CN105062175A - Antifouling biological adhesive agent and antifouling biological adhesive coating - Google Patents
Antifouling biological adhesive agent and antifouling biological adhesive coating Download PDFInfo
- Publication number
- CN105062175A CN105062175A CN201510485615.2A CN201510485615A CN105062175A CN 105062175 A CN105062175 A CN 105062175A CN 201510485615 A CN201510485615 A CN 201510485615A CN 105062175 A CN105062175 A CN 105062175A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- silicon dioxide
- agent
- quaternary ammonium
- hollow microsphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides an antifouling biological adhesive agent and an antifouling biological adhesive coating. The antifouling biological adhesive agent is organosilicon quaternary ammonium salt surface-modified antibacterial-agent-carried zinc oxide/silicon dioxide hollow microspheres. The adhesive agent comprises organosilicon quaternary ammonium salt, an antibacterial agent and zinc oxide/silicon dioxide hollow microspheres, wherein the mass ratio of the organosilicon quaternary ammonium salt to the antibacterial agent to the zinc oxide/silicon dioxide hollow microspheres is (1-3): (6-50): 5, and the mass ratio of zinc oxide to silicon dioxide in the zinc oxide/silicon dioxide hollow microspheres is 5: (0.1-3). By using a technical scheme in the invention, through organic-inorganic compound synergistic effects, more efficient and more long-term antibacterial and anti-biological adhesive performances are realized, and good biocompatibility, environmental compatibility and use safety are obtained.
Description
Technical field
The invention belongs to antifouling paint technical field, particularly relate to a kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating.
Background technology
The process utilized along with ocean space is accelerated, marine concrete structure engineering, as more and more extensive in application such as harbour, breakwater, off-shore airport, offshore lighthouse, subbottom tunnel and bridge spanning the seas.Due to long-term immersion, various biologies in ocean, as the attachment of sea grass, shellfish, mollusk etc., cause deep layer by surface damage to destroy, marine concrete structure is caused to be subject to serious stained, not only cause financial loss, and serious harm is caused to marine concrete structure security and weather resistance.
Coating technology is the most frequently used effective guard technology, mainly have studied the protective coating that polyurethane coating series, series of acrylate, chlorinated rubber series, epoxy series and alkyd series etc. are conventional at present both at home and abroad.What work in anti-halobios adhersion coating is anti-halobios adhersion agent, and for a long time, maritime concrete adopts high pollution, highly toxic organic tin antifouling paint in a large number, and International Maritime Organizaton has prohibitted the use such stain control agent.Along with international community is to the growing interest of environmental problem, development environment friendly marine antifouling coating has more real economy and social effect.
Summary of the invention
For above technical problem, the invention discloses a kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating, by the synergy of organic materials and inorganic materials compound, realize the performance of more efficient more permanent antibacterial and anti-halobios adhersion, there is good biocompatibility, environment compatibility and safety in utilization.
To this, the technical solution used in the present invention is:
A kind of anti-fouling biological attachment agent, described anti-fouling biological attachment agent is the zinc oxide/silicon dioxide hollow microsphere being loaded with antiseptic-germicide of organosilicon quaternary ammonium salt surface modification, it comprises organosilicon quaternary ammonium salt, antiseptic-germicide, zinc oxide/silicon dioxide hollow microsphere, described organosilicon quaternary ammonium salt: antiseptic-germicide: the mass ratio of zinc oxide/silicon dioxide hollow microsphere is (1 ~ 3): (6 ~ 50): 5, the silicon-dioxide in wherein said zinc oxide/silicon dioxide hollow microsphere and the mass ratio of zinc oxide are 5:(0.1 ~ 3).
Zinc oxide be the earliest for one of antibacterial metal oxide, there is good biocompatibility, environment compatibility and safety in utilization.Nano zine oxide has the features such as the surface energy that particle diameter is little, specific surface area large, surface atom number is many, Atomic coordinate is not enough and high, compared with organic antibacterial agent, has wide spectrum, lasting, safe, nontoxic feature.
The duct charge capacity that is regular and hollow material that hollow mesoporous silicon oxide has had mesoporous silicon oxide concurrently is large.Simultaneously the cavity size of hollow hole Jie silicon-dioxide and thickness adjustable, loading capacity and the release rate of regulating drug can be come by the result changing hollow silica, thus possess the feature of medicament slow release.
Organosilicon quaternary ammonium salt is cats product, has high temperature resistant, water-fastness, lasting effect, the feature that scope of restraining fungi is wide and effectively antibacterial; And cheap, antibacterial speed is fast, practicality is comparatively strong, has the microbial processs such as good kill bacteria, algae due to it.
Adopt technical scheme of the present invention, organosilicon quaternary ammonium salt can play the effect of surface modification zinc oxide, makes both play common synergy, improves its antibacterial anti-halobios adhersion performance in coating.Silicon dioxide microsphere has that specific surface area is large, porous nickel, void content are high and has certain porosity, to macromolecular organic compound and bacterium, there is stronger adsorptive power, there is certain adsorptivity to nano inoganic particle simultaneously, because its hollow structure possesses certain carried medicine sustained-release performance, it is combined with organosilicon quaternary ammonium salt and zinc oxide, better can strengthens antibacterial antifouling effect.In addition, using hollow nano silicon as internal layer, the effect strengthening zinc oxide shell and make it not easily cave in can also be played.Therefore, technical scheme of the present invention is by the synergy of Organic-inorganic composite, make described anti-fouling biological attachment agent effectively can prevent the attachment of algae and other fouling organisms, improve antibacterial scavenging effect, thus realize the performance of more efficiently permanent antibacterial anti-halobios adhersion.
Preferred further, described zinc oxide is nano zine oxide.Nano zine oxide has the features such as the surface energy that particle diameter is little, specific surface area large, surface atom number is many, Atomic coordinate is not enough and high, compared with organic antibacterial agent, has wide spectrum, lasting, safe, nontoxic feature.
Preferred further, described silicon-dioxide is nano silicon.It is large that nano silica microsphere has specific surface area, has the performance of more efficiently permanent antibacterial anti-halobios adhersion.
As a further improvement on the present invention, described organosilicon quaternary ammonium salt: antiseptic-germicide: the mass ratio of zinc oxide/silicon dioxide hollow microsphere is (1.5 ~ 2.5): (10 ~ 40): 5, and wherein in zinc oxide/silicon dioxide hollow microsphere, the mass ratio of silicon-dioxide and zinc oxide is 5:(0.2 ~ 2).
As a further improvement on the present invention, described antiseptic-germicide is at least one in imidazoline quaternary ammonium salt or potassium sorbate.In this technical scheme, described imidazoline quaternary ammonium salt, except possessing certain antibacterial properties, also plays the performance of inhibition to the metallic surface of marine ship etc.
As a further improvement on the present invention, described anti-fouling biological attachment agent adopts following steps preparation:
Step S1: prepare organic template, makes organic template/silica core-shell microspheres;
Step S2: prepare zinc oxide/silicon dioxide hollow microsphere;
Step S3: prepare organosilicon quaternary ammonium salt surface modification zinc oxide/silicon dioxide hollow microsphere;
Step S4: the zinc oxide/silicon dioxide hollow microsphere being loaded with antiseptic-germicide preparing organosilicon quaternary ammonium salt surface modification;
Wherein, described organic template is vinylbenzene and acrylic acid copolymer microballoon or cetyl trimethylammonium bromide.
