ~ 4 that adipic acid dihydrazide stirring is added
Mixing is to get hydrophobic coating.
Hydrophobic coating is stirred condition in the step (2) are as follows: is stirred 30 ~ 40min in 25 ~ 35 DEG C.
The preparation method of the hydrophilic additive, includes the following steps:
S1. it takes L-Aspartic acid 3 ~ 7:2 in mass ratio ~ 4 that the phosphoric acid that mass fraction is 85% is added, is kept the temperature in 180 ~ 200 DEG C, done
It is dry, it pulverizes and sieves, collects sieving particle, take sieving particle 1 ~ 3:10 in mass ratio ~ 14 that n,N-Dimethylformamide mixing is added,
The gamma-aminopropyl-triethoxy-silane for adding polysuccinimide quality 30 ~ 40% is stirred, and must stir mixture a；
S2. take stirring mixture a 1 ~ 3:7 in mass ratio ~ 10 be added dehydrated alcohol, stand, filter, take filter slag in mass ratio 3 ~
5:10 ~ 13 is added distilled water and is stirred 30 ~ 40min, adds the hydrogen-oxygen for filtering that the concentration of slag amount 10 ~ 20% is 2mol/L
Change sodium solution, stands 1 ~ 2h, it is dry to get hydrophilic additive.
The stirring mixture a's of the step S1 is stirred condition are as follows: is stirred 2 ~ 4h in 55 ~ 65 DEG C.
The preparation method of the surface reactive material, includes the following steps:
It takes tetradecy lamine 2 ~ 5:3 in mass ratio ~ 7:10 ~ 15 that n,N-dimethylacetamide is added, is stirred 30 ~ 40min, in 35 ~
The phosphorus oxychloride of 40 DEG C of addition tetradecy lamine quality 20 ~ 30%, is stirred 10 ~ 12h, rotary evaporation obtains rotary evaporation object, takes rotation
Turn evaporant 1 ~ 4:6 in mass ratio ~ 10 and dehydrated alcohol is added, stands, take precipitating drying, obtain dried object, take dried object by quality
Fatty acid methyl ester sulfonate mixing is added to get surface reactive material than 3 ~ 6:1 ~ 3.
The preparation method of the antifouling activity agent, includes the following steps:
Take graphene oxide 1 ~ 3:100 in mass ratio ~ 150 that deionized water is added, ultrasonic disperse obtains ultrasonic disperse object, takes ultrasound
Sodium hydroxide, chloroacetic acid is added in dispersion 80 ~ 100:5 in mass ratio ~ 7:3 ~ 5, is stirred in 70 ~ 80 DEG C, dry, obtains dry
Dry object, take dried object be added 4, N-(2,4,6- trichlorophenyls) maleimide, capsaicine mixing to get antifouling activity agent.
The dried object and 4, N-(2,4,6- trichlorophenyl) maleimide, capsaicine mass ratio be 5 ~ 9:2 ~ 3:1 ~
3。
The present invention is compared with other methods, and advantageous effects are:
(1) present invention is using methyl methacrylate, the own ester of acrylic acid hexyl and dodecylacrylate monomer as primary raw material
The copolymer of synthesis becomes the derivatives resin of acrylic compounds, is referred to as acrylic resin paint using it as the coating of film forming binder,
It introduces methyl methacrylate and improves the hardness of basement membrane, adhesive force, the introducing of the own ester of acrylic acid hexyl improves the soft of basement membrane
Toughness, dodecylacrylate improve the water resistance of basement membrane, and acrylic acid is added and introduces carboxyl, improves the hydrophobicity of coating
Can, using L-Aspartic acid and catalyst phosphoric acid as raw material, form body polysuccinimide, gamma-aminopropyl-triethoxy-silane pair
It is modified, wherein containing a large amount of hydrophilic radical, such as carboxyl, amide groups, has preferable hydrophily, the two is answered
Conjunction forms antifouling paint matrix object；
(2) in the present invention after coating and water contact, system hydroaropic substance resin starts water swelling, and part water-absorbing resin is then
Gel can be formed on surface, keep film coated surface smooth, even if marine fouling organism is attached to, water flow caused by ship running
After scouring force can also make it peel off water-absorbing resin expansion easily, keep coating surface tension uneven, generate the concave-convex gauffer of left and right,
