CN105062175B - A kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating - Google Patents
A kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating Download PDFInfo
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- CN105062175B CN105062175B CN201510485615.2A CN201510485615A CN105062175B CN 105062175 B CN105062175 B CN 105062175B CN 201510485615 A CN201510485615 A CN 201510485615A CN 105062175 B CN105062175 B CN 105062175B
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- zinc oxide
- silicon dioxide
- quaternary ammonium
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Abstract
The invention provides a kind of anti-fouling biological attachment agent and anti-fouling biological attachment coating, the anti-fouling biological attachment agent is the zinc oxide/silicon dioxide hollow microsphere for being loaded with antiseptic that organosilicon quaternary ammonium salt surface is modified, it includes organosilicon quaternary ammonium salt, antiseptic, zinc oxide/silicon dioxide hollow microsphere, the organosilicon quaternary ammonium salt：Antiseptic：The mass ratio of zinc oxide/silicon dioxide hollow microsphere is（1~3）：（6~50）：5, wherein the silica and the mass ratio of zinc oxide in the zinc oxide/silicon dioxide hollow microsphere are 5:（0.1~3）.Using technical scheme, by the synergy of organo-mineral complexing, the performance of more efficient more permanent antibacterial and anti-halobios adhersion is realized, with good biocompatibility, environment compatibility and safety in utilization.
Description
Technical field
The invention belongs to antifouling paint technical field, more particularly to a kind of anti-fouling biological attachment agent and anti-fouling biology it is attached
Coating.
Background technology
The process utilized with ocean space accelerates, marine concrete structure engineering, such as harbour, breakwater, off-shore airport,
The application such as offshore lighthouse, seabed tunnel and bridge spanning the sea is more and more extensive.Due to long-term immersion, the various biologies in ocean,
Such as attachment of sea grass, shellfish, mollusk, triggers deep layer to destroy by surface damage, causes marine concrete structure to be subject to tight
Being stained for weight, not only causes economic loss, and cause serious harm to marine concrete structure security and durability.
Coating technology is the most frequently used effective guard technology, mainly have studied polyurethane coating series, third both at home and abroad at present
The conventional protective coatings such as olefin(e) acid ester series, chlorinated rubber series, epoxy series and alkyd series.In anti-halobios adhersion coating
What is worked is anti-halobios adhersion agent, and for a long time, maritime concrete is largely antifouling using high pollution, highly toxic organic tin
Coating, International Maritime Organization has prohibitted the use of such anti-fouling agent.As international community is to the growing interest of environmental problem, exploitation
Environmentally friendly marine antifouling coating has more real economy and social effect.
The content of the invention
For above technical problem, applied the invention discloses a kind of anti-fouling biological attachment agent and anti-fouling biological attachment
Material, by the compound synergy of organic material and inorganic material, realizes more efficient more permanent antibacterial and anti-halobios adhersion
Performance, with good biocompatibility, environment compatibility and safety in utilization.
In this regard, the technical solution adopted by the present invention is：
A kind of anti-fouling biological attachment agent, the anti-fouling biological attachment agent is that organosilicon quaternary ammonium salt surface is modified to be loaded with
Zinc oxide/the silicon dioxide hollow microsphere of antiseptic, it includes organosilicon quaternary ammonium salt, antiseptic, zinc oxide/hollow silica
Microballoon, the organosilicon quaternary ammonium salt：Antiseptic：The mass ratio of zinc oxide/silicon dioxide hollow microsphere is (1~3)：(6~50)：
5, wherein the silica and the mass ratio of zinc oxide in the zinc oxide/silicon dioxide hollow microsphere are 5:(0.1~3).
Zinc oxide is one of earliest metal oxide for antibacterial, with good biocompatibility, environmental harmony
Property and safety in utilization.Nano zine oxide has that particle diameter is small, specific surface area big, surface atom number is more, Atomic coordinate is not enough and height
Surface can the features such as, compared with organic antibacterial agent, with wide spectrum, it is lasting, safe and nontoxic the characteristics of.
The duct rule that hollow mesoporous silicon oxide has had mesoporous silicon oxide concurrently is big with the load capacity of hollow material.Simultaneously
The cavity size and thickness of hollow hole Jie's silica are adjustable, can be by changing the result of hollow silica come regulating drug
Useful load and rate of release, the characteristics of so as to possess medicament slow release.
Organosilicon quaternary ammonium salt is cationic surfactant, with high temperature resistant, water-fastness, lasting effect, scope of restraining fungi
Wide and effectively antibacterial the characteristics of；And cheap, antibacterial speed is fast, practicality is stronger, due to its have good killing bacterium,
The microbial actions such as algae.
Using technical scheme, organosilicon quaternary ammonium salt can play a part of surface modified zinc oxide, make both
Common synergy is played, its antibacterial anti-halobios adhersion performance in coating is improved.Silicon dioxide microsphere have specific surface area it is big,
Hole is uniform, the porosity is high and with certain porosity, has stronger energy of adsorption to macromolecular organic compound and bacterium
Power, while have certain adsorptivity to nano inoganic particle, because its hollow structure possesses certain carried medicine sustained-release performance, by it
Combined with organosilicon quaternary ammonium salt and zinc oxide, can preferably be strengthened the antifouling effect of antibacterial.In addition, with hollow nano silicon
Used as internal layer, may also operate as enhancing zinc oxide shell makes it be difficult the effect caved in.Therefore, technical scheme passes through
The synergy of Organic-inorganic composite so that the anti-fouling biological attachment agent can effectively prevent algae to be stained life with other
The attachment of thing, improves antibacterial scavenging effect, so as to realize the performance of more efficient permanent antibacterial anti-halobios adhersion.
It is further preferred that the zinc oxide is nano zine oxide.Nano zine oxide has that particle diameter is small, specific surface area big,
Surface atom number is more, Atomic coordinate is not enough and surface high can the features such as, compared with organic antibacterial agent, with wide spectrum, persistently, peace
Entirely, nontoxic the characteristics of.
It is further preferred that the silica is nano silicon.Nano silica microsphere has specific surface area
Greatly, with the performance of more efficient permanent antibacterial anti-halobios adhersion.
As a further improvement on the present invention, the organosilicon quaternary ammonium salt：Antiseptic：Zinc oxide/hollow silica is micro-
The mass ratio of ball is (1.5~2.5)：(10~40)：5, silica and oxidation wherein in zinc oxide/silicon dioxide hollow microsphere
The mass ratio of zinc is 5:(0.2~2).