As a further improvement on the present invention, described organic template is vinylbenzene and acrylic acid copolymer microballoon, and its making step is: N is being housed
2oxygen scavenging container in add ethanol, polyethylene pyrrole network alkane ketone, vinylformic acid and be dissolved with the vinylbenzene of Diisopropyl azodicarboxylate, stir into homogeneous system; Then be warming up to 60 ~ 80 DEG C, isothermal reaction 24 ~ 36h obtains polymerized emulsion; Again that polymerized emulsion is centrifugal, abandoning supernatant, washs, dries, drying obtains vinylbenzene and acrylic acid copolymer microballoon.
As a further improvement on the present invention, in step S1, described making organic template/silica core-shell microspheres comprises the following steps: in organic template, add dehydrated alcohol carry out ultrasonic disperse, then tetraethyl orthosilicate is added after adding water and ammoniacal liquor stirring 5 ~ 30min, sealing bottleneck, at 20 ~ 40 DEG C of reaction 3 ~ 15h; Centrifugal, washing, dry.
As a further improvement on the present invention, in step S2, the preparation of described zinc oxide/silicon dioxide hollow microsphere adopts following steps preparation: in the container that distilled water is housed, add organic template/silica core-shell microspheres and soluble zinc salt, Trisodium Citrate is added after stirring, add in ammoniacal liquor to solution when producing precipitation and disappear immediately after abundant stirring, then container is placed in oil bath and is heated to 110 ~ 180 DEG C of stirring and refluxing 3 ~ 12h; By gained precipitation and centrifugal separation, and with obtaining zinc oxide/organic template/silica core-shell microspheres after washed with de-ionized water, drying; Finally by zinc oxide/organic template/silica core-shell microspheres under air atmosphere, be warming up to 400 DEG C ~ 650 DEG C, temperature rise rate is 0.5 ~ 2 DEG C/min, insulation 3 ~ 7h, cooling obtain zinc oxide/silicon dioxide hollow microsphere; Wherein, the mol ratio of described Trisodium Citrate and zinc salt is 1:1.5 ~ 6.
Preferably, the concentration of described soluble zinc salt is 0.01 ~ 0.05mol/L.
As a further improvement on the present invention, in step S3, the preparation method of described organosilicon quaternary ammonium salt surface modification zinc oxide/silicon dioxide hollow microsphere is: added by zinc oxide/silicon dioxide hollow microsphere in organosilicone quaternary ammonium salts solution, mix and blend 2 ~ 4h under normal temperature, then adjust ph to 3 ~ 4, after leaving standstill 12 ~ 24h, carry out supersound washing, in 80 ~ 120 DEG C of dryings, grinding.
Preferably, under whipped state, oxalic acid adjust ph is dropwise added; Preferred further, described concentration of oxalic acid is 0.1 ~ 2mol/L.
As a further improvement on the present invention, in step S4, the described step being loaded with the zinc oxide/silicon dioxide hollow microsphere of antiseptic-germicide preparing organosilicon quaternary ammonium salt surface modification is: bleed zinc oxide/silicon dioxide hollow microsphere decompression 15 ~ 30min, drip antiseptic-germicide, open Vltrasonic device simultaneously, until the complete submergence zinc oxide/silicon dioxide microsphere of antiseptic-germicide and ultrasonic disperse evenly after, withdraw from reliever, stirred at ambient temperature 7 ~ 9h, and at interval of the ultrasonic 1min of 2h; Centrifugal, to discard after supernatant liquid vacuum-drying 12 ~ 24h at 60 DEG C.Preferably, the concentration of described antiseptic-germicide is 0.03g/mL ~ 0.5g/mL.
Preferably, described antiseptic-germicide is imidazoline quaternary ammonium salt; Described imidazoline quaternary ammonium salt is obtained through modification by imidazoline intermediate, comprises the following steps:
Steps A: add catalyzer and water-removal agent in the mixture of organic acid acetic and organic amine, carry out dealcoholization, then carry out intramolecular cyclization dehydration reaction and obtain imidazoline intermediate; The mol ratio of described organic acid acetic and organic amine is 1:(1 ~ 1.3); The temperature of reaction of described intermolecular dealcoholization is 120 ~ 160 DEG C, reaction times 2 ~ 5h; The temperature of reaction of described intramolecular cyclization dehydration reaction is 180 ~ 230 DEG C, reaction times 3 ~ 6h;
Wherein, described organic acid acetic is at least one in the saturated stearate of C12 ~ C18 or the carboxylicesters of C12 ~ C18;
Described organic amine is at least one in diethylenetriamine, triethylene tetramine, tetraethylene pentamine or hydroxyethylethylene diamine;
Described catalyzer is the one in activated alumina, boric acid or zinc granule;
Described water-removal agent is calcium oxide;
Step B: add water-soluble modified dose in the imidazoline intermediate obtained in step and mix, carries out isothermal reaction 2 ~ 5h, obtains imidazoline quaternary ammonium salt under 90 ~ 110 DEG C of environment; Wherein, the mol ratio of described imidazoline intermediate and water-soluble modified dose is 1:(1 ~ 1.1); Described water-soluble modified dose is at least one in Benzyl Chloride, sodium chloroacetate, Mono Chloro Acetic Acid or Glacial acetic acid.
Present invention also offers a kind of anti-fouling biological attachment coating, described anti-fouling biological attachment coating by A, B two component form, wherein, the component that component A comprises and weight percent thereof are: polyisocyanates 50-70%, polyether glycol 30-50%, the component that B component comprises and weight percent thereof are: polyaspartate 40-70%, anti-fouling biological attachment agent 1 ~ 15%, pigment 5 ~ 25%, filler 5-25%, auxiliary agent 0.5-5%; Wherein, described anti-fouling biological attachment agent is anti-fouling biological attachment agent as above.
As a further improvement on the present invention, the component that comprises of described anti-fouling biological attachment coating and weight percent thereof are: polyisocyanates 50-65%, polyether glycol 35-50%; Polyaspartate 55-65%, anti-fouling biological attachment agent 1 ~ 10%, pigment 5 ~ 20%, filler 5-20%, auxiliary agent 1-5%.
Wherein, described auxiliary agent is at least one in wetting dispersing agent, coupling agent, flow agent and defoamer.
As a further improvement on the present invention, described polyisocyanates is 2, at least one in 4 '-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, described polyether glycol is at least one in polypropylene glycol ether or PTMG.
Preferably, described polyaspartate is that ethyl maleate and primary amine are obtained by Michael addition reaction, and wherein said primary amine is polyoxytrimethylene polyamine or the polyoxyethylene polyamine of two functional groups or trifunctional.
As a further improvement on the present invention, described filler is at least one in oyster shell whiting, quartz sand powder or talcum powder.
As a further improvement on the present invention, described pigment is titanium dioxide.
As a further improvement on the present invention, described filler and/or filler are adopt surface-modifying agent to carry out surface-treated; Described surface-modifying agent is at least one in stearates, aluminate coupling agent, titanate coupling agent, silane coupling agent.
Described defoamer is silicone based defoamer or calcium oxide.