When fluid passes through, part is had in concave surface and forms vortex, plays the role of ball bearing, to achieve the effect that drag reduction, is absorbed water
Substance internal network space is channel, to system external penetration, carries out a part to the fouling organism for being attached to coating surface
Poisoning；
(3) present invention is formed with tetradecy lamine, DMAC N,N' dimethyl acetamide under the catalytic action of phosphorus oxychloride with amidine group
Surface-active substance, the addition of surfactant can improve the surface nature of coating, be unfavorable for biological attachment, in addition, surface-active
Object is self-assembly of vesica in coating matrix, in use, as the biology metabolism for being attached to film coated surface produces
Raw great amount of carbon dioxide, to make gas concentration lwevel in paint film ambient enviroment increase, so that the amidine in copolymer molecule structure
Group can act on carbon dioxide at normal temperature and take charge, be caused in vesica due to like charges repulsive interaction
The volume of portion's cavity expands, and the enlarged degree of volume increases with surface aufwuch quantity and increased, and final capsules rupture is led
The biology of surface attachment is caused to fall off, vesica makes antifouling activity agent exposure in system, be sustained in rupture process, extends anti-
The dirty time；
(4) present invention is raw material using graphene oxide, sodium hydroxide, chloroacetic acid is added, so that the hydroxyl on graphene oxide
Base and epoxy group are converted into carboxyl, and carboxyl is negatively charged, and the microorganism in ocean is generally negatively charged, and like charges repel each other,
Prevent microorganism adds 4, N-(2,4,6- trichlorophenyls from being adhered to marine surfaces) maleimide, capsaicine is to sea
Foreign microorganism is killed, and the pollution of microorganism is reduced.
Specific embodiment
Hydrophobic coating: (1) it takes dimethylbenzene 1 ~ 3:1 in mass ratio ~ 4 that butyl acetate is added and is stirred 20 ~ 30min, obtain mixed
It closes liquid and takes 6 ~ 10 parts of methyl methacrylates, the own ester of 5 ~ 10 parts of acrylic acid hexyls, 5 ~ 9 parts of acrylic acid 12 according to the mass fraction
Arrcostab, 90 ~ 120 portions of mixed liquors, are stirred 40 ~ 50min, then instill 1 ~ 3 times of methyl methacrylate quality of acrylic acid,
1 ~ 2h of time for adding is controlled, mixture is obtained；
(2) it takes mixture 70 ~ 80:1 in mass ratio ~ 3 that benzoyl peroxide is added, is warming up to 110 ~ 120 DEG C of 30 ~ 40min of heat preservation,
Mixture must be stirred, takes stirring mixture 5 ~ 8:3 in mass ratio ~ 6 that polyethylene is added, then be warming up to 140 ~ 160 DEG C and be stirred 1
~ 2h, is cooled to room temperature, and obtains cooled material, adjusts pH to 7.5 ~ 8 with ammonium hydroxide, cooled material 10 ~ 20:1 in mass ratio ~ 4 is taken to be added two
Acid dihydrazide is stirred 30 ~ 40min in 25 ~ 35 DEG C to get hydrophobic coating.
Hydrophilic additive: S1. takes L-Aspartic acid 3 ~ 7:2 in mass ratio ~ 4 that the phosphoric acid that mass fraction is 85% is added, in
180 ~ 200 DEG C of 1 ~ 2h of heat preservation, dry, pulverize and sieve with 100 mesh sieve, and collect sieving particle, take sieving particle 1 ~ 3:10 ~ 14 in mass ratio
N,N-Dimethylformamide is added and mixes 20 ~ 30min, adds three second of γ-aminopropyl of polysuccinimide quality 30 ~ 40%
Oxysilane is stirred 2 ~ 4h in 55 ~ 65 DEG C, must stir mixture a；
S2. take stirring mixture a 1 ~ 3:7 in mass ratio ~ 10 be added dehydrated alcohol, stand 30 ~ 40min, filter, take filter slag by
3 ~ 5:10 of mass ratio ~ 13 is added distilled water and is stirred 30 ~ 40min, and adding and filtering the concentration of slag amount 10 ~ 20% is 2mol/
The sodium hydroxide solution of L stands 1 ~ 2h, dry to get hydrophilic additive.