As a further improvement on the present invention, the antiseptic is at least in imidazoline quaternary ammonium salt or potassium sorbate
Kind.In this technical scheme, the imidazoline quaternary ammonium salt in addition to possessing certain antibacterial properties, also to the metal of marine ship etc.
Play the performance of inhibition in surface.
As a further improvement on the present invention, the anti-fouling biological attachment agent is prepared using following steps：
Step S1：Prepare organic template, make organic template/silica core-shell microspheres；
Step S2：Prepare zinc oxide/silicon dioxide hollow microsphere；
Step S3：Prepare organosilicon quaternary ammonium salt surface modified zinc oxide/silicon dioxide hollow microsphere；
Step S4：Prepare the modified zinc oxide/silicon dioxide hollow microsphere for being loaded with antiseptic in organosilicon quaternary ammonium salt surface；
Wherein, the organic template is styrene and acrylic acid copolymer microballoon or cetyl trimethylammonium bromide.
As a further improvement on the present invention, the organic template is styrene and acrylic acid copolymer microballoon, its making
Step is：Equipped with N2Oxygen scavenging container in add ethanol, polyethylene pyrrole network alkanone, acrylic acid and be dissolved with the isobutyl of azo two
The styrene of nitrile, stirs into homogeneous system；60~80 DEG C are then heated to, 24~36h of isothermal reaction obtains polymerized emulsion；Again will
Polymerized emulsion is centrifuged, and abandoning supernatant is washed, dried, being dried to obtain styrene and acrylic acid copolymer microballoon.
As a further improvement on the present invention, in step S1, the making organic template/silica core-shell microspheres bag
Include following steps：In organic template add absolute ethyl alcohol carry out ultrasonic disperse, be subsequently adding water and ammoniacal liquor stirring 5~
Tetraethyl orthosilicate is added after 30min, bottleneck is sealed, 3~15h is reacted at 20~40 DEG C；It is centrifuged, wash, dries.
As a further improvement on the present invention, in step S2, the preparation of the zinc oxide/silicon dioxide hollow microsphere is used
It is prepared by following steps：Organic template/silica core-shell microspheres and soluble zinc salt are added in the container equipped with distilled water,
Sodium citrate is added after stirring, when generation is precipitated and disappeared immediately in addition ammoniacal liquor to solution after being sufficiently stirred for, then container is put
110~180 DEG C are heated in oil bath and are stirred at reflux 3~12h；By gained precipitation and centrifugal separation, and cleaned with deionized water, done
Zinc oxide/organic template/silica core-shell microspheres are obtained after dry；Finally by zinc oxide/organic template/silica core
In under air atmosphere, being warming up to 400 DEG C~650 DEG C, heating rate is 0.5~2 DEG C/min to shell microballoon, is incubated 3~7h, is cooled down
To zinc oxide/silicon dioxide hollow microsphere；Wherein, the sodium citrate and the mol ratio of zinc salt are 1:1.5~6.
Preferably, the concentration of the soluble zinc salt is 0.01~0.05mol/L.
As a further improvement on the present invention, in step S3, the organosilicon quaternary ammonium salt surface modified zinc oxide/titanium dioxide
The preparation method of silicon hollow microsphere is：During zinc oxide/silicon dioxide hollow microsphere added into organosilicone quaternary ammonium salting liquid, under normal temperature
2~4h is mixed, pH value to 3~4 is then adjusted, after standing 12~24h, supersound washing is carried out, in 80~120 DEG C of dryings,
Grinding.
Preferably, careless acid for adjusting pH value is added dropwise under stirring；It is further preferred that the concentration of oxalic acid is
0.1~2mol/L.
As a further improvement on the present invention, in step S4, it is described prepare organosilicon quaternary ammonium salt surface it is modified be loaded with it is anti-
The step of zinc oxide/silicon dioxide hollow microsphere of microbial inoculum is：By zinc oxide/silicon dioxide hollow microsphere decompression pumping 15~
30min, is added dropwise antiseptic, while opening Vltrasonic device, treats that antiseptic is totally submerged zinc oxide/silicon dioxide microsphere and ultrasound point
After dissipating uniformly, decompressor is withdrawn from, 7~9h is stirred at room temperature, and at interval of 2h ultrasounds 1min；Centrifugation, after discarding supernatant liquor
12~24h is vacuum dried at 60 DEG C.Preferably, the concentration of the antiseptic is 0.03g/mL~0.5g/mL.
Preferably, the antiseptic is imidazoline quaternary ammonium salt；The imidazoline quaternary ammonium salt is modified by imidazoline intermediate
It is obtained, comprises the following steps：
Step A：Catalyst and deicer are added in the mixture of organic acid esters and organic amine, dealcoholization is carried out, so
After carry out intramolecular cyclization dehydration and obtain imidazoline intermediate；The organic acid esters is 1 with the mol ratio of organic amine:(1~
1.3)；The reaction temperature of the intermolecular dealcoholization is 120~160 DEG C, 2~5h of reaction time；The intramolecular cyclization takes off
The reaction temperature of water reaction is 180~230 DEG C, 3~6h of reaction time；
Wherein, the organic acid esters is at least in the saturation stearate of C12~C18 or the carboxylate of C12~C18
Kind；
The organic amine is at least in diethylenetriamine, triethylene tetramine, TEPA or AEEA
Kind；
The catalyst is the one kind in activated alumina, boric acid or zinc granule；
The deicer is calcium oxide；
Step B：Water-soluble modified dose is added in the imidazoline intermediate for obtaining in step and is well mixed, 90~
2~5h of isothermal reaction is carried out under 110 DEG C of environment, imidazoline quaternary ammonium salt is obtained；Wherein, the imidazoline intermediate changes with water solubility
Property agent mol ratio be 1:(1~1.1)；Described water-soluble modified dose in benzyl chloride, sodium chloroacetate, monoxone or glacial acetic acid
It is at least one.