The anti-fouling biological attachment agent that technical scheme of the present invention adopts is the zinc oxide/silicon dioxide hollow microsphere being loaded with antiseptic-germicide of organosilicon quaternary ammonium salt surface modification.Wherein, organosilicon quaternary ammonium salt is cats product, has high temperature resistant, water-fastness, lasting effect, the feature that scope of restraining fungi is wide and effectively antibacterial; Zinc oxide be the earliest for one of antibacterial metal oxide, there is good biocompatibility, environment compatibility and safety in utilization.Nano zine oxide has the features such as the surface energy that particle diameter is little, specific surface area large, surface atom number is many, Atomic coordinate is not enough and high, compared with organic antibacterial agent, has wide spectrum, lasting, safe, nontoxic feature.
Compared with prior art, beneficial effect of the present invention is:
First, zinc oxide, silicon-dioxide, organosilicon quaternary ammonium salt, antiseptic-germicide itself possess the performance of the microorganisms such as good kill bacteria, algae, adopt technical scheme of the present invention, by load antiseptic-germicide in zinc oxide/silicon dioxide hollow microsphere, then in conjunction with organosilicon quaternary ammonium salt, reach the synergy of Organic-inorganic composite, realize the performance of more efficient more permanent antibacterial and anti-halobios adhersion, there is good biocompatibility, environment compatibility and safety in utilization.
The second, adopt technical scheme of the present invention, make coating surface can be very low, marine organisms effectively can be prevented in the attachment of concrete surface, play lasting long-acting and anti-fouling effect.
3rd, adopt technical scheme of the present invention, the erosion to concrete structure such as corrosive ion in seawater, seawater can be stoped, realize the permanent protection to maritime concrete, extend its work-ing life.
Accompanying drawing explanation
Fig. 1 is the structural representation of the anti-fouling biological attachment agent described in an embodiment of the present invention.
Mark in figure: 1-silicon-dioxide, 2-zinc oxide, 3-organosilicon quaternary ammonium salt, 4-imidazoline quaternary ammonium salt.
Embodiment
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail.
Embodiment 1
Step1. polyaspartate is prepared, code name PAE-a
Amino Terminated polyether(ATPE) JeffamineD-2000 and ethyl maleate are pressed amount of substance than n (-NH
2): n (-C=C-)=1:1 metering.JeffamineD-2000 is added in the reactor being equipped with agitator, heating temperature control device; logical nitrogen is also warmed up to 40 DEG C; drip ethyl maleate; rate of addition be every two seconds one; after dropwising; stirred under nitrogen atmosphere is heated to 80 DEG C, and insulation 24h, cooling discharge is polyaspartate.
Step2. poly aspartic acid ester paint component A is prepared
2,4 '-diphenylmethanediisocyanate MDI-50 and polyoxypropyleneglycol PPG2000 consumption are measured by NCO%=15% in the prepolymer generated.2 are added in the reactor being equipped with agitator, heating temperature control device; 4 '-diphenylmethanediisocyanate MDI-50; logical nitrogen is also warmed up to 40 DEG C, drips polyoxypropyleneglycol PPG2000, rate of addition be every two seconds one; after dropwising; stirred under nitrogen atmosphere is heated to 75 DEG C, and METHOD FOR CONTINUOUS DETERMINATION NCO content, the stopped reaction when NCO mass percent change≤0.05%; the cooling discharging that stirs is Isocyanate prepolymers body, as coating component A.
Step3. surface modification oyster shell whiting is prepared
By waste shell through recovery and rinsing, alkali cleaning 24h, clean water, dry, grind the oyster shell whiting obtained, its median size is 0.1 μm ~ 100 μm.Take the appropriate oyster shell whiting after grinding, be 1:10 by solid-to-liquid ratio, be added to the water, be warming up to 90 DEG C of constant temperature 30min and obtain shell slurry; The addition of surface-modifying agent sodium stearate is 1% of oyster shell whiting quality, is added after dissolving in a small amount of hot water, adds after reacting 30min in the shell slurry of constant temperature, suction filtration, dry, and grinding, obtains modified oyster shell whiting.
Step4. anti-fouling biological attachment agent is prepared
(1) preparation of vinylbenzene and acrylic acid copolymer microsphere template
In 250mL there-necked flask, add 100mL dehydrated alcohol successively, 1.25g polyethylene pyrrole network alkane ketone, 0.5mL vinylformic acid and be dissolved with the vinylbenzene 28mL of 0.30g Diisopropyl azodicarboxylate, stir and make formation homogeneous system.Pass into N in advance
2deoxygenation 30min, then rapid temperature increases to 70 DEG C, isothermal reaction 24h.And polymerized emulsion is centrifugal, abandoning supernatant.With washing with alcohol several times after, naturally dry under room temperature, be then placed in finish-drying under infrared lamp, obtain white vinylbenzene and acrylic acid copolymer microsphere powder.
(2) preparation of white vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres
Take white vinylbenzene and acrylic acid copolymer microsphere template 0.4g, with 20mL dehydrated alcohol ultrasonic disperse.In this dispersion liquid, add 0.4mL water, 0.4mL ammoniacal liquor stirs 5min, then adds 0.6mL tetraethyl orthosilicate, seals bottleneck with preservative film, isothermal reaction 8h at 30 DEG C.Centrifugal, washing, dry vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres.
(3) preparation of zinc oxide/silicon dioxide hollow microsphere
Take 3mmol zinc nitrate hexahydrate and 4.5g vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres and be placed in 250mL round-bottomed flask, add 200mL distilled water, abundant stirring, add Trisodium Citrate 0.5mmol, ammoniacal liquor 30mL is added after abundant stirring, produce white precipitate in solution and disappear immediately, flask being placed in oil bath pan and being heated to 120 DEG C of stirring and refluxing.By the centrifugation of gained white precipitate, and fully clean with deionized water, zinc oxide/vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres after drying, can be obtained in atmosphere.Finally zinc oxide/vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres are placed in crucible, in air atmosphere, are slowly warming up to 400 DEG C, and are incubated 5h, temperature rise rate is 1 DEG C/min.
(4) silicone Quaternary Ammonium Salt Antimicrobial Agent surface modification zinc oxide/silicon dioxide hollow microsphere
Take appropriate 5g zinc oxide/silicon dioxide hollow microsphere and 1g organosilicon quaternary ammonium salt is dissolved in 100mL deionized water, low speed mixing stirs 3h at normal temperatures, under whipped state, then dropwise adds 1mol/L oxalic acid regulate mixing solutions pH to 3.After leaving standstill 24h, supersound washing repeatedly, 110 DEG C of dryings, grinding.
(5) preparation of imidazoline quaternary ammonium salt
A small amount of ceramic particle and 0.13mol tetraethylene pentamine is added in the there-necked flask being connected with thermometer, spherical condensation tube, agitator, be warmed up to 110 DEG C and add 6.5g calcium oxide as water-removal agent, 0.1mol laurate is dropwise added with constant voltage separating funnel, drip off in 30 minutes, be warmed up to 150-160 DEG C, carry out intermolecular amidation dealcoholization 5h; Continue stirring and be warming up to 210-220 DEG C, carry out intramolecular cyclization dehydration reaction 5h, obtain imidazoline intermediate; Above-mentioned imidazoline intermediate is cooled to 90-100 DEG C, and the ratio being 1:1.1 in the mol ratio of imidazoline intermediate and sodium chloroacetate drips sodium chloroacetate, and constant temperature stirs and carries out quaterisation 5h, obtained imidazoline quaternary ammonium salt.