Surface reactive material: taking tetradecy lamine 2 ~ 5:3 in mass ratio ~ 7:10 ~ 15 that n,N-dimethylacetamide is added, and stirring is mixed
30 ~ 40min is closed, the phosphorus oxychloride of tetradecy lamine quality 20 ~ 30% is added in 35 ~ 40 DEG C, is stirred 10 ~ 12h, rotary evaporation obtains
Rotary evaporation object takes rotary evaporation object 1 ~ 4:6 in mass ratio ~ 10 that dehydrated alcohol is added, and stands 4 ~ 6h, takes precipitating drying, obtain dry
Dry object takes dried object 3 ~ 6:1 in mass ratio ~ 3 that fatty acid methyl ester sulfonate mixing is added to get surface reactive material.
Antifouling activity agent: take graphene oxide 1 ~ 3:100 in mass ratio ~ 150 be added deionized water, ultrasonic disperse 5 ~
10min obtains ultrasonic disperse object, takes ultrasonic disperse object 80 ~ 100:5 in mass ratio ~ 7:3 ~ 5 that sodium hydroxide, chloroacetic acid is added, in
70 ~ 80 DEG C are stirred 30 ~ 40min, dry, obtain dried object, and dried object 5 ~ 9:2 in mass ratio ~ 3:1 ~ 3 is taken to be added 4, N-(2,
4,6- trichlorophenyls) maleimide, capsaicine mixing to get antifouling activity agent.
A kind of marine antifouling coating, according to the mass fraction, including 50 ~ 70 parts of hydrophobic coatings, 30 ~ 40 parts of hydrophilic additives, 8
~ 12 parts of surface reactive materials, 15 ~ 20 parts of antifouling activity agent, 10 ~ 15 parts of polyvinyl alcohol, 2 ~ 4 parts of zinc stearates, 80 ~ 100 parts of water
Mixing is to get marine antifouling coating.
Embodiment 1
Hydrophobic coating: (1) it takes dimethylbenzene 1:1 in mass ratio that butyl acetate is added and is stirred 20min, mixed liquor is obtained, by quality
Number meter takes 6 parts of methyl methacrylates, the own ester of 5 parts of acrylic acid hexyls, 5 parts of dodecylacrylates, 90 portions of mixed liquors,
It is stirred 40min, then instills 1 times of methyl methacrylate quality of acrylic acid, time for adding 1h is controlled, obtains mixture；
(2) it takes mixture 70:1 in mass ratio that benzoyl peroxide is added, is warming up to 110 DEG C of heat preservation 30min, must be stirred
Object takes stirring mixture 5:3 in mass ratio that polyethylene is added, then is warming up to 140 DEG C and is stirred 1h, is cooled to room temperature, obtains cold
But object adjusts pH to 7.5 with ammonium hydroxide, takes cooled material 10:1 in mass ratio that adipic acid dihydrazide is added, be stirred in 25 DEG C
30min is to get hydrophobic coating.
Hydrophilic additive: S1. takes L-Aspartic acid 3:2 in mass ratio that the phosphoric acid that mass fraction is 85% is added, in 180 DEG C
1h is kept the temperature, dry, pulverize and sieve with 100 mesh sieve, collects sieving particle, takes sieving particle 1:10 in mass ratio that N, N- dimethyl methyl is added
Amide mixing 20min, adds the gamma-aminopropyl-triethoxy-silane of polysuccinimide quality 30%, is stirred in 55 DEG C
2h must stir mixture a；
S2. it takes stirring mixture a 1:7 in mass ratio that dehydrated alcohol is added, stands 30min, filter, take and filter slag in mass ratio 3:
10 addition distilled water are stirred 30min, add the sodium hydroxide solution for filtering that the concentration of slag amount 10% is 2mol/L, quiet
1h is set, it is dry to get hydrophilic additive.