Present invention also offers a kind of anti-fouling biological attachment coating, the anti-fouling biological attachment coating is by two groups of A, B
It is grouped into, wherein, the component and its percentage by weight that component A includes are：Polyisocyanates 50-70%, PPG 30-
50%, the component and its percentage by weight that B component includes be：Polyaspartate 40-70%, anti-fouling biological attachment agent 1~
15%, pigment 5~25%, filler 5-25%, auxiliary agent 0.5-5%,；Wherein, the anti-fouling biological attachment agent is as described above
Anti-fouling biological attachment agent.
As a further improvement on the present invention, the anti-fouling biological attachment coating includes component and its percentage by weight
For：Polyisocyanates 50-65%, PPG 35-50%；Polyaspartate 55-65%, anti-fouling biological attachment agent 1
~10%, pigment 5~20%, filler 5-20%, auxiliary agent 1-5%.
Wherein, the auxiliary agent is at least one in wetting dispersing agent, coupling agent, levelling agent and defoamer.
As a further improvement on the present invention, the polyisocyanates is 2,4 '-methyl diphenylene diisocyanate, different Buddhist
At least one in your ketone diisocyanate, hexamethylene diisocyanate, the PPG is polypropylene glycol ether or poly-
At least one in tetrahydrofuran ether.
Preferably, the polyaspartate is obtained for diethyl maleate with primary amine by Michael addition reactions, its
Described in primary amine be two functional groups or trifunctional PPOX polyamine or polyethylene glycol oxide polyamine.
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, the pigment is titanium dioxide.
As a further improvement on the present invention, described filler and/or filler are to be surface-treated using surface modifier
Cross；The surface modifier be stearates, aluminate coupling agent, titanate coupling agent, silane coupler at least
It is a kind of.
The defoamer is organic silicon defoamer or calcium oxide.
The anti-fouling biological attachment agent that technical scheme is used is being loaded with that organosilicon quaternary ammonium salt surface is modified
Zinc oxide/the silicon dioxide hollow microsphere of antiseptic.Wherein, organosilicon quaternary ammonium salt is cationic surfactant, with resistance to height
Warm, water-fastness, lasting effect, the characteristics of scope of restraining fungi is wide and effectively antibacterial；Zinc oxide is the earliest metal for antibacterial
One of oxide, with good biocompatibility, environment compatibility and safety in utilization.Nano zine oxide have particle diameter it is small,
Specific surface area is big, surface atom number is more, Atomic coordinate is not enough and the features such as surface energy high, compared with organic antibacterial agent, has
Wide spectrum, it is lasting, safe and nontoxic the characteristics of.
Compared with prior art, beneficial effects of the present invention are：
First, zinc oxide, silica, organosilicon quaternary ammonium salt, antiseptic possess good killing bacterium, algae etc. in itself
The performance of microorganism, using technical scheme, antiseptic is loaded by zinc oxide/silicon dioxide hollow microsphere,
Then in conjunction with organosilicon quaternary ammonium salt, the synergy of Organic-inorganic composite is reached, realize more efficient more permanent antibacterial and anti-life
The performance of thing attachment, with good biocompatibility, environment compatibility and safety in utilization.
Second, using technical scheme so that coating surface can be very low, marine organisms can be effectively prevented mixed
The attachment on solidifying soil surface, plays lasting long-acting and anti-fouling effect.
3rd, using technical scheme, corrosive ion in seawater, seawater etc. can be prevented to concrete knot
The erosion of structure, realizes the permanent protection to maritime concrete, extends its service life.
Brief description of the drawings
Fig. 1 is the structural representation of the anti-fouling biological attachment agent described in an embodiment of the present invention.
Marked in figure：1- silica, 2- zinc oxide, 3- organosilicon quaternary ammonium salts, 4- imidazoline quaternary ammonium salts.
Specific embodiment
Below in conjunction with the accompanying drawings, preferably embodiment of the invention is described in further detail.
Embodiment 1
Step1. polyaspartate, code name PAE-a are prepared
Amine terminated polyether JeffamineD-2000 and diethyl maleate are pressed into the amount of material than n (- NH2)：N (- C=
C -)=1:1 metering.JeffamineD-2000 is added in agitator, the reactor of heating temperature control device is equipped with, logical nitrogen is simultaneously
40 DEG C are warmed up to, diethyl maleate is added dropwise, rate of addition is every two seconds drops, and after completion of dropping, stirred under nitrogen atmosphere adds
Heat is incubated 24h to 80 DEG C, and cooling discharge is polyaspartate.
Step2. poly-aspartate ester paint component A is prepared
By 2,4 '-methyl diphenylene diisocyanate MDI-50 and polyoxypropyleneglycol PPG2000 consumptions by generation
NCO%=15% meterings in prepolymer.2,4 '-diphenylmethyl is added in agitator, the reactor of heating temperature control device is equipped with
Alkane diisocyanate MDI-50, logical nitrogen is simultaneously warmed up to 40 DEG C, and polyoxypropyleneglycol PPG2000 is added dropwise, and rate of addition is every
Drip within two seconds one, after completion of dropping, stirred under nitrogen atmosphere is heated to 75 DEG C, and METHOD FOR CONTINUOUS DETERMINATION NCO content, when NCO mass percentages
Stop reaction during number change≤0.05%, cooling stirs discharging for Isocyanate prepolymers body, used as coating component A.
Step3. the modified oyster shell whiting in surface is prepared
The recovered cleaning of waste shell, alkali cleaning 24h, clear water cleaning are dried, the oyster shell whiting that grinding is obtained, its average grain
Footpath is 0.1 μm~100 μm.The appropriate oyster shell whiting after grinding is weighed, is 1 by solid-to-liquid ratio:10, it is added into water, it is warming up to 90
DEG C constant temperature 30min obtains shell slurry；The addition of surface modifier odium stearate is the 1% of oyster shell whiting quality, is added into
After being dissolved in a small amount of hot water, after reacting 30min in the shell slurry of addition constant temperature, suction filtration is dried, and grinding obtains modified
Oyster shell whiting.
Step4. anti-fouling biological attachment agent is prepared
(1) preparation of styrene and acrylic acid copolymer microsphere template
In 250mL there-necked flasks, 100mL absolute ethyl alcohols, 1.25g polyethylene pyrrole network alkanones, 0.5mL propylene are sequentially added
Styrene 28mL that is sour and being dissolved with 0.30g azodiisobutyronitriles, stirring makes to form homogeneous system.It is passed through N in advance2Deoxygenation
30min, is then brought rapidly up to 70 DEG C, isothermal reaction 24h.And polymerized emulsion is centrifuged, abandoning supernatant.Washed with ethanol
After several times, dry naturally at room temperature, be subsequently placed under infrared lamp and thoroughly dry, obtain final product white styrene and acrylic acid copolymer is micro-
Ball powder.