(6) preparation of the modification zinc oxide/silicon dioxide hollow microsphere of antiseptic-germicide is loaded with
Take 0.5g modified zinc oxide/silicon dioxide hollow microsphere, add that 40mL concentration is housed is in the there-necked flask of the imidazoline quaternary ammonium salt of 40mg/mL, decompression is bled 15min, removes the air in flask and zinc oxide/silicon dioxide hollow microsphere.Open funnel stopcock, open Vltrasonic device simultaneously, until the complete submergence zinc oxide/silicon dioxide microsphere of liquid and ultrasonic disperse evenly after, withdraw from reliever, stirring at room temperature 8h.At interval of the ultrasonic 1min of 2h during this stirs.Centrifugal, discard supernatant liquid, hollow microsphere is vacuum-drying 24h at 60 DEG C, obtains anti-fouling biological attachment agent.As shown in Figure 1, described anti-fouling biological attachment agent is the hollow microsphere of zinc oxide 2/ silica 1 being loaded with imidazoline quaternary ammonium salt 4 of organosilicon quaternary ammonium salt 3 surface modification, wherein, described imidazoline quaternary ammonium salt 4 is carried in the hollow core of the hollow microsphere of zinc oxide 2/ silica 1, and organosilicon quaternary ammonium salt 3 is on the surface of the hollow microsphere of zinc oxide 2/ silica 1.
Step5. poly aspartic acid ester paint B component is prepared
Take polyaspartate PAE-a65 part of Step1, oyster shell whiting 10 parts, titanium dioxide 10 parts, talcum powder 8 parts, anti-halobios adhersion agent 5 parts, auxiliary agent 2 parts, joins successively in scuffing of cylinder bore, high-speed stirring 1h, mixes discharging, as coating B component.
During use by-NCO in component A with the-NH mol ratio in B component for 1.05-1.1:1 mixes.
Embodiment 2
Step1. polyaspartate is prepared, code name PAE-b
Amino Terminated polyether(ATPE) JeffamineT-5000 and ethyl maleate are pressed amount of substance than n (-NH
2): n (-C=C-)=1:1 metering.JeffamineT-5000 is added in the reactor being equipped with agitator, heating temperature control device; logical nitrogen is also warmed up to 40 DEG C; drip ethyl maleate; rate of addition be every two seconds one; after dropwising; stirred under nitrogen atmosphere is heated to 80 DEG C, and insulation 24h, cooling discharge is polyaspartate.
Step2. poly aspartic acid ester paint component A is prepared
2,4 '-diphenylmethanediisocyanate MDI-50 and polyoxypropyleneglycol PPG2000 consumption measure by NCO%=15% in the prepolymer that generates.2 are added in the reactor being equipped with agitator, heating temperature control device; 4 '-diphenylmethanediisocyanate MDI-50; logical nitrogen is also warmed up to 40 DEG C; drip polyoxypropyleneglycol PPG2000; logical nitrogen is also warmed up to 40 DEG C; drip polyoxypropyleneglycol PPG2000; rate of addition be every two seconds one; after dropwising; stirred under nitrogen atmosphere is heated to 75 DEG C, and METHOD FOR CONTINUOUS DETERMINATION NCO content, the stopped reaction when NCO mass percent change≤0.05%; the cooling discharging that stirs is Isocyanate prepolymers body, as coating component A.
Step3. surface modification oyster shell whiting is prepared
By waste shell through recovery and rinsing, alkali cleaning 18h, clean water, dry, grind the oyster shell whiting obtained, its median size is 0.1 μm ~ 100 μm.Take the appropriate oyster shell whiting after grinding, by solid-to-liquid ratio 1:10, be added to the water, be warming up to 80 DEG C of constant temperature 30min.The addition of surface-modifying agent aluminate coupling agent is 1.5% of oyster shell whiting quality, is added after dissolving in a small amount of toluene, adds after reacting 30min in the shell slurry of constant temperature, suction filtration, vacuum-drying, and grinding, obtains modified oyster shell whiting.
Step4. anti-fouling biological attachment agent is prepared
(1) preparation of vinylbenzene and acrylic acid copolymer microsphere template
The same with experiment condition described in embodiment 1.
(2) preparation of white vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres
Take white vinylbenzene and acrylic acid copolymer microsphere template 0.4g, with 50mL dehydrated alcohol ultrasonic disperse.In this dispersion liquid, add 1mL water, 0.75mL ammoniacal liquor stirs 10min, then adds 0.6mL tetraethyl orthosilicate, seals bottleneck with preservative film, isothermal reaction 12h at 25 DEG C.Centrifugal, washing, dry vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres.
(3) preparation of zinc oxide/silicon dioxide hollow microsphere
Take 3mmol zinc nitrate hexahydrate and 4.5g vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres and be placed in 250mL round-bottomed flask, add 200mL distilled water, abundant stirring, add Trisodium Citrate 1mmol, ammoniacal liquor 30mL is added after abundant stirring, produce white precipitate in solution and disappear immediately, flask being placed in oil bath pan and being heated to 160 DEG C of stirring and refluxing 12h.By the centrifugation of gained white precipitate, and fully clean with deionized water, zinc oxide/vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres after drying, can be obtained in atmosphere.Finally zinc oxide/vinylbenzene and acrylic acid copolymer microballoon/silica core-shell microspheres are placed in crucible, in air atmosphere, are slowly warming up to 500 DEG C, and are incubated 5h, temperature rise rate is 1 DEG C/min.
(4) silicone Quaternary Ammonium Salt Antimicrobial Agent surface modification zinc oxide/silicon dioxide hollow microsphere
Take appropriate 5g zinc oxide/silicon dioxide hollow microsphere and 2g organosilicon quaternary ammonium salt is dissolved in 100mL deionized water, low speed mixing stirs 3h at normal temperatures, under whipped state, then dropwise adds 0.5mol/L oxalic acid regulate mixing solutions pH to 3.After leaving standstill 24h, supersound washing repeatedly, 100 DEG C of dryings, grinding.
(5) preparation of imidazoline quaternary ammonium salt
A small amount of ceramic particle and 0.18mol diethylenetriamine is added in the there-necked flask being connected with thermometer, spherical condensation tube, agitator, be warmed up to 110 DEG C and add 6.5g calcium oxide as water-removal agent, 0.15mol Witconol 2301 is dropwise added with constant voltage separating funnel, drip off in 30min, be warmed up to 140-150 DEG C, carry out intermolecular amidation dealcoholization 3.5h; Continue stirring and be warming up to 200-210 DEG C, carry out intramolecular cyclization dehydration reaction 3h, obtain imidazoline intermediate; Above-mentioned imidazoline intermediate is cooled to 90-100 DEG C, and the ratio being 1:1.1 in the mol ratio of imidazoline intermediate and Benzyl Chloride drips Benzyl Chloride, constant temperature, stirs quaterisation 3.5h, obtained imidazoline quaternary ammonium salt.
(6) preparation of the modification zinc oxide/silicon dioxide hollow microsphere of antiseptic-germicide is loaded with
Take 0.5g modified zinc oxide/silicon dioxide hollow microsphere, add that 40mL concentration is housed is in the there-necked flask of the imidazoline quaternary ammonium salt of 50mg/mL, decompression is bled 15min, removes the air in flask and zinc oxide/silicon dioxide hollow microsphere.Open funnel stopcock, open Vltrasonic device simultaneously, until the complete submergence zinc oxide/silicon dioxide microsphere of liquid and ultrasonic disperse evenly after, withdraw from reliever, stirring at room temperature 10h.At interval of the ultrasonic 2min of 2h during this stirs.Centrifugal, discard supernatant liquid, hollow microsphere is vacuum-drying 24h at 60 DEG C, obtains anti-fouling biological attachment agent.