Surface reactive material: it takes tetradecy lamine 2:3:10 in mass ratio that n,N-dimethylacetamide is added, is stirred
The phosphorus oxychloride of tetradecy lamine quality 20% is added in 35 DEG C, is stirred 10h, rotary evaporation obtains rotary evaporation object, takes by 30min
Dehydrated alcohol is added in rotary evaporation object 1:6 in mass ratio, stands 4h, takes precipitating drying, obtain dried object, take dried object in mass ratio
Fatty acid methyl ester sulfonate mixing is added to get surface reactive material in 3:1.
Antifouling activity agent: taking graphene oxide 1:100 in mass ratio that deionized water is added, and ultrasonic disperse 5min is obtained ultrasonic
Dispersion takes ultrasonic disperse object 80:5:3 in mass ratio that sodium hydroxide, chloroacetic acid is added, is stirred 30min in 70 DEG C, does
Dry, dried object obtained, takes dried object 5:2:1 in mass ratio that 4, N-(2,4,6- trichlorophenyls are added) maleimide, capsaicine be mixed
It closes to get antifouling activity agent.
A kind of marine antifouling coating, according to the mass fraction, including 50 parts of hydrophobic coatings, 30 parts of hydrophilic additives, 8 parts of surfaces
Active material, 15 parts of antifouling activity agent, 10 parts of polyvinyl alcohol, 2 parts of zinc stearates, 80 parts of water mixing are to get marine antifouling coating.
Embodiment 2
Hydrophobic coating: (1) it takes dimethylbenzene 2:3 in mass ratio that butyl acetate is added and is stirred 25min, mixed liquor is obtained, by quality
Number meter takes 8 parts of methyl methacrylates, the own ester of 8 parts of acrylic acid hexyls, 7 parts of dodecylacrylates, 105 portions of mixed liquors,
It is stirred 45min, then instills 2 times of methyl methacrylate quality of acrylic acid, time for adding 1.5h is controlled, obtains mixture；
(2) it takes mixture 75:2 in mass ratio that benzoyl peroxide is added, is warming up to 115 DEG C of heat preservation 35min, must be stirred
Object takes stirring mixture 7:5 in mass ratio that polyethylene is added, then is warming up to 150 DEG C and is stirred 1.5h, is cooled to room temperature, obtains
Cooled material adjusts pH to 7.8 with ammonium hydroxide, takes cooled material 15:3 in mass ratio that adipic acid dihydrazide is added, be stirred in 30 DEG C
35min is to get hydrophobic coating.
Hydrophilic additive: S1. takes L-Aspartic acid 5:3 in mass ratio that the phosphoric acid that mass fraction is 85% is added, in 190 DEG C
1.5h is kept the temperature, dry, pulverize and sieve with 100 mesh sieve, collects sieving particle, takes sieving particle 2:12 in mass ratio that N, N- dimethyl is added
Formamide mixing 25min, adds the gamma-aminopropyl-triethoxy-silane of polysuccinimide quality 35%, mixed in 60 DEG C of stirrings
3h is closed, mixture a must be stirred；
S2. it takes stirring mixture a 2:9 in mass ratio that dehydrated alcohol is added, stands 35min, filter, take and filter slag in mass ratio 4:
12 addition distilled water are stirred 35min, add the sodium hydroxide solution for filtering that the concentration of slag amount 15% is 2mol/L, quiet
1.5h is set, it is dry to get hydrophilic additive.
Surface reactive material: it takes tetradecy lamine 4:5:13 in mass ratio that n,N-dimethylacetamide is added, is stirred
The phosphorus oxychloride of tetradecy lamine quality 25% is added in 38 DEG C, is stirred 11h, rotary evaporation obtains rotary evaporation object, takes by 35min
Dehydrated alcohol is added in rotary evaporation object 3:8 in mass ratio, stands 5h, takes precipitating drying, obtain dried object, take dried object in mass ratio
Fatty acid methyl ester sulfonate mixing is added to get surface reactive material in 5:2.