(2) preparation of white styrene and acrylic acid copolymer microballoon/silica core-shell microspheres
White styrene and acrylic acid copolymer microsphere template 0.4g are weighed, with 20mL absolute ethyl alcohol ultrasonic disperses.To this point
0.4mL water, 0.4mL ammoniacal liquor stirring 5min is added to be subsequently adding 0.6mL tetraethyl orthosilicates, use preservative film air-tight bottle in dispersion liquid
Mouthful, the isothermal reaction 8h at 30 DEG C.Centrifugation, washing, dry styrene and acrylic acid copolymer microballoon/silica core-shell are micro-
Ball.
(3) preparation of zinc oxide/silicon dioxide hollow microsphere
3mmol zinc nitrate hexahydrates are weighed to be placed in 4.5g styrene and acrylic acid copolymer microballoon/silica core-shell microspheres
In 250mL round-bottomed flasks, 200mL distilled water is added, be sufficiently stirred for, add sodium citrate 0.5mmol, be sufficiently stirred for rear ammonification water
30mL, produces in solution and white precipitate and disappears immediately, flask is placed in oil bath pan and is heated to 120 DEG C and is stirred at reflux.By institute
White precipitate centrifugation is obtained, and is fully cleaned with deionized water, zinc oxide/styrene and propylene can be obtained after drying in atmosphere
Sour copolymerization microsphere/silica core-shell microspheres.Finally by zinc oxide/styrene and acrylic acid copolymer microballoon/silica core-shell
Microballoon is placed in crucible, in air atmosphere, is to slowly warm up to 400 DEG C, and is incubated 5h, and heating rate is 1 DEG C/min.
(4) silicone Quaternary Ammonium Salt Antimicrobial Agent surface modified zinc oxide/silicon dioxide hollow microsphere
Weigh appropriate 5g zinc oxide/silicon dioxide hollow microsphere and be dissolved in 100mL deionizations with 1g organosilicon quaternary ammonium salts
In water, then the 3h of mixed on low speed stirring at normal temperatures is added dropwise over 1mol/L oxalic acid regulation mixed solution pH under stirring
To 3.After standing 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 are added in the there-necked flask of thermometer, spherical condensation tube, agitator is connected with
TEPA, is warmed up to 110 DEG C and adds 6.5g calcium oxide as deicer, and the 0.1mol months are added dropwise over constant pressure separatory funnel
Cinnamic acid ester, drips off in 30 minutes, is warmed up to 150-160 DEG C, carries out intermolecular amidatioon dealcoholization 5h；Continue stirring to be warming up to
210-220 DEG C, intramolecular cyclization dehydration 5h is carried out, obtain final product imidazoline intermediate；Above-mentioned imidazoline intermediate is cooled to
90-100 DEG C, be 1 by the mol ratio of imidazoline intermediate and sodium chloroacetate:1.1 ratio is added dropwise sodium chloroacetate, constant temperature stir into
Row quaterisation 5h, is obtained imidazoline quaternary ammonium salt.
(6) it is loaded with the preparation of the modified zinc oxide/silicon dioxide hollow microsphere of antiseptic
0.5g modified zinc oxides/silicon dioxide hollow microsphere is weighed, the imidazoline for 40mg/mL equipped with 40mL concentration is added
In the there-necked flask of quaternary ammonium salt, decompression pumping 15min, the air in removal flask and zinc oxide/silicon dioxide hollow microsphere.Beat
Funnel stopcock is opened, while opening Vltrasonic device, treats that liquid is totally submerged zinc oxide/silicon dioxide microsphere and ultrasonic disperse is uniform
Afterwards, decompressor is withdrawn from, 8h is stirred at room temperature.At interval of 2h ultrasounds 1min during stirring herein.Centrifugation, discards supernatant liquor, in
Empty microballoon is vacuum dried 24h at 60 DEG C, obtains anti-fouling biological attachment agent.As shown in figure 1, the anti-fouling biological attachment agent
It is the hollow microsphere of the silica 1 of zinc oxide 2/ for being loaded with imidazoline quaternary ammonium salt 4 that the surface of organosilicon quaternary ammonium salt 3 is modified, wherein,
The imidazoline quaternary ammonium salt 4 is carried in the hollow core of the hollow microsphere of the silica 1 of zinc oxide 2/, and organosilicon quaternary ammonium salt 3 exists
The surface of the hollow microsphere of the silica 1 of zinc oxide 2/.
Step5. poly-aspartate ester paint B component is prepared
65 parts of the polyaspartate PAE-a of Step1 is weighed, 10 parts of oyster shell whiting, 10 parts of titanium dioxide, 8 parts of talcum powder is prevented
5 parts of biological attachment agent, 2 parts of auxiliary agent, is added sequentially in scuffing of cylinder bore, high-speed stirred 1h, discharging is well mixed, as coating B component.
By-NH the mol ratios in-NCO in component A and B component it is 1.05-1.1 when using:1 is mixed.
Embodiment 2
Step1. polyaspartate, code name PAE-b are prepared
Amine terminated polyether Jeffamine T-5000 and diethyl maleate are pressed into the amount of material than n (- NH2)：n(—C
=C -)=1:1 metering.Jeffamine T-5000 are added in agitator, the reactor of heating temperature control device is equipped with, leads to nitrogen
Gas is simultaneously warmed up to 40 DEG C, and diethyl maleate is added dropwise, and rate of addition is every two seconds drops, after completion of dropping, is stirred under nitrogen protection
Mix and be heated to 80 DEG C, be incubated 24h, cooling discharge is polyaspartate.
Step2. poly-aspartate ester paint component A is prepared
2,4 '-methyl diphenylene diisocyanate MDI-50 and polyoxypropyleneglycol PPG2000 consumptions are pre- by generation
NCO%=15% meterings in polymers.2,4 '-diphenyl methane is added in agitator, the reactor of heating temperature control device is equipped with
Diisocyanate MDI-50, logical nitrogen is simultaneously warmed up to 40 DEG C, and polyoxypropyleneglycol PPG2000 is added dropwise, and logical nitrogen is simultaneously warmed up to
40 DEG C, polyoxypropyleneglycol PPG2000 is added dropwise, rate of addition is every two seconds drops, after completion of dropping, stirred under nitrogen atmosphere
75 DEG C, and METHOD FOR CONTINUOUS DETERMINATION NCO content are heated to, reaction is stopped when NCO mass percents change≤0.05%, cooling stirring is equal
Even discharging is Isocyanate prepolymers body, used as coating component A.