Step5. poly aspartic acid ester paint B component is prepared
Take polyaspartate PAE-b60 part of Step1, oyster shell whiting 8 parts, quartz sand 8 parts, titanium dioxide 8 parts, talcum powder 5 parts, anti-halobios adhersion agent 8 parts, auxiliary agent 3 parts, joins successively in scuffing of cylinder bore, high-speed stirring 1h, mixes discharging, as coating B component.
During use by-NCO in component A with the-NH mol ratio in B component for 1.05-1.1:1 mixes.
Embodiment 3
Step1. polyaspartate is prepared, code name PAE-c
Amino Terminated polyether(ATPE) JeffamineT-403 and ethyl maleate are pressed amount of substance than n (-NH
2): n (-C=C-)=1:1 metering.JeffamineT-403 is added in the reactor being equipped with agitator, heating temperature control device; logical nitrogen is also warmed up to 40 DEG C; drip ethyl maleate; rate of addition be every two seconds one; after dropwising; stirred under nitrogen atmosphere is heated to 80 DEG C, and insulation 24h, cooling discharge is polyaspartate.
Step2. poly aspartic acid ester paint component A is prepared
2,4 '-diphenylmethanediisocyanate MDI-50 and polyoxypropyleneglycol PPG2000 consumption measure by NCO%=15% in the prepolymer that generates.2 are added in the reactor being equipped with agitator, heating temperature control device; 4 '-diphenylmethanediisocyanate MDI-50; logical nitrogen is also warmed up to 40 DEG C; drip polyoxypropyleneglycol PPG2000; logical nitrogen is also warmed up to 40 DEG C; drip polyoxypropyleneglycol PPG2000; rate of addition be every two seconds one; after dropwising; stirred under nitrogen atmosphere is heated to 75 DEG C, and METHOD FOR CONTINUOUS DETERMINATION NCO content, the stopped reaction when NCO mass percent change≤0.05%; the cooling discharging that stirs is Isocyanate prepolymers body, as coating component A.
Step3. surface modification oyster shell whiting is prepared
By waste shell through recovery and rinsing, alkali cleaning 12h, clean water, dry, grind the oyster shell whiting obtained, its median size is 0.1 μm ~ 100 μm.Take the appropriate oyster shell whiting after grinding and put into homogenizer, rotating speed is 1500rpm.The mode that the employing of surface-modifying agent aluminate coupling agent is sprayed is added to have in the homogenizer of oyster shell whiting and stirs 15min.Then the mode that same employing is sprayed adds properties-correcting agent sodium stearate and carries out composite modified to shell powder, and churning time is 10min, discharging, dry, obtains product.
Step4. anti-fouling biological attachment agent is prepared
(1) preparation of cetyl trimethylammonium bromide/silica core-shell microspheres
In 250mL there-necked flask, add 15mL ethanol successively, 25 water, 0.5 ammoniacal liquor and 0.08g cetyl trimethylammonium bromide, access 0.5 tetraethyl orthosilicate after 25 stirring and dissolving, and reaction 3h stopped reaction, washing and filtering, dries sample in 120 DEG C.
(2) preparation of zinc oxide/silicon dioxide hollow microsphere
Take 5mmol zinc nitrate hexahydrate and 4.5g cetyl trimethylammonium bromide/silica core-shell microspheres is placed in 250mL round-bottomed flask, add 200mL distilled water, abundant stirring, add Trisodium Citrate 0.5mmol, ammoniacal liquor 50mL is added after abundant stirring, produce white precipitate in solution and disappear immediately, flask being placed in oil bath pan and being heated to 150 DEG C of stirring and refluxing 12h.By the centrifugation of gained white precipitate, and fully clean with deionized water, zinc oxide/cetyl trimethylammonium bromide/silica core-shell microspheres can be obtained after drying in atmosphere.Finally zinc oxide/cetyl trimethylammonium bromide/silica core-shell microspheres is placed in crucible, in air atmosphere, is slowly warming up to 400 DEG C, and is incubated 5h, temperature rise rate is 1 DEG C/min.
(4) silicone Quaternary Ammonium Salt Antimicrobial Agent surface modification zinc oxide/silicon dioxide hollow microsphere
Take appropriate 5g zinc oxide/silicon dioxide hollow microsphere and 1.5g organosilicon quaternary ammonium salt is dissolved in 100mL deionized water, low speed mixing stirs 3h at normal temperatures, under whipped state, then dropwise adds 0.3mol/L oxalic acid regulate mixing solutions pH to 3.After leaving standstill 24h, supersound washing repeatedly, 110 DEG C of dryings, grinding.
(5) preparation of the modification zinc oxide/silicon dioxide hollow microsphere of antiseptic-germicide is loaded with
Take 1.25g modified zinc oxide/silicon dioxide hollow microsphere, add that 50mL concentration is housed is in the there-necked flask of the potassium sorbate of 50mg/mL, decompression is bled 15min, removes the air in flask and zinc oxide/silicon dioxide hollow microsphere.Open funnel stopcock, open Vltrasonic device simultaneously, until the complete submergence zinc oxide/silicon dioxide microsphere of liquid and ultrasonic disperse evenly after, withdraw from reliever, stirring at room temperature 8h.At interval of the ultrasonic 1min of 2h during this stirs.Centrifugal, discard supernatant liquid, hollow microsphere is vacuum-drying 24h at 60 DEG C, obtains anti-fouling biological attachment agent.
Step5. poly aspartic acid ester paint B component is prepared
Take polyaspartate PAE-c55 part of Step1, oyster shell whiting 8 parts, quartz sand 7 parts, talcum powder 7 parts, titanium dioxide 10 parts, anti-halobios adhersion agent 10 parts, auxiliary agent 3 parts, joins successively in scuffing of cylinder bore, high-speed stirring 1h, mixes discharging, as coating B component.
During use by-NCO in component A with the-NH mol ratio in B component for 1.05-1.1:1 mixes.
Comparative example 1
Carbamide paint and organosilicon quaternary ammonium salt are carried out mixing to obtain, wherein organosilicon quaternary ammonium salt accounts for 12% of carbamide paint.
Comparative example 2
Carbamide paint and imidazoline quaternary ammonium salt are carried out mixing to obtain, wherein imidazoline quaternary ammonium salt accounts for 15% of carbamide paint.
Comparative example 3
Carbamide paint and nano zine oxide are carried out mixing to obtain, wherein nano zine oxide accounts for 8% of carbamide paint.
Comparative example 4
Carbamide paint and nano silicon are carried out mixing to obtain, wherein nano silicon accounts for 10% of carbamide paint.
Embodiment 4
Marine microalgae antifouling property is tested
(1) chlorella and Nitzschia closterium minutissima algae liquid are cultivated
Seawater is after glass sand core funnel filters, and scalding, f/2 Algae culture solution is prepared in cooling.Be placed in growth cabinet by algae liquid and cultivate, intensity of illumination is 2500lx.
With 0.45 μm of aperture membrane filtration 1L nature seawater, regulate pH to 8.0 with the HCl solution of NaOH or 1mol/L of 1mol/L.Sterilizing 20min at 121 DEG C, is cooled to room temperature for subsequent use and determine algae liquid concentration-light absorption value curve, according to curve, the algae liquid Algae culture solution of cultivating exponential phase of growth is diluted to 3 × 10
5individual/mL.