Antifouling activity agent: taking graphene oxide 2:130 in mass ratio that deionized water is added, and ultrasonic disperse 8min is obtained ultrasonic
Dispersion takes ultrasonic disperse object 90:6:4 in mass ratio that sodium hydroxide, chloroacetic acid is added, is stirred 35min in 75 DEG C, does
It is dry, obtain dried object, take dried object 7:2.5:2 in mass ratio that 4, N-(2,4,6- trichlorophenyls are added) maleimide, capsaicine
Mixing is to get antifouling activity agent.
A kind of marine antifouling coating, according to the mass fraction, including 60 parts of hydrophobic coatings, 35 parts of hydrophilic additives, 10 parts of tables
Face active material, 18 parts of antifouling activity agent, 13 parts of polyvinyl alcohol, 3 parts of zinc stearates, 90 parts of water mixing are to get marine anti-pollution painting
Material.
Embodiment 3
Hydrophobic coating: (1) it takes dimethylbenzene 3:4 in mass ratio that butyl acetate is added and is stirred 30min, mixed liquor is obtained, by quality
Number meter takes 10 parts of methyl methacrylates, the own ester of 10 parts of acrylic acid hexyls, 9 parts of dodecylacrylates, 120 parts of mixing
Liquid is stirred 50min, then instills 3 times of methyl methacrylate quality of acrylic acid, controls time for adding 2h, obtains mixture；
(2) it takes mixture 80:3 in mass ratio that benzoyl peroxide is added, is warming up to 120 DEG C of heat preservation 40min, must be stirred
Object takes stirring mixture 8:6 in mass ratio that polyethylene is added, then is warming up to 160 DEG C and is stirred 2h, is cooled to room temperature, obtains cold
But object adjusts pH to 8 with ammonium hydroxide, takes cooled material 20:4 in mass ratio that adipic acid dihydrazide is added, be stirred in 35 DEG C
40min is to get hydrophobic coating.
Hydrophilic additive: S1. takes L-Aspartic acid 7:4 in mass ratio that the phosphoric acid that mass fraction is 85% is added, in 200 DEG C
2h is kept the temperature, dry, pulverize and sieve with 100 mesh sieve, collects sieving particle, takes sieving particle 3:14 in mass ratio that N, N- dimethyl methyl is added
Amide mixing 30min, adds the gamma-aminopropyl-triethoxy-silane of polysuccinimide quality 40%, is stirred in 65 DEG C
4h must stir mixture a；
S2. it takes stirring mixture a 3:10 in mass ratio that dehydrated alcohol is added, stands 40min, filter, take and filter slag in mass ratio
5:13 is added distilled water and is stirred 40min, adds the sodium hydroxide solution for filtering that the concentration of slag amount 20% is 2mol/L,
2h is stood, it is dry to get hydrophilic additive.
Surface reactive material: it takes tetradecy lamine 5:7:15 in mass ratio that n,N-dimethylacetamide is added, is stirred
The phosphorus oxychloride of tetradecy lamine quality 30% is added in 40 DEG C, is stirred 12h, rotary evaporation obtains rotary evaporation object, takes by 40min
Dehydrated alcohol is added in rotary evaporation object 4:10 in mass ratio, stands 6h, takes precipitating drying, obtain dried object, take dried object by quality
Fatty acid methyl ester sulfonate mixing is added to get surface reactive material than 6:3.
Antifouling activity agent: taking graphene oxide 3:150 in mass ratio that deionized water is added, and ultrasonic disperse 10min obtains ultrasonic disperse
Object takes ultrasonic disperse object 100:7:5 in mass ratio that sodium hydroxide, chloroacetic acid is added, is stirred 40min in 80 DEG C, dry,
Dried object is obtained, takes dried object 9:3:3 in mass ratio that 4, N-(2,4,6- trichlorophenyls are added) maleimide, capsaicine mixing,
Up to antifouling activity agent.