Step3. the modified oyster shell whiting in surface is prepared
The recovered cleaning of waste shell, alkali cleaning 18h, clear water cleaning are dried, the oyster shell whiting that grinding is obtained, its average grain
Footpath is 0.1 μm~100 μm.The appropriate oyster shell whiting after grinding is weighed, by solid-to-liquid ratio 1:10, it is added into water, it is warming up to 80 DEG C
Constant temperature 30min.The addition of surface modifier aluminate coupling agent is the 1.5% of oyster shell whiting quality, is added into a small amount of toluene
After middle dissolving, after reacting 30min in the shell slurry of addition constant temperature, suction filtration, vacuum drying, grinding obtains modified shell
Powder.
Step4. anti-fouling biological attachment agent is prepared
(1) preparation of styrene and acrylic acid copolymer microsphere template
It is the same with experiment condition described in embodiment 1.
(2) preparation of white styrene and acrylic acid copolymer microballoon/silica core-shell microspheres
White styrene and acrylic acid copolymer microsphere template 0.4g are weighed, with 50mL absolute ethyl alcohol ultrasonic disperses.To this point
1mL water, 0.75mL ammoniacal liquor stirring 10min is added to be subsequently adding 0.6mL tetraethyl orthosilicates, use preservative film air-tight bottle in dispersion liquid
Mouthful, the isothermal reaction 12h at 25 DEG C.Centrifugation, washing, dry styrene and acrylic acid copolymer microballoon/silica core-shell are micro-
Ball.
(3) preparation of zinc oxide/silicon dioxide hollow microsphere
3mmol zinc nitrate hexahydrates are weighed to be placed in 4.5g styrene and acrylic acid copolymer microballoon/silica core-shell microspheres
In 250mL round-bottomed flasks, 200mL distilled water is added, be sufficiently stirred for, add sodium citrate 1mmol, be sufficiently stirred for rear ammonification water
30mL, produces in solution and white precipitate and disappears immediately, flask is placed in oil bath pan and is heated to 160 DEG C and is stirred at reflux 12h.Will
Gained white precipitate centrifugation, and fully cleaned with deionized water, can obtain zinc oxide/styrene and third after drying in atmosphere
Olefin(e) acid copolymerization microsphere/silica core-shell microspheres.Finally by zinc oxide/styrene and acrylic acid copolymer microballoon/silica core
Shell microballoon is placed in crucible, in air atmosphere, is to slowly warm up to 500 DEG C, and is incubated 5h, and heating rate is 1 DEG C/min.
(4) silicone Quaternary Ammonium Salt Antimicrobial Agent surface modified zinc oxide/silicon dioxide hollow microsphere
Weigh appropriate 5g zinc oxide/silicon dioxide hollow microsphere and be dissolved in 100mL deionizations with 2g organosilicon quaternary ammonium salts
In water, then the 3h of mixed on low speed stirring at normal temperatures is added dropwise over 0.5mol/L oxalic acid regulation mixed solution under stirring
PH to 3.After standing 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 are added in the there-necked flask of thermometer, spherical condensation tube, agitator is connected with
Diethylenetriamine, is warmed up to 110 DEG C and adds 6.5g calcium oxide as deicer, and 0.15mol is added dropwise over constant pressure separatory funnel
Methyl oleate, drips off in 30min, is warmed up to 140-150 DEG C, carries out intermolecular amidatioon dealcoholization 3.5h；Continue to stir and rise
Temperature carries out intramolecular cyclization dehydration 3h to 200-210 DEG C, obtains final product imidazoline intermediate；Above-mentioned imidazoline intermediate is cold
But it is 1 by the mol ratio of imidazoline intermediate and benzyl chloride to 90-100 DEG C:1.1 ratio is added dropwise benzyl chloride, constant temperature, stirring
Quaterisation 3.5h, is obtained imidazoline quaternary ammonium salt.
(6) it is loaded with the preparation of the modified zinc oxide/silicon dioxide hollow microsphere of antiseptic
0.5g modified zinc oxides/silicon dioxide hollow microsphere is weighed, the imidazoline for 50mg/mL equipped with 40mL concentration is added
In the there-necked flask of quaternary ammonium salt, decompression pumping 15min, the air in removal flask and zinc oxide/silicon dioxide hollow microsphere.Beat
Funnel stopcock is opened, while opening Vltrasonic device, treats that liquid is totally submerged zinc oxide/silicon dioxide microsphere and ultrasonic disperse is uniform
Afterwards, decompressor is withdrawn from, 10h is stirred at room temperature.At interval of 2h ultrasounds 2min during stirring herein.Centrifugation, discards supernatant liquor, in
Empty microballoon is vacuum dried 24h at 60 DEG C, obtains anti-fouling biological attachment agent.
Step5. poly-aspartate ester paint B component is prepared
Weigh 60 parts of the polyaspartate PAE-b of Step1,8 parts of oyster shell whiting, 8 parts of quartz sand, 8 parts of titanium dioxide, talcum
5 parts of powder, 8 parts of anti-halobios adhersion agent, 3 parts of auxiliary agent is added sequentially in scuffing of cylinder bore, high-speed stirred 1h, discharging is well mixed, as painting
Material B component.
By-NH the mol ratios in-NCO in component A and B component it is 1.05-1.1 when using:1 is mixed.
Embodiment 3
Step1. polyaspartate, code name PAE-c are prepared
Amine terminated polyether Jeffamine T-403 and diethyl maleate are pressed into the amount of material than n (- NH2)：N (- C=
C -)=1:1 metering.Jeffamine T-403 are added in agitator, the reactor of heating temperature control device is equipped with, logical nitrogen is simultaneously
40 DEG C are warmed up to, diethyl maleate is added dropwise, rate of addition is every two seconds drops, and after completion of dropping, stirred under nitrogen atmosphere adds
Heat is incubated 24h to 80 DEG C, and cooling discharge is polyaspartate.