Be coated on the sheet glass that specification is 10 × 10 × 0.1cm ± 0.5 by coating to be tested, surface covered is about 90cm
2, naturally dry, for subsequent use.
Test panel is placed on grillage, print is placed in the glass jar filling tested algae liquid, 20 DEG C, soak 7 days under the condition of 3000lx.
(2) model detects: taken out by test panel, with filtering through glass sand core funnel and repeatedly rinsing with the seawater elutriant of 121 sterilizing 20min, the frond of the attachment on model is to the greatest extent all swept away, by the algae liquid constant volume that sweeps away to 25mL, measure OD value and algal control rate by microplate reader, test result refers to table 1.
As can be known from Table 1, embodiment 1 ~ 3 is compared with blank example, comparative example 1 ~ 4, the inhibiting rate of anti-halobios adhersion coating to marine microalgae of embodiment 1 ~ 3 is significantly higher than blank example and comparative example 1 ~ 4, adopt technical scheme of the present invention, substantially increase the inhibiting rate to marine microalgae, serve the effect of good anti-fouling biological attachment.
The various coating of table 1 is to the algal control rate of marine microalgae
Remarks: table empty example is do not add the carbamide paint of antibacterial stain control agent, lower same.
Embodiment 5
Taking Mytilus edulis as biological subject, by calculating the lethality rate of mussel, evaluating the anti-fouling effect of the antibacterial antifouling paint of the present invention.AB is measured component mixing and be sprayed on (sheet glass surrounding glass bar surrounds) on the sheet glass of 100mm × 5mm × 1mm, dry; With seawater flushing several, then dry, for subsequent use.Each test panel evenly places several tested materials, and in about 20 DEG C sea water immersions, oxygenation simultaneously maintains the oxygen level in seawater.Mussel adhesion condition is observed in timing, and experimental result refers to table 2.
As can be known from Table 2, embodiment 1 ~ 3 is compared with blank example, comparative example 1 ~ 4, there is good anti-Mytilus edulis adhesive ability, to the lethality rate of Mytilus edulis up to 100%, adopt the antibacterial antifouling paint of technical scheme of the present invention to have good anti-adhesion effect to Mytilus edulis.
The anti-Mytilus edulis adhesion property of the various coating of table 2
Remarks: table empty example is do not add the carbamide paint of antibacterial stain control agent, lower same.
Embodiment 6
Microbial culture: dilute as matter sample attached with a certain amount of antiseptic sea water, get supernatant liquid, be seeded on the plate culture medium of numbering in advance respectively with coating method, be placed in 25 DEG C of incubators, cultivate 3 ~ 5 days, observe, be separated and purifying, be then inoculated in inclined-plane, glycerine fluid-tight, preserves under low temperature.
Liquid nutrient medium: Chen Haishui 1000ml will be housed, peptone 5g, yeast extract paste 1g, first add in the beaker of ferric sesquichloride 0.11g and be less than the required water yield, stir evenly with glass stick, then heating makes it dissolve, after medicine dissolves completely, make up water to required cumulative volume, then by liquid subpackage in Erlenmeyer flask.
Be coated on the sheet glass that specification is 10 × 10 × 0.1cm ± 0.5 by coating to be tested, surface covered is about 90cm
2, naturally dry, for subsequent use.
The preparation of elutriant: seawater used through glass sand core funnel filter after, 121 sterilizing 20min, for subsequent use.
The preparation of bacteria suspension: get each 1 ring of bacterial classification that inclined-plane is preserved, be inoculated in the liquid nutrient medium of 50ml, 25 DEG C, under 180r/min condition, cultured continuously 6h, chooses the suspension of absorbancy before 0.1 ~ 0.6, for subsequent use.
Indoor link plate method: respectively in 6 glass jars (specification 630 × 370 × 500mm), add 10L antiseptic sea water, and cultivate each 1mL of tested bacteria suspension after 6h, keep temperature 25 DEG C, after cultivating 6h, the sheet glass scribbling coating is put in glass jar, is placed on self-control support, cultured continuously 24h, sheet glass is taken out, with the drip washing of liquid culture based method, constant volume in leacheate and 50mL volumetric flask, survey its OD value thus calculate bacteriostasis rate, result is as shown in table 3.
As shown in Table 3, embodiment 1 ~ 3 is compared with blank example, comparative example 1 ~ 4, and bacteriostasis rate, up to about 90%, has good fungistatic effect.
The bacteriostasis rate of the various coating of table 3
| Project | Blank example | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| R/％ | — | 67.52 | 53.21 | 73.50 | 62.26 | 90.35 | 89.67 | 90.12 |
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. an anti-fouling biological attachment agent, it is characterized in that: described anti-fouling biological attachment agent is the zinc oxide/silicon dioxide hollow microsphere being loaded with antiseptic-germicide of organosilicon quaternary ammonium salt surface modification, it comprises organosilicon quaternary ammonium salt, antiseptic-germicide, zinc oxide/silicon dioxide hollow microsphere, described organosilicon quaternary ammonium salt: antiseptic-germicide: the mass ratio of zinc oxide/silicon dioxide hollow microsphere is (1 ~ 3): (6 ~ 50): 5, the silicon-dioxide in wherein said zinc oxide/silicon dioxide hollow microsphere and the mass ratio of zinc oxide are 5:(0.1 ~ 3).
2. anti-fouling biological attachment agent according to claim 1, it is characterized in that, described organosilicon quaternary ammonium salt: antiseptic-germicide: the mass ratio of zinc oxide/silicon dioxide hollow microsphere is (1.5 ~ 2.5): (10 ~ 40): 5, and wherein in zinc oxide/silicon dioxide hollow microsphere, the mass ratio of silicon-dioxide and zinc oxide is 5:(0.2 ~ 2).
3. anti-fouling biological attachment agent according to claim 1 and 2, is characterized in that: described antiseptic-germicide is at least one in imidazoline quaternary ammonium salt or potassium sorbate.
4. anti-fouling biological attachment agent according to claim 3, is characterized in that: described anti-fouling biological attachment agent adopts following steps preparation:
Step S1: prepare organic template, makes organic template/silica core-shell microspheres;
Step S2: prepare zinc oxide/silicon dioxide hollow microsphere;
Step S3: prepare organosilicon quaternary ammonium salt surface modification zinc oxide/silicon dioxide hollow microsphere;
Step S4: the zinc oxide/silicon dioxide hollow microsphere being loaded with antiseptic-germicide preparing organosilicon quaternary ammonium salt surface modification;
Wherein, described organic template is vinylbenzene and acrylic acid copolymer microballoon or cetyl trimethylammonium bromide.
5. anti-fouling biological attachment agent according to claim 4, it is characterized in that: in step S1, described making organic template/silica core-shell microspheres comprises the following steps: in organic template, add dehydrated alcohol carry out ultrasonic disperse, then tetraethyl orthosilicate is added after adding water and ammoniacal liquor stirring 5 ~ 30min, sealing bottleneck, at 20 ~ 40 DEG C of reaction 3 ~ 15h; Centrifugal, washing, dry.