A kind of marine antifouling coating, according to the mass fraction, including 70 parts of hydrophobic coatings, 40 parts of hydrophilic additives, 12 parts of tables
Face active material, 20 parts of antifouling activity agent, 15 parts of polyvinyl alcohol, 4 parts of zinc stearates, 100 parts of water mixing are to get marine anti-pollution painting
Material.
Comparative example 1: it is essentially identical with the preparation method of embodiment 3, it has only the difference is that lacking hydrophobic coating.
Comparative example 2: it is essentially identical with the preparation method of embodiment 3, it has only the difference is that lacking hydrophilic additive.
Comparative example 3: it is essentially identical with the preparation method of embodiment 3, it has only the difference is that lacking surface reactive material.Comparison
Example 4: it is essentially identical with the preparation method of embodiment 3, it has only the difference is that lacking antifouling activity agent.
Comparative example 5: the marine antifouling coating of certain company production in the market.
The marine anti-pollution according to " GB/T 9286-1998 " standard prepared by embodiment 1,2,3 and comparative example 1,2,3,4,5
Coating irony is imitated hull surface and is tested for the property, test result record such as table 1.
Table 1:
As shown in Table 1, marine antifouling coating anti-fouling effect prepared by the present invention is strong, and adhesive force is preferable, and impact resistance foot, antifouling
Phase effect length, be worth promoting use.
Claims (7)
1. a kind of marine antifouling coating includes following component, 10 ~ 15 parts of polyvinyl alcohol, 2 ~ 4 parts of stearic acid according to parts by weight
Zinc, 80 ~ 100 parts of water, which is characterized in that further include 50 ~ 70 parts of hydrophobic coatings, 30 ~ 40 parts of hydrophilic additives, 8 ~ 12 parts of surfaces work
Property substance, 15 ~ 20 parts of antifouling activity agent；
The preparation method of the hydrophobic coating, includes the following steps:
(1) it takes dimethylbenzene 1 ~ 3:1 in mass ratio ~ 4 that butyl acetate is added to be stirred, obtains mixed liquor, according to the mass fraction, take 6 ~
10 parts of methyl methacrylates, the own ester of 5 ~ 10 parts of acrylic acid hexyls, 5 ~ 9 parts of dodecylacrylates, 90 ~ 120 portions of mixed liquors,
It is stirred 40 ~ 50min, then instills 1 ~ 3 times of methyl methacrylate quality of acrylic acid, obtains mixture；
(2) it takes mixture 70 ~ 80:1 in mass ratio ~ 3 that benzoyl peroxide is added, is warming up to 110 ~ 120 DEG C of heat preservations, must stir mixed
Object is closed, takes stirring mixture 5 ~ 8:3 in mass ratio ~ 6 that polyethylene is added, then be warming up to 140 ~ 160 DEG C and be stirred, is cooled to room
Temperature obtains cooled material, adjusts pH to 7.5 ~ 8 with ammonium hydroxide, takes cooled material 10 ~ 20:1 in mass ratio ~ 4 that adipic acid dihydrazide stirring is added
Mixing is to get hydrophobic coating.
2. marine antifouling coating according to claim 1, which is characterized in that the stirring of hydrophobic coating in the step (2)
Mixing condition are as follows: be stirred 30 ~ 40min in 25 ~ 35 DEG C.
3. marine antifouling coating according to claim 1, which is characterized in that the preparation method of the hydrophilic additive, packet
Include following steps:
S1. it takes L-Aspartic acid 3 ~ 7:2 in mass ratio ~ 4 that the phosphoric acid that mass fraction is 85% is added, is kept the temperature in 180 ~ 200 DEG C, done
It is dry, it pulverizes and sieves, collects sieving particle, take sieving particle 1 ~ 3:10 in mass ratio ~ 14 that n,N-Dimethylformamide mixing is added,
The gamma-aminopropyl-triethoxy-silane for adding polysuccinimide quality 30 ~ 40% is stirred, and must stir mixture a；
S2. take stirring mixture a 1 ~ 3:7 in mass ratio ~ 10 be added dehydrated alcohol, stand, filter, take filter slag in mass ratio 3 ~
5:10 ~ 13 is added distilled water and is stirred 30 ~ 40min, adds the hydrogen-oxygen for filtering that the concentration of slag amount 10 ~ 20% is 2mol/L
Change sodium solution, stands 1 ~ 2h, it is dry to get hydrophilic additive.
4. marine antifouling coating according to claim 3, which is characterized in that the stirring mixture a's of the step S1 stirs
Mix mixing condition are as follows: be stirred 2 ~ 4h in 55 ~ 65 DEG C.
5. marine antifouling coating according to claim 1, which is characterized in that the preparation method of the surface reactive material,
Include the following steps:
It takes tetradecy lamine 2 ~ 5:3 in mass ratio ~ 7:10 ~ 15 that n,N-dimethylacetamide is added, is stirred 30 ~ 40min, in 35 ~
The phosphorus oxychloride of 40 DEG C of addition tetradecy lamine quality 20 ~ 30%, is stirred 10 ~ 12h, rotary evaporation obtains rotary evaporation object, takes rotation
Turn evaporant 1 ~ 4:6 in mass ratio ~ 10 and dehydrated alcohol is added, stands, take precipitating drying, obtain dried object, take dried object by quality
Fatty acid methyl ester sulfonate mixing is added to get surface reactive material than 3 ~ 6:1 ~ 3.
6. marine antifouling coating according to claim 1, which is characterized in that the preparation method of the antifouling activity agent, packet
Include following steps:
Take graphene oxide 1 ~ 3:100 in mass ratio ~ 150 that deionized water is added, ultrasonic disperse obtains ultrasonic disperse object, takes ultrasound
Sodium hydroxide, chloroacetic acid is added in dispersion 80 ~ 100:5 in mass ratio ~ 7:3 ~ 5, is stirred in 70 ~ 80 DEG C, dry, obtains dry
Dry object, take dried object be added 4, N-(2,4,6- trichlorophenyls) maleimide, capsaicine mixing to get antifouling activity agent.
7. marine antifouling coating according to claim 6, which is characterized in that the dried object and 4, N-(2,4,6- trichlorines
Phenyl) maleimide, capsaicine mass ratio be 5 ~ 9:2 ~ 3:1 ~ 3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810727174.6A CN108948837A (en) | 2018-07-05 | 2018-07-05 | A kind of marine antifouling coating |
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| CN201810727174.6A CN108948837A (en) | 2018-07-05 | 2018-07-05 | A kind of marine antifouling coating |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529637A (en) * | 2018-12-18 | 2019-03-29 | 曲靖师范学院 | A kind of preparation method of resisting microbial contamination polyvinylidene fluoride separation membrane |
| BE1028533B1 (en) * | 2020-08-24 | 2022-09-08 | Chaohu Guoli Hangbiao Equipment Co Ltd | METHOD OF IMPROVING THE CORROSION RESISTANCE OF A NAVIGATION FLOAT LAMP HOLDER |
| CN115850559A (en) * | 2022-11-18 | 2023-03-28 | 湘潭大学 | Zinc acrylate/capsaicinoid copolymer as well as preparation method and application thereof |
-
2018
- 2018-07-05 CN CN201810727174.6A patent/CN108948837A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529637A (en) * | 2018-12-18 | 2019-03-29 | 曲靖师范学院 | A kind of preparation method of resisting microbial contamination polyvinylidene fluoride separation membrane |
| CN109529637B (en) * | 2018-12-18 | 2021-08-03 | 曲靖师范学院 | Preparation method of polyvinylidene fluoride separation membrane resisting microbial contamination |
| BE1028533B1 (en) * | 2020-08-24 | 2022-09-08 | Chaohu Guoli Hangbiao Equipment Co Ltd | METHOD OF IMPROVING THE CORROSION RESISTANCE OF A NAVIGATION FLOAT LAMP HOLDER |
| CN115850559A (en) * | 2022-11-18 | 2023-03-28 | 湘潭大学 | Zinc acrylate/capsaicinoid copolymer as well as preparation method and application thereof |
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