Step2. poly-aspartate ester paint component A is prepared
2,4 '-methyl diphenylene diisocyanate MDI-50 and polyoxypropyleneglycol PPG2000 consumptions are pre- by generation
NCO%=15% meterings in polymers.2,4 '-diphenyl methane is added in agitator, the reactor of heating temperature control device is equipped with
Diisocyanate MDI-50, logical nitrogen is simultaneously warmed up to 40 DEG C, and polyoxypropyleneglycol PPG2000 is added dropwise, and logical nitrogen is simultaneously warmed up to
40 DEG C, polyoxypropyleneglycol PPG2000 is added dropwise, rate of addition is every two seconds drops, after completion of dropping, stirred under nitrogen atmosphere
75 DEG C, and METHOD FOR CONTINUOUS DETERMINATION NCO content are heated to, reaction is stopped when NCO mass percents change≤0.05%, cooling stirring is equal
Even discharging is Isocyanate prepolymers body, used as coating component A.
Step3. the modified oyster shell whiting in surface is prepared
The recovered cleaning of waste shell, alkali cleaning 12h, clear water cleaning are dried, the oyster shell whiting that grinding is obtained, its average grain
Footpath is 0.1 μm~100 μm.Weigh the appropriate oyster shell whiting after grinding to be put into homogenizer, rotating speed is 1500rpm.By surface
Modifying agent aluminate coupling agent using sprinkling by the way of add oyster shell whiting homogenizer in stir 15min.Then it is same
Modifying agent odium stearate is added to carry out shell powder by the way of sprinkling composite modified, mixing time is 10min, discharging,
Dry, obtain final product product.
Step4. anti-fouling biological attachment agent is prepared
(1) preparation of cetyl trimethylammonium bromide/silica core-shell microspheres
To sequentially adding 15mL ethanol, 25 water, 0.5 ammoniacal liquor and 0.08g cetyl trimethyl bromines in 250mL there-necked flasks
Change ammonium, 0.5 tetraethyl orthosilicate is accessed after 25 stirring and dissolvings, reaction 3h stops reaction, and washing and filtering dries sample in 120 DEG C.
(2) preparation of zinc oxide/silicon dioxide hollow microsphere
5mmol zinc nitrate hexahydrates are weighed to be placed in 4.5g cetyl trimethylammonium bromides/silica core-shell microspheres
In 250mL round-bottomed flasks, 200mL distilled water is added, be sufficiently stirred for, add sodium citrate 0.5mmol, be sufficiently stirred for rear ammonification water
50mL, produces in solution and white precipitate and disappears immediately, flask is placed in oil bath pan and is heated to 150 DEG C and is stirred at reflux 12h.Will
Gained white precipitate centrifugation, and fully cleaned with deionized water, can obtain zinc oxide/cetyl three after drying in atmosphere
Methyl bromide ammonium/silica core-shell microspheres.It is finally that zinc oxide/cetyl trimethylammonium bromide/silica core-shell is micro-
Ball is placed in crucible, in air atmosphere, is to slowly warm up to 400 DEG C, and is incubated 5h, and heating rate is 1 DEG C/min.
(4) silicone Quaternary Ammonium Salt Antimicrobial Agent surface modified zinc oxide/silicon dioxide hollow microsphere
Weigh appropriate 5g zinc oxide/silicon dioxide hollow microsphere and 1.5g organosilicon quaternary ammonium salts be dissolved in 100mL go from
In sub- water, then the 3h of mixed on low speed stirring at normal temperatures is added dropwise over the regulation mixing of 0.3mol/L oxalic acid molten under stirring
Liquid pH to 3.After standing 24h, supersound washing repeatedly, 110 DEG C of dryings, grinding.
(5) it is loaded with the preparation of the modified zinc oxide/silicon dioxide hollow microsphere of antiseptic
1.25g modified zinc oxides/silicon dioxide hollow microsphere is weighed, the sorb for 50mg/mL equipped with 50mL concentration is added
In the there-necked flask of sour potassium, decompression pumping 15min, the air in removal flask and zinc oxide/silicon dioxide hollow microsphere.Open
Funnel stopcock, at the same open Vltrasonic device, after liquid be totally submerged zinc oxide/silicon dioxide microsphere and ultrasonic disperse it is uniform after,
Decompressor is withdrawn from, 8h is stirred at room temperature.At interval of 2h ultrasounds 1min during stirring herein.Centrifugation, discards supernatant liquor, hollow micro-
Ball is vacuum dried 24h at 60 DEG C, obtains anti-fouling biological attachment agent.
Step5. poly-aspartate ester paint B component is prepared
Weigh 55 parts of the polyaspartate PAE-c of Step1,8 parts of oyster shell whiting, 7 parts of quartz sand, 7 parts of talcum powder, titanium white
10 parts of powder, 10 parts of anti-halobios adhersion agent, 3 parts of auxiliary agent is added sequentially in scuffing of cylinder bore, high-speed stirred 1h, is well mixed discharging, as
Coating B component.
By-NH the mol ratios in-NCO in component A and B component it is 1.05-1.1 when using:1 is mixed.
Comparative example 1
Carbamide paint and organosilicon quaternary ammonium salt are mixed to prepare, wherein organosilicon quaternary ammonium salt accounts for carbamide paint
12%.
Comparative example 2
Carbamide paint and imidazoline quaternary ammonium salt are mixed to prepare, wherein imidazoline quaternary ammonium salt accounts for carbamide paint
15%.
Comparative example 3
Carbamide paint and nano zine oxide are mixed to prepare, wherein nano zine oxide accounts for the 8% of carbamide paint.
Comparative example 4
Carbamide paint and nano silicon are mixed to prepare, wherein nano silicon accounts for carbamide paint
10%.
Embodiment 4
Marine microalgae antifouling property is tested
(1) chlorella and Nitzschia closterium minutissima algae solution culture
After seawater is filtered through glass sand core funnel, scalding, cooling prepares f/2 Algae culture solutions.Algae solution is placed on people
Culture in work climate box, intensity of illumination is 2500lx.
With 0.45 μm of aperture membrane filtration 1L nature seawater, adjusted with the HCl solution of the NaOH or 1mol/L of 1mol/L
PH to 8.0.Sterilize 20min at 121 DEG C, and it is standby and determine algae solution concentration-light absorption value curve to be cooled to room temperature, will according to curve
The algae solution Algae culture solution cultivated to exponential phase of growth is diluted to 3 × 105Individual/mL.