6. anti-fouling biological attachment agent according to claim 4, it is characterized in that: in step S2, the preparation of described zinc oxide/silicon dioxide hollow microsphere adopts following steps preparation: in the container that distilled water is housed, add organic template/silica core-shell microspheres and soluble zinc salt, Trisodium Citrate is added after stirring, add in ammoniacal liquor to solution when producing precipitation and disappear immediately after abundant stirring, then container is placed in oil bath and is heated to 110 ~ 180 DEG C of stirring and refluxing 3 ~ 12h; By gained precipitation and centrifugal separation, and with obtaining zinc oxide/organic template/silica core-shell microspheres after washed with de-ionized water, drying; Finally by zinc oxide/organic template/silica core-shell microspheres under air atmosphere, be warming up to 400 DEG C ~ 650 DEG C, temperature rise rate is 0.5 ~ 2 DEG C/min, insulation 3 ~ 7h, cooling obtain zinc oxide/silicon dioxide hollow microsphere; Wherein, the mol ratio of described Trisodium Citrate and zinc salt is 1:1.5 ~ 6.
7. anti-fouling biological attachment agent according to claim 6, it is characterized in that: in step S3, the preparation method of described organosilicon quaternary ammonium salt surface modification zinc oxide/silicon dioxide hollow microsphere is: added by zinc oxide/silicon dioxide hollow microsphere in organosilicone quaternary ammonium salts solution, mix and blend 2 ~ 4h under normal temperature, then adjust ph to 3 ~ 4, after leaving standstill 12 ~ 24h, carry out supersound washing, in 80 ~ 120 DEG C of dryings, grinding;
In step S4, the described step being loaded with the zinc oxide/silicon dioxide hollow microsphere of antiseptic-germicide preparing organosilicon quaternary ammonium salt surface modification is: bleed zinc oxide/silicon dioxide hollow microsphere decompression 15 ~ 30min, drip antiseptic-germicide, open Vltrasonic device simultaneously, until the complete submergence zinc oxide/silicon dioxide microsphere of antiseptic-germicide and ultrasonic disperse evenly after, withdraw from reliever, stirred at ambient temperature 7 ~ 9h, and at interval of the ultrasonic 1min of 2h; Centrifugal, to discard after supernatant liquid vacuum-drying 12 ~ 24h at 60 DEG C.
8. an anti-fouling biological attachment coating, is characterized in that: by A, B two component form, wherein the composition that comprises of component A and weight percent thereof are: polyisocyanates 50-70%, polyether glycol 30-50%; The composition that B component comprises and weight percent thereof are: polyaspartate 40-70%, anti-fouling biological attachment agent 1 ~ 15%, pigment 5 ~ 25%, filler 5-25%, auxiliary agent 0.5-5%, wherein, described anti-fouling biological attachment agent is the anti-fouling biological attachment agent as described in claim 1 ~ 7 any one.
9. anti-fouling biological attachment coating according to claim 8, is characterized in that: the composition that described component A comprises and weight percent thereof are: polyisocyanates 50-65%, polyether glycol 35-50%; The composition that B component comprises and weight percent thereof are: polyaspartate 50-65%, anti-fouling biological attachment agent 1 ~ 10%, pigment 5 ~ 20%, filler 5-20%, auxiliary agent 1-5%; Wherein, described auxiliary agent is at least one in defoamer, wetting dispersing agent, flow agent, coupling agent.
10. anti-fouling biological attachment coating according to claim 9, is characterized in that:
Described polyisocyanates is 2, at least one in 4 '-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate; Described polyether glycol is at least one in polyglycol ether, polypropylene glycol ether, polyglycerol ether or PTMG;
Described polyaspartate is that ethyl maleate and primary amine are obtained by Michael addition reaction, and wherein said primary amine is polyoxytrimethylene polyamine or the polyoxyethylene polyamine of two functional groups or trifunctional;
Described filler is at least one in oyster shell whiting, quartz sand powder or talcum powder; Described pigment is titanium dioxide;
Described filler and pigment are adopt surface-modifying agent to carry out surface-treated, and wherein said surface-modifying agent is at least one in stearates, aluminate coupling agent, titanate coupling agent or silane coupling agent;
Described defoamer is silicone based defoamer or calcium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510485615.2A CN105062175B (en) | 2015-08-10 | 2015-08-10 | A kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510485615.2A CN105062175B (en) | 2015-08-10 | 2015-08-10 | A kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105062175A true CN105062175A (en) | 2015-11-18 |
| CN105062175B CN105062175B (en) | 2017-06-16 |
Family
ID=54491711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510485615.2A Active CN105062175B (en) | 2015-08-10 | 2015-08-10 | A kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105062175B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106263908A (en) * | 2016-08-09 | 2017-01-04 | 海宁市现代汽车座套有限公司 | A kind of manufacture method of the pillowcase of wear-resistant antibacterial |
| CN107685042A (en) * | 2017-07-18 | 2018-02-13 | 浦江县协盈动物饲料技术开发有限公司 | A kind of particle drying unit |
| WO2018214619A1 (en) * | 2017-05-26 | 2018-11-29 | 中国船舶重工集团公司第七二五研究所 | Controlled release material for fouling organism-sensitive response anti-fouling agent, and method for manufacturing same |
| CN109535773A (en) * | 2018-12-18 | 2019-03-29 | 浙江大学自贡创新中心 | A kind of preparation method of imidazoline-zinc oxide composite powder |
| CN109549665A (en) * | 2018-11-15 | 2019-04-02 | 青岛海信医疗设备股份有限公司 | A kind of ultrasonic device detection system |
| CN109749616A (en) * | 2018-12-29 | 2019-05-14 | 西安交通大学 | A kind of anti-fouling coating and preparation method thereof that can discharge anti-fouling agent |
| CN110433739A (en) * | 2019-08-26 | 2019-11-12 | 青岛农业大学 | A method of antifouling anti-rotten function microcapsules are prepared based on Pickering lotion |
| CN110528110A (en) * | 2019-09-27 | 2019-12-03 | 浙江正堂实业股份有限公司 | The DTY silk and DTY production technology of staining antibacterial before a kind of spinning |
| CN111205725A (en) * | 2020-01-10 | 2020-05-29 | 佛山市三水伯马絮凝剂厂 | Antifouling material and preparation method thereof |
| CN111286260A (en) * | 2020-04-14 | 2020-06-16 | 烟台恒诺新材料有限公司 | Preparation method of high-light-transmittance thermal-insulation impact-resistant composite material |
| CN111807711A (en) * | 2020-07-24 | 2020-10-23 | 江苏秀强玻璃工艺股份有限公司 | Manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass |
| CN113549343A (en) * | 2021-06-30 | 2021-10-26 | 科迈特新材料有限公司 | Modified nano zinc oxide compound for plastics and preparation method thereof |
| CN114409559A (en) * | 2022-01-07 | 2022-04-29 | 湖南航天三丰科工有限公司 | Preparation method and application of environment-friendly antifouling agent for marine coating |
| WO2023087854A1 (en) * | 2021-11-16 | 2023-05-25 | 哈尔滨工程大学 | Antifouling coating and use method therefor and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09110607A (en) * | 1995-10-19 | 1997-04-28 | Rasa Ind Ltd | Antimicrobial composition and its production |
| CN101352676A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing nano zinc oxide using shell powder as carrier |
| CN102612317A (en) * | 2009-09-15 | 2012-07-25 | 巴斯夫欧洲公司 | Aqueous dispersions containing antimicrobials in a hybrid network |