Coating to be tested is coated on the sheet glass that specification is 10 × 10 × 0.1cm ± 0.5, spreading area is about 90cm2,
Naturally dry, it is standby.
Test board is placed on grillage, print is placed in the glass jar for filling tested algae solution, 20 DEG C, the bar of 3000lx
Soaked 7 days under part.
(2) model detection：Test board is taken out, with by glass sand core funnel filter and with 121 sterilizing 20min seawater
Eluent is rinsed repeatedly, and the frond of the attachment on model is all swept away to the greatest extent, and the algae solution constant volume that will be swept away uses ELIASA to 25mL
OD values and algal control rate are determined, test result refers to table 1.
As can be known from Table 1, embodiment 1~3 is with blank example, compared with comparative example 1~4, the anti-halobios adhersion of embodiment 1~3
Coating is significantly higher than blank example and comparative example 1~4 to the inhibiting rate of marine microalgae, using technical scheme, carries significantly
The inhibiting rate to marine microalgae high, serves the effect of good anti-fouling biological attachment.
Algal control rate of the various coating of table 1 to marine microalgae
Remarks：Blank example is the carbamide paint for being not added with antibacterial anti-fouling agent in table, similarly hereinafter.
Embodiment 5
With Mytilus galloprovincialis as biological subject, by calculating the fatal rate of mussel, the antifouling of antibacterial antifouling paint of the present invention is evaluated
Effect.AB amount components are mixed and is sprayed on the glass plate of 100mm × 5mm × 1mm (glass plate surrounding is surrounded with glass bar), dried in the air
It is dry；With seawater flushing for several times, then dry, it is standby.Several tested materials are uniformly placed on each test board, in 20 DEG C or so seawater
Immersion, while oxygenation maintains the oxygen content in seawater.Timing observation mussel adhesion condition, experimental result refers to table 2.
As can be known from Table 2, embodiment 1~3 is adhered to compared with blank example, comparative example 1~4 with anti-Mytilus galloprovincialis well
Ability, the fatal rate to Mytilus galloprovincialis is up to 100%, and the antibacterial antifouling paint using technical scheme has to Mytilus galloprovincialis
Good anti-adhesion effect.
The anti-Mytilus galloprovincialis adhesion property of the various coating of table 2
Remarks：Blank example is the carbamide paint for being not added with antibacterial anti-fouling agent in table, similarly hereinafter.
Embodiment 6
Bacteria Culture：Attached crop sample is diluted with a certain amount of antiseptic sea water, takes supernatant liquor, distinguished with rubbing method
It is seeded on the plating medium of advance numbering, is placed in 25 DEG C of incubators, cultivate 3~5 days, observes, separates and purify, then
Inclined-plane is inoculated in, glycerine fluid-tight is preserved under low temperature.
Fluid nutrient medium：Chen Haishui 1000ml, peptone 5g, yeast extract 1g are will be equipped with, in the beaker of ferric sesquichloride 0.11g
The water less than required for is first added, is stirred evenly with glass bar, then heating dissolves it, after medicine is completely dissolved, replenishes water to institute
The cumulative volume for needing, then by liquid subpackage to conical flask.
Coating to be tested is coated on the sheet glass that specification is 10 × 10 × 0.1cm ± 0.5, spreading area is about 90cm2,
Naturally dry, it is standby.
The preparation of eluent：Seawater used through glass sand core funnel filter after, 121 sterilizing 20min, it is standby.
The preparation of bacteria suspension：Each 1 ring of strain of inclined-plane preservation is taken, is inoculated in the fluid nutrient medium of 50ml, 25 DEG C,
Under the conditions of 180r/min, 6h is continuously cultivated, choose suspension of the absorbance before 0.1~0.6, it is standby.
Indoor hanging plate method：Respectively in 6 glass jars (630 × 370 × 500mm of specification), 10L antiseptic sea waters are added,
And each 1mL of tested bacteria suspension after culture 6h, 25 DEG C of keeping temperature, after culture 6h, the glass plate that will scribble coating is put into glass
In glass cylinder, be placed on self-control support, continuously cultivate 24h, glass plate is taken out, with Liquid Culture based method drip washing, leacheate with
Constant volume in 50mL volumetric flasks, surveys its OD value so as to calculate bacteriostasis rate, as a result as shown in table 3.
As shown in Table 3, compared with blank example, comparative example 1~4, bacteriostasis rate is up to 90% or so to embodiment 1~3, with very
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 to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should be all considered as belonging to of the invention
Protection domain.
Claims (7)
1. a kind of anti-fouling biological attachment agent, it is characterised in that：The anti-fouling biological attachment agent is organosilicon quaternary ammonium salt surface
Modified zinc oxide/the silicon dioxide hollow microsphere for being loaded with antiseptic, it includes organosilicon quaternary ammonium salt, antiseptic, zinc oxide/bis-
Silica hollow microsphere, the organosilicon quaternary ammonium salt：Antiseptic：The mass ratio of zinc oxide/silicon dioxide hollow microsphere is（1~
3）：（6~50）：5, wherein the silica and the mass ratio of zinc oxide in the zinc oxide/silicon dioxide hollow microsphere are 5:
（0.1~3）；The antiseptic is imidazoline quaternary ammonium salt or potassium sorbate；The anti-fouling biological attachment agent uses following steps system
It is standby：
Step S1：Prepare organic template, make organic template/silica core-shell microspheres；
Step S2：Prepare zinc oxide/silicon dioxide hollow microsphere；
Step S3：Prepare organosilicon quaternary ammonium salt surface modified zinc oxide/silicon dioxide hollow microsphere；
Step S4：Prepare the modified zinc oxide/silicon dioxide hollow microsphere for being loaded with antiseptic in organosilicon quaternary ammonium salt surface；Its
In, the organic template is styrene and acrylic acid copolymer microballoon or cetyl trimethylammonium bromide；
In step S3, the preparation method of the organosilicon quaternary ammonium salt surface modified zinc oxide/silicon dioxide hollow microsphere is：By oxygen
Change during zinc/silicon dioxide hollow microsphere adds organosilicone quaternary ammonium salting liquid, 2 ~ 4h mixed under normal temperature, then adjust pH value to
3 ~ 4, after standing 12 ~ 24h, supersound washing is carried out, in 80 ~ 120 DEG C of dryings, grinding；
In step S4, described to prepare the modified zinc oxide/hollow silica for being loaded with antiseptic in organosilicon quaternary ammonium salt surface micro-
The step of ball is：By the organosilicon quaternary ammonium salt surface modified zinc oxide/silicon dioxide hollow microsphere decompression 15 ~ 30min of pumping,
Antiseptic is added dropwise, while opening Vltrasonic device, treats that antiseptic is totally submerged zinc oxide/silicon dioxide microsphere and ultrasonic disperse is uniform
Afterwards, decompressor is withdrawn from, 7 ~ 9h is stirred at room temperature, and at interval of 2h ultrasounds 1min；Centrifugation, discards after supernatant liquor at 60 DEG C
12 ~ 24 h of vacuum drying.
2. anti-fouling biological attachment agent according to claim 1, it is characterised in that the organosilicon quaternary ammonium salt：Antiseptic：
The mass ratio of zinc oxide/silicon dioxide hollow microsphere is（1.5~2.5）：（10~40）：5, wherein zinc oxide/hollow silica
Silica and the mass ratio of zinc oxide are 5 in microballoon:（0.2~2）.
3. anti-fouling biological attachment agent according to claim 2, it is characterised in that：In step S1, the making organic matter
Template/silica core-shell microspheres are comprised the following steps：Absolute ethyl alcohol is added in organic template carries out ultrasonic disperse, then
Add water and ammoniacal liquor to add tetraethyl orthosilicate after stirring 5 ~ 30min, seal bottleneck, 3 ~ 15h is reacted at 20 ~ 40 DEG C；It is centrifuged, washes
Wash, dry.
4. anti-fouling biological attachment agent according to claim 2, it is characterised in that：In step S2, the zinc oxide/dioxy
The preparation of SiClx hollow microsphere is prepared using following steps：Organic template/titanium dioxide is added in the container equipped with distilled water
Silicon core-shell particles and soluble zinc salt, add sodium citrate after stirring, generation precipitation in ammoniacal liquor to solution is added after being sufficiently stirred for
And when disappearing immediately, then container is placed in oil bath is heated to 110 ~ 180 DEG C and is stirred at reflux 3 ~ 12h；By gained pelleting centrifugation point
From, and cleaned with deionized water, dry after obtain zinc oxide/organic template/silica core-shell microspheres；Finally will oxidation
In under air atmosphere, being warming up to 400 DEG C ~ 650 DEG C, heating rate is 0.5 ~ 2 to zinc/organic template/silica core-shell microspheres
DEG C/min, and 3 ~ 7h is incubated, cooling obtains zinc oxide/silicon dioxide hollow microsphere；Wherein, the sodium citrate and zinc salt mole
Than being 1:1.5~6.
5. a kind of anti-fouling biological attachment coating, it is characterised in that：Be made up of the component of A, B two, composition that wherein component A includes and
Its percentage by weight is：Polyisocyanates 50-70%, PPG 30-50%；Composition and its weight percent that B component includes
Than for：Polyaspartate 40-70%, anti-fouling biological attachment agent 1 ~ 15%, pigment 5 ~ 25%, filler 5-25%, auxiliary agent 0.5-5%,
Wherein, the anti-fouling biological attachment agent is the anti-fouling biological attachment agent as described in claim 1 ~ 4 any one.
6. anti-fouling biological attachment coating according to claim 5, it is characterised in that：Composition that the component A includes and
Its percentage by weight is：Polyisocyanates 50-65%, PPG 35-50%；Composition and its weight percent that B component includes
Than for：Polyaspartate 50-65%, anti-fouling biological attachment agent 1 ~ 10%, pigment 5 ~ 20%, filler 5-20%, auxiliary agent 1-5%；Its
In, the auxiliary agent is at least one in defoamer, wetting dispersing agent, levelling agent, coupling agent.
7. anti-fouling biological attachment coating according to claim 6, it is characterised in that：
The polyisocyanates is different 2,4 '-methyl diphenylene diisocyanate, IPDI, hexa-methylene two
At least one in cyanate, dicyclohexyl methyl hydride diisocyanate；The PPG is polyglycol ether, polypropylene glycol
At least one in ether, polyglycerol ether or PTMG；
The polyaspartate is obtained with primary amine for diethyl maleate by Michael addition reactions, wherein the primary amine
It is two functional groups or the PPOX polyamine or polyethylene glycol oxide polyamine of trifunctional；
Described filler is at least one in oyster shell whiting, quartz sand powder or talcum powder；The pigment is titanium dioxide；
Described filler and pigment be carried out using surface modifier it is surface-treated, wherein the surface modifier be stearic acid
At least one in salt, aluminate coupling agent, titanate coupling agent or silane coupler；
The defoamer is organic silicon defoamer or calcium oxide.
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| CN107083095B (en) * | 2017-05-26 | 2019-03-19 | 中国船舶重工集团公司第七二五研究所 | A kind of fouling organism sensitivity response anti-fouling agent controlled-release material and preparation method thereof |
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| 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 |
| CN109749616B (en) * | 2018-12-29 | 2020-03-13 | 西安交通大学 | Antifouling coating capable of releasing antifouling agent and preparation method thereof |
| CN110433739B (en) * | 2019-08-26 | 2021-11-02 | 青岛农业大学 | Method for preparing antifouling and corrosion-resistant functional microcapsules based on Pickering emulsion |
| 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 |
| 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 |
| CN111807711B (en) * | 2020-07-24 | 2022-05-13 | 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 |
| 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 |
| CN113736059A (en) * | 2021-09-15 | 2021-12-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Asparagus polyurea resin system with marine antifouling function and coating composition |
| CN113881329B (en) * | 2021-11-16 | 2022-04-22 | 哈尔滨工程大学 | Antifouling paint and use method 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3684634B2 (en) * | 1995-10-19 | 2005-08-17 | ラサ工業株式会社 | Antibacterial composition and method for producing the same |
| KR102070449B1 (en) * | 2013-06-12 | 2020-01-28 | 삼성전자주식회사 | Anti-bacterial and Anti-fingerprint coating composition, film using the same, the method of the same, and the coated product |
-
2015
- 2015-08-10 CN CN201510485615.2A patent/CN105062175B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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