| CN103572594A (en) * | 2013-11-20 | 2014-02-12 | 苏州大学 | Antibacterial agent containing fluorinated alkyl quaternary ammonium salt, and preparation method and application of antibacterial agent |
| US20140370306A1 (en) * | 2013-06-12 | 2014-12-18 | Samsung Electronics Co., Ltd. | Anti-bacterial and anti-fingerprint coating composition, film comprising the same, method of coating the same and article coated with the same |
-
2015
- 2015-08-10 CN CN201510485615.2A patent/CN105062175B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09110607A (en) * | 1995-10-19 | 1997-04-28 | Rasa Ind Ltd | Antimicrobial composition and its production |
| CN101352676A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing nano zinc oxide using shell powder as carrier |
| CN102612317A (en) * | 2009-09-15 | 2012-07-25 | 巴斯夫欧洲公司 | Aqueous dispersions containing antimicrobials in a hybrid network |
| US20140370306A1 (en) * | 2013-06-12 | 2014-12-18 | Samsung Electronics Co., Ltd. | Anti-bacterial and anti-fingerprint coating composition, film comprising the same, method of coating the same and article coated with the same |
| CN103572594A (en) * | 2013-11-20 | 2014-02-12 | 苏州大学 | Antibacterial agent containing fluorinated alkyl quaternary ammonium salt, and preparation method and application of antibacterial agent |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107119464B (en) * | 2016-08-09 | 2019-04-09 | 杭州宝丝逸家纺有限公司 | The production method of the pillowcase of the wear-resistant antibacterial of improvement |
| CN107119464A (en) * | 2016-08-09 | 2017-09-01 | 海宁市现代汽车座套有限公司 | The preparation method of the pillowcase of the wear-resistant antibacterial of improvement |
| CN106263908A (en) * | 2016-08-09 | 2017-01-04 | 海宁市现代汽车座套有限公司 | A kind of manufacture method of the pillowcase of wear-resistant antibacterial |
| WO2018214619A1 (en) * | 2017-05-26 | 2018-11-29 | 中国船舶重工集团公司第七二五研究所 | Controlled release material for fouling organism-sensitive response anti-fouling agent, and method for manufacturing same |
| US11000034B2 (en) | 2017-05-26 | 2021-05-11 | Luoyang Ship Material Research Institute | Controlled-release material for antifouling agent sensitive and response to fouling organisms and preparation method thereof |
| CN107685042A (en) * | 2017-07-18 | 2018-02-13 | 浦江县协盈动物饲料技术开发有限公司 | A kind of particle drying unit |
| CN109549665B (en) * | 2018-11-15 | 2021-06-22 | 青岛海信医疗设备股份有限公司 | Ultrasonic equipment detection system |
| CN109549665A (en) * | 2018-11-15 | 2019-04-02 | 青岛海信医疗设备股份有限公司 | A kind of ultrasonic device detection system |
| CN109535773B (en) * | 2018-12-18 | 2020-12-11 | 浙江大学自贡创新中心 | Preparation method of imidazoline-zinc oxide composite powder |
| CN109535773A (en) * | 2018-12-18 | 2019-03-29 | 浙江大学自贡创新中心 | A kind of preparation method of imidazoline-zinc oxide composite powder |
| CN109749616A (en) * | 2018-12-29 | 2019-05-14 | 西安交通大学 | A kind of anti-fouling coating and preparation method thereof that can discharge anti-fouling agent |
| CN110433739A (en) * | 2019-08-26 | 2019-11-12 | 青岛农业大学 | A method of antifouling anti-rotten function microcapsules are prepared based on Pickering lotion |
| CN110528110A (en) * | 2019-09-27 | 2019-12-03 | 浙江正堂实业股份有限公司 | The DTY silk and DTY production technology of staining antibacterial before a kind of spinning |
| CN111205725A (en) * | 2020-01-10 | 2020-05-29 | 佛山市三水伯马絮凝剂厂 | Antifouling material and preparation method thereof |
| CN111286260A (en) * | 2020-04-14 | 2020-06-16 | 烟台恒诺新材料有限公司 | Preparation method of high-light-transmittance thermal-insulation impact-resistant composite material |
| CN111286260B (en) * | 2020-04-14 | 2021-11-16 | 烟台恒诺新材料有限公司 | Preparation method of high-light-transmittance thermal-insulation impact-resistant composite material |
| CN111807711A (en) * | 2020-07-24 | 2020-10-23 | 江苏秀强玻璃工艺股份有限公司 | Manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass |
| CN113549343A (en) * | 2021-06-30 | 2021-10-26 | 科迈特新材料有限公司 | Modified nano zinc oxide compound for plastics and preparation method thereof |
| CN113549343B (en) * | 2021-06-30 | 2022-05-27 | 科迈特新材料有限公司 | Modified nano zinc oxide compound for plastics and preparation method thereof |
| WO2023087854A1 (en) * | 2021-11-16 | 2023-05-25 | 哈尔滨工程大学 | Antifouling coating and use method therefor and application thereof |
| CN114409559A (en) * | 2022-01-07 | 2022-04-29 | 湖南航天三丰科工有限公司 | Preparation method and application of environment-friendly antifouling agent for marine coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105062175B (en) | 2017-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105062175B (en) | A kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating | |
| CN105017830B (en) | A kind of antibacterial anti-fouling agent and antibacterial antifouling paint | |
| CN103820995B (en) | The preparation method of the waterproofing agent of organosilicon of reinforced waterproof mildew-resistant | |
| CN107083094A (en) | A kind of microcapsules, its preparation method, bionical antifouling paint and bionical nonpolluting coating | |
| CN101955697A (en) | Ceramic non-stick coating with bacteriostasis action and coating method thereof | |
| CN1322720A (en) | Antibiotic & antifouling oxathiazine and its oxide | |
| ES2853073T3 (en) | Gel particles charged for antifouling compositions | |
| CN101531865B (en) | Method for preparing pollution-proof surface material suitably applied in marine environment | |
| CN111286273A (en) | Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof | |
| CN104479487A (en) | Biological antibacterial and antifouling low surface energy coating with surface micro-structure and preparation method of biological antibacterial and antifouling low surface energy coating | |
| CN108675383A (en) | The method for preventing bacterium algae in water body | |
| CN106797955A (en) | Antifouling algicide of environment-protection nano and preparation method thereof | |
| Xiong et al. | Effect of the properties of long afterglow phosphors on the antifouling performance of silicone fouling-release coating | |
| CN105418972B (en) | A kind of organic antibacterial agent intercalation modifying montmorillonite and its application | |
| Zhao et al. | pH-responsive intelligent antibacterial coatings based on 2D-COF for controlled release of capsaicin | |
| CN112251141B (en) | Graphene modified nano silver-copper-zinc-aluminum composite coating and preparation method and application thereof | |
| CN110358345B (en) | Microcapsule type antifouling agent and preparation method thereof, antifouling coating and preparation method thereof | |
| CN108264645A (en) | A kind of patterning hydrogel anti-fouling material and preparation method thereof | |
| CN109651940A (en) | Aquiculture net cage antifouling paint | |
| CN107446402A (en) | Charge transfer type autoxidation reduced nano material, its preparation method and application and marine antifoulant and marine antifouling coating | |
| CN106189542A (en) | A kind of marine organisms prevent and kill off coating and preparation method thereof | |
| CN111808481B (en) | Monoatomic algae-killing and sterilizing water tank coating and preparation method thereof | |
| CN108047797A (en) | Composite nano materials, its preparation method and application | |
| CN114574046A (en) | Novel biological sound-insulation diatom interior wall coating and preparation method thereof | |
| CN103044351A (en) | N-substituted propylene acyloxy methyl benzisothiazolinone functional monomer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |