CN107955524A - Organic silicon antifouling paint of the quaternary ammonium salt containing PEG/ and preparation method thereof - Google Patents
Organic silicon antifouling paint of the quaternary ammonium salt containing PEG/ and preparation method thereof Download PDFInfo
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- CN107955524A CN107955524A CN201711170754.1A CN201711170754A CN107955524A CN 107955524 A CN107955524 A CN 107955524A CN 201711170754 A CN201711170754 A CN 201711170754A CN 107955524 A CN107955524 A CN 107955524A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
Organic silicon antifouling paint the present invention relates to a kind of quaternary ammonium salt containing PEG/ and preparation method thereof.The present invention combines self assembly PEG monolayers or the advantage of crosslinked PEG hydrogel layer and quaternary ammonium salt, and quaternary ammonium salt is incorporated into the Semi-IPN cross-linked network nonpolluting coating of organosilicon containing PEG, obtains one kind and contains PEG（Polyethylene glycol）The organic silicon antifouling paint of/quaternary ammonium salt.The advantages that coating of the present invention has excellent anti-albumen, anti-algae, antibacterial concurrently, is with a wide range of applications in marine anti-pollution field.
Description
Technical field
Contain organic silicon antifouling paint of polyethylene glycol (PEG)/quaternary ammonium salt and preparation method thereof the present invention relates to one kind,
Background technology
As the mankind development activities and go deep into ocean research in ocean, the problem of marine biofouling, also becomes day
It is beneficial serious, just like have become a global problem, cause huge loss every year.By taking marine ship as an example, marime fouling
The attachment of biology can accelerate the failure hull surface, increase hull surface roughness, so as to increase fuel consumption during navigation, reduce boat
Scanning frequency degree, increases maintenance cost, shortens the service life of hull.Statistics according to the study, if not coating nonpolluting coating, ship
Body can increase by nearly 40% fuel consumption after six months.International Maritime Organization (IMO) explicitly indicates that：If do not take corresponding
The measure anti-soil technology new with introduction, the gas emissions to the year two thousand twenty World Ship transport fuel consumption will increase 38%-
72%.Therefore, it is necessary to the attachment for the fouling organism that takes effective measure to prevent, antifouling paint is exactly to develop under this overall background
Get up.
Self assembly PEG monolayers or crosslinked PEG hydrogel layer have good anti-protein adsorption performance.It is but hydrophilic
PEG is easily swollen in water, causes the antifouling validity of coating to decline, so as to be difficult to apply in marine antifouling coating.And contain
Such issues that polymer of PEG group is less prone to, the reason is that it can form one layer of tool in water with hydrophilic PEG chain segment
There is the hydrated sheath of anti-protein adsorption ability.For this reason, hydrophilic PEG is incorporated into low-surface-energy anti-fouling system by researcher, originally,
PEG is incorporated into anti-fouling system after being prepared to homopolymer in a manner of blending, but this mode is easy to cause homopolymer exists
Leaked out during preparing film.In further research, PEG segments are prepared into parents notion by researcher, then
Mixed with PVDF, the anti-fouling effect of coating is more prominent.This result of study also promotes scholars and antifouling field parents is total to
The research of polymers, the parents notion containing PEG chain segment are increasingly becoming the new focus of antifouling research field.
Quaternary ammonium salt is a kind of cationic surfactant, is mainly nitrogenous organic amine derivatives, since nitrogen is former in molecule
Son has lone pair electrons, so with the hydrogen in acid molecule with Hydrogenbond amino can be made to become positively charged lotus.It is primarily used as killing
Bacterium algicide, antistatic additive and fabric fibre softener etc..In marine anti-pollution field, researcher is antifouling to organosilicone quaternary ammonium salt
Agent is more paid close attention to, frequently as cationic surfactant.The chemism of general quaternary ammonium salt is relatively low, and works as and replace season with siloxanes
During alkyl on ammonium salt, great changes will take place for its performance.Its activity can greatly improve first, can react with active group,
The Si-O keys formed by hydrolysis-condensation reaction, are intimately associated with active group, form firm film, so that quaternary ammonium salt is anti-
Dirty effect is more lasting.
The content of the invention
It is an object of the present invention to combine self assembly PEG monolayers or crosslinked PEG hydrogel layer and quaternary ammonium
The advantage of salt, quaternary ammonium salt is incorporated into the Semi-IPN cross-linked network nonpolluting coating of organosilicon containing PEG, is obtained one kind and is contained poly- second two
The organic silicon antifouling paint of alcohol (PEG)/quaternary ammonium salt.
The second object of the present invention is the preparation method for providing the coating.This method is adapted to industrialized production；Carry at the same time
For naval stores made from one kind implementation this method, it can preferably meet the requirement of Marine Antifouling Coatings auxiliary resin.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that to realize：
A kind of organic silicon antifouling paint containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the composition and quality hundred of the coating
Point content is：
Component A 80%~96%
Component B 2%~10%
Component C 2%~10%；
The composition and mass percent of the wherein described component A be：
The composition 2 is：
Wherein, n is 20~500；P is 5~50；M is 2~7.
The composition and mass percent of the component B be：
Tetrabutylammonium chloride 0.6%~6%
4-methyl-2 pentanone 94%~99.4%
The component C is that the toluene for the methyl triacetoxysilane that mass percent concentration is 25%~50% is molten
Liquid.
Above-mentioned organic silicon substrate resin structure formula is：Wherein, n for 200~
600。
Above-mentioned quaternary ammonium salt is：Alkyldimethylbenzylammonium quaternary ammonium salt, trimethoxy silicon substrate propyl group-N, N, N- trimethyl chlorine
Change ammonium, dodecyl benzyl dimethyl ammonium chloride, dodecyldimethylamine base (3- trimethoxy silicon substrates propyl group) ammonium chloride, octadecane
At least one of base dimethyl (3- trimethoxy silicon substrates propyl group) ammonium chloride.
The preparation method of combinations of the above thing 2 is：
A. under inert atmosphere protection, polyethylene glycol diallyl ether is dissolved in toluene, adds the catalysis of catalytic amount
Agent, 3~15min of back flow reaction, obtains reaction mixture；
B. it is 1 according to end hydrogen silicone oil and the molar ratio of polyethylene glycol diallyl ether:1.1~1:6 ratio, in step a
The toluene solution of end hydrogen silicone oil, 5~8h of back flow reaction are added dropwise in gained mixed reaction solution；Light yellow transparent solution is obtained, is removed
Solvent toluene, then removes unreacted polyethylene glycol diallyl ether with ice methanol extraction, obtains composition 1；
The structural formula of the end hydrogen silicone oil isWherein, n 20-500；
C. under inert atmosphere protection, step b resulting compositions 1 and trimethoxy hydrogen silane are pressed 1:2.1~1:6
Molar ratio is dissolved in toluene, 10~15min of back flow reaction；The catalyst of catalytic amount is added dropwise again, keeps the temperature 2~5h；Obtain faint yellow
Transparency liquid, removes solvent and excessive trimethoxy hydrogen silane, can obtain composition 2.
Above-mentioned polyethylene glycol diallyl ether number-average molecular weight is 200-2000.
Above-mentioned catalyst is：Dibutyl tin laurate, dibutyltin diacetate, Karstedt catalyst or protochloride
Tin.
A kind of method for preparing the above-mentioned organic silicon antifouling paint containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the party
Method concretely comprises the following steps：By component A, component B, component C mix, be stirred at room temperature it is uniformly mixed, then on the surface of base material
Form one layer of uniform film；Under conditions of temperature is 5~50 DEG C, relative humidity is 10%~80%, make curing of coating simultaneously
It is attached on base material, the protective film that a layer thickness is 80~200 microns is formed on the surface of the base material；In 25~125 DEG C of bars
Under part, dry 2~12h.
The coating of the present invention has good excellent of good low-surface-energy, stability, sea water resistance immersion, environmentally protective, antifouling property
Point.The advantages that having excellent anti-albumen, anti-algae, antibacterial concurrently, is with a wide range of applications in marine anti-pollution field.
Brief description of the drawings
1. Fig. 1 is example one, example two, example three, the anti-albumen aptitude tests figure of example four.
Its anti-protein capability test is mainly tested by using the labeled bovine serum albumin of fluorescein.In darkroom bar
Under part, quantitative protein solution is taken out with liquid-transfering gun, is taking same amount of PBS buffer solutions half-and-half to dilute, after mixing, will
Solution drops in coating sample surface, then covered, makes solution extravagant uniformly.Sample is placed into 2h, then removes lid glass
Piece, then articles for use surface is cleaned with PBS buffer solutions, after drying to be coated, with fluorescence microscope, then with ImageJ softwares
Reason, calculates the relative gray values of coating sample.Final data are represented with average gray value (MGV).Detailed data processing
It is as follows：
MGVsample=(MGVFITC-BSA-MGVFITC-BSA-free) × coefficient note： MGVFITC-BSA:Attachment
The gray value of fluorescin；MGVFITC-BSA-free:The gray value of unstressed configuration protein domain；Coefficient=255/ (blank print
MGVFITC-BSA- blank print MGVFITC-BSA-free).
2. Fig. 2 is example one, example two, example three, the anti-algae adhesive ability test chart of example four.
The algae-resistant adhesion property of coating is tested using boat-shaped algae Navicula, and boat-shaped algae is in illumination condition
2000Lux, temperature are cultivate 21 days at 25 DEG C, manually seawater dilution original diatom liquid, and acquisition concentration is 1 × 105cells mL-
1 algae solution is spare.Coating sample is immersed in artificial seawater 2 days in advance, the sample soaked is respectively placed in culture dish
In, respectively take the algae solution of 1 × 105cells of 25ml mL-1 to be added in culture dish, sample is fully immersed in algae solution, and put
(temperature is 25 DEG C, illumination condition 2000Lux) culture 4h is put in illumination box.Then coating sample is taken out, repeatedly
Manually seawater washes away the diatom being not adhered on coating, after drying to be coated, in the attached of fluorescence microscopy Microscopic observation diatom
The amount of wearing.Each sample chooses 15 regions, seeks out average value with software processing, counts the adhesion amount of diatom on coating, according to this
To judge the algae-resistant adhesion property of coating.
3. Fig. 3 is example one, example two, example three, four antibacterial ability test chart of example.
Antibacterial experiment is mainly characterized by following：Coating sample to be measured is first cut into the disk of 1cm, is put into 24
Orifice plate bottom.The remote blue or green vibrios bacteria suspension for being in stationary phase is taken, 2ml is instilled into each orifice plate, 25 DEG C in constant incubator
Under the conditions of cultivate 70h, carry out bacterium attachment experiment.Deionized water lavage specimens product surface is used after experiment, is then contaminated with DAPI
Toner dyes 10~15 minutes, in fluorescence microscopy Microscopic observation.3 Duplicate Samples of each sample, choose 10 visuals field and are counted,
Finally take the average of particle-bound bacteria.
4. Fig. 4 is the anti-albumen aptitude tests figure of embodiment three, five, six.
5. Fig. 5 is the anti-algae adhesive ability test chart of embodiment three, five, six.
6. Fig. 6 is the antibacterial ability test chart of embodiment three, five, six.
Embodiment
Embodiment one：Organic silicon antifouling paint provided in this embodiment containing polyethylene glycol/quaternary ammonium salt and preparation method thereof
It is characterized in that, it comprises the following steps：
(1) composition 1 is prepared：
The polyethylene glycol diallyl ether, 60g toluene that 16.75g number-average molecular weights are 500 are weighed, after mixing, then will
Mixed liquor is added to together with 0.053g Karstedt catalyst equipped with reflux condensing tube, constant pressure funnel, nitrogen gas-guide tube
In the four round flask of mechanical agitator, 85 DEG C are warming up under the atmosphere of nitrogen, and keeps this temperature reflux 10min.
The end hydrogen silicone oil and 40g toluene that 75g number-average molecular weights are 12500 are weighed, pours into constant pressure funnel after mixing,
It is added in 90min in four-hole boiling flask, 100 DEG C is warming up to after dripping and keeps the temperature 6h.Reaction is completed at this time, is gone out after waiting cooling
Material, product is light yellow transparent solution.Above-mentioned solution is poured into clean revolving bottle, solvent first is removed with Rotary Evaporators
Benzene, then pours into separatory funnel by the solution for removing solvent, unreacted polyethylene glycol diallyl is removed with ice methanol extraction
Ether, obtains composition 1.
(2) composition 2 is prepared：
20g compositions 1,30g toluene and 0.0424g Karstedt catalyst are weighed, is added to together equipped with reflux condensation mode
Pipe, constant pressure funnel, nitrogen gas-guide tube and mechanical agitator four round flask in, be warming up to 80 in a nitrogen atmosphere
DEG C, and this temperature reflux 10min is kept, 0.3g trimethoxies hydrogen silane and 10g toluene are weighed, pours into constant pressure after mixing
Dropping funel, is added in four round flask in 1h, keeps the temperature 3h.Reaction is completed at this time, cooling discharge, and product is faint yellow
Transparency liquid.Above-mentioned solution is poured into clean revolving bottle, solvent and excessive trimethoxy hydrogen are removed with Rotary Evaporators
Silane, can obtain composition 2.
(3) component A is prepared：
Weigh 0.56g compositions 2,7g organic silicon substrates resin (n=600), 2g solvent toluenes, 0.01g trimethoxy silicon
Base propyl-N,N,N-trimethylammonium chloride mixes, and component A is made；
(4) component B is prepared：
The tetrahydrofuran solution for taking 12.5ml concentration to be 1mol/L tetrabutylammonium chlorides with graduated cylinder pours into the capacity of 250 ml
In bottle, drained with glass bar and add 4-methyl-2 pentanone, be 50 mmol/L by solution constant volume concentration, obtain component B.
(5) component C is prepared：
Component C is made to clarifying using dilution with toluene in 1.05g methyl triacetoxysilanes.
(6) by component A, component B, component C mix be stirred at room temperature 2 it is small when, by coating to institute by way of dip-coating
The base material that need to be coated is coated action, the surface of base material is formed one layer of uniform film；
(7) coating action finishes, temperature be 50 DEG C, relative humidity be that 60% at room temperature, curing of coating is simultaneously attached to
On base material, the protective film that a layer thickness is 150 microns is formed on the surface of the base material；
(8) it is put into electric heating constant-temperature blowing drying box, under the conditions of 100 DEG C, dry 3h.
Embodiment two：It please change a catalyst.Change the polyethylene glycol diallyl ether and end hydrogen silicone oil of a molecular weight.
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
Example one is roughly the same, its difference is：
The amount of trimethoxy silicon substrate propyl group-N, N, the N- trimethyl ammonium chloride used in preparation process is 0.616g.
Example three：It please change a catalyst.Change the polyethylene glycol diallyl ether and end hydrogen silicone oil of a molecular weight.
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
Example two is essentially identical, its difference is：
The catalyst used in preparation process is dibutyl tin laurate, the quaternary ammonium salt chemical combination used in preparation process
Thing is dodecyldimethylamine base (3- trimethoxy silicon substrates propyl group) ammonium chloride.
Example four：It please change a catalyst.Change the polyethylene glycol diallyl ether and end hydrogen silicone oil of a molecular weight.
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
It is essentially identical to apply example two, its difference is：
The quaternary ammonium compound used in preparation process is octadecyldimethyl (3- trimethoxy silicon substrates propyl group) chlorine
Change ammonium.
Example five：
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
It is essentially identical to apply example three, its difference is：
The end hydrogen silicone oil molecular weight used in preparation process is 2000.
Example six：
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
It is essentially identical to apply example three, its difference is：
The end hydrogen silicone oil molecular weight used in preparation process is 4000.
Example seven：
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
It is essentially identical to apply example two, its difference is：
The quaternary ammonium compound used in this case step (3) is octadecyldimethyl (3- trimethoxies silicon substrate third
Base) ammonium chloride, the amount of addition is 0.308g.
Example eight：
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
It is essentially identical to apply example seven, its difference is：
The catalyst added in preparation process is dibutyltin diacetate；The quaternary ammonium salt used in this case step (3)
Compound is dodecyl benzyl dimethyl ammonium chloride, and the amount of addition is 1.232g.
Example nine：
The preparation method and product of the bionical antifouling resin of organic fluorinated silicone provided in this embodiment, its component and step with reality
It is essentially identical to apply example five, its difference is：
The polyethylene glycol diallyl ether molecular weight used in this example is 2000.
The invention is not restricted to above-described embodiment, such as using the preparation side with the same or similar technical characteristic of above example
Method, all falls in the scope of protection of the present invention.
Fig. 1, Fig. 2, Fig. 3 illustrate that quaternary ammonium salt is added in organic silicon antifouling paint can effectively improve the anti-egg of coating respectively
In vain, anti-algae attachment and antibacterial ability.
Fig. 4, Fig. 5, Fig. 6 illustrate the end hydrogen silicone oil for adding different molecular weight, its anti-albumen, the attachment of anti-algae and antibacterial energy respectively
Power will be different, and three best results of example.
Claims (7)
1. a kind of organic silicon antifouling paint containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the composition and quality percentage of the coating
Content is：
Component A 80%~96%
Component B 2%~10%
Component C 2%~10%；
The composition and mass percent of the wherein described component A be：
Composition 2 5%~10%
Organic silicon substrate resin 40%~70%
Quaternary ammonium salt 0%~20%, and do not include 0
Toluene 10%~20%
The structural formula of the composition 2 is：
Wherein, n is 20~500；P is 5~50；M is 2~7；
The composition and mass percent of the component B be：
Tetrabutylammonium chloride 0.6%~6%
4-methyl-2 pentanone 94%~99.4%
The component C is the toluene solution for the methyl triacetoxysilane that mass percent concentration is 25%~50%.
2. the organic silicon antifouling paint according to claim 1 containing polyethylene glycol/quaternary ammonium salt, it is characterised in that described has
Machine silicone matrix resins structural formula is：Wherein, n is 200~600.
3. the organic silicon antifouling paint according to claim 1 containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the season
Ammonium salt is：Alkyldimethylbenzylammonium quaternary ammonium salt, trimethoxy silicon substrate propyl group-N, N, N- trimethyl ammonium chloride, dimethyl
Base benzyl ammonium chloride, dodecyldimethylamine base（3- trimethoxy silicon substrate propyl group）Ammonium chloride, octadecyldimethyl（3- trimethoxies
Base silicon substrate propyl group）At least one of ammonium chloride.
4. the organic silicon antifouling paint according to claim 1 containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the group
The preparation method of compound 2 is：
A. under inert atmosphere protection, polyethylene glycol diallyl ether is dissolved in toluene, adds the catalyst of catalytic amount, is returned
Stream 3~15 min of reaction, obtain reaction mixture；
B. it is 1 according to end hydrogen silicone oil and the molar ratio of polyethylene glycol diallyl ether:1.1~1:6 ratio, in step a institutes
Obtain the toluene solution that end hydrogen silicone oil is added dropwise in mixed reaction solution, 5~8 h of back flow reaction；Light yellow transparent solution is obtained, is removed molten
Agent toluene, then removes unreacted polyethylene glycol diallyl ether with ice methanol extraction, obtains composition 1；The end hydrogen
The structural formula of silicone oil isWherein, n 20-500；
C. under inert atmosphere protection, step b resulting compositions 1 and trimethoxy hydrogen silane are pressed 1:2.1~1:6 mole
Than being dissolved in toluene, 10~15 min of back flow reaction；The catalyst of catalytic amount is added dropwise again, keeps the temperature 2~5 h；Obtain faint yellow
Prescribed liquid, removes solvent and excessive trimethoxy hydrogen silane, can obtain composition 2.
5. the organic silicon antifouling paint according to claim 1 containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the poly- second
Glycol diallyl ether number-average molecular weight is 200-2000.
6. the organic silicon antifouling paint according to claim 1 containing polyethylene glycol/quaternary ammonium salt, it is characterised in that the catalysis
Agent is：Dibutyl tin laurate, dibutyltin diacetate, Karstedt catalyst or stannous chloride.
7. a kind of prepare the organic silicon antifouling paint according to claim 1 containing polyethylene glycol/quaternary ammonium salt, it is characterised in that
This method concretely comprises the following steps：By component A, component B, component C mix, be stirred at room temperature it is uniformly mixed, then in base material
Surface forms one layer of uniform film；Under conditions of temperature is 5~50 DEG C, relative humidity is 10%~80%, make curing of coating
And be attached on base material, the protective film that a layer thickness is 80~200 microns is formed on the surface of the base material；25~125
Under the conditions of DEG C, dry 2~12 h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110726804A (en) * | 2019-07-11 | 2020-01-24 | 浙江省海洋开发研究院 | Quick evaluation method for antifouling performance of bionic and low-surface-energy marine antifouling coating |
| CN111875803A (en) * | 2020-07-03 | 2020-11-03 | 湖南航天三丰科工有限公司 | Organic silicon containing polyethylene glycol and preparation method thereof |
| CN112029102A (en) * | 2020-08-18 | 2020-12-04 | 集美大学 | Multi-block copolymer, multi-block amphiphilic polymer and preparation method and application thereof |
| CN112552765A (en) * | 2020-12-02 | 2021-03-26 | 江南大学 | Quaternary ammonium salt cation antibacterial antifouling coating and preparation method and application thereof |
| CN112940616A (en) * | 2021-03-26 | 2021-06-11 | 华南理工大学 | Hydrophobic antibacterial coating containing quaternary ammonium salt and preparation method and application thereof |
| CN113845838A (en) * | 2021-08-30 | 2021-12-28 | 盖科(浙江)生物科技有限公司 | Amphiphilic siloxane gel and preparation method thereof |
| CN115785803A (en) * | 2021-09-09 | 2023-03-14 | 涂创时代(苏州)科技开发有限公司 | Nontoxic amphiphilic organic silicon polymer-based marine antifouling paint and preparation method and application thereof |
| CN115806686A (en) * | 2021-09-15 | 2023-03-17 | 齐鲁工业大学 | Antibacterial and anti-protein coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005054035A (en) * | 2003-08-01 | 2005-03-03 | Ishihara Chem Co Ltd | Stain-resistant water repellant composition |
| CN104877421A (en) * | 2015-06-10 | 2015-09-02 | 上海大学 | Polyethyleneglycol-containing fluorinated polysiloxane modification acrylic acid antifouling paint and preparing method thereof |
-
2017
- 2017-11-22 CN CN201711170754.1A patent/CN107955524B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005054035A (en) * | 2003-08-01 | 2005-03-03 | Ishihara Chem Co Ltd | Stain-resistant water repellant composition |
| CN104877421A (en) * | 2015-06-10 | 2015-09-02 | 上海大学 | Polyethyleneglycol-containing fluorinated polysiloxane modification acrylic acid antifouling paint and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 仇春红: "季铵盐海洋防污涂层研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 翁斌 等: "含氟/PEG的有机硅基双亲防污涂层的制备及性能", 《高分子学报》 * |
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| CN110726804A (en) * | 2019-07-11 | 2020-01-24 | 浙江省海洋开发研究院 | Quick evaluation method for antifouling performance of bionic and low-surface-energy marine antifouling coating |
| CN111875803A (en) * | 2020-07-03 | 2020-11-03 | 湖南航天三丰科工有限公司 | Organic silicon containing polyethylene glycol and preparation method thereof |
| CN112029102A (en) * | 2020-08-18 | 2020-12-04 | 集美大学 | Multi-block copolymer, multi-block amphiphilic polymer and preparation method and application thereof |
| CN112552765A (en) * | 2020-12-02 | 2021-03-26 | 江南大学 | Quaternary ammonium salt cation antibacterial antifouling coating and preparation method and application thereof |
| CN112552765B (en) * | 2020-12-02 | 2022-02-01 | 江南大学 | Quaternary ammonium salt cation antibacterial antifouling coating and preparation method and application thereof |
| CN112940616A (en) * | 2021-03-26 | 2021-06-11 | 华南理工大学 | Hydrophobic antibacterial coating containing quaternary ammonium salt and preparation method and application thereof |
| CN113845838A (en) * | 2021-08-30 | 2021-12-28 | 盖科(浙江)生物科技有限公司 | Amphiphilic siloxane gel and preparation method thereof |
| CN113845838B (en) * | 2021-08-30 | 2022-04-05 | 盖科(浙江)生物科技有限公司 | Amphiphilic siloxane gel and preparation method thereof |
| CN115785803A (en) * | 2021-09-09 | 2023-03-14 | 涂创时代(苏州)科技开发有限公司 | Nontoxic amphiphilic organic silicon polymer-based marine antifouling paint and preparation method and application thereof |
| CN115806686A (en) * | 2021-09-15 | 2023-03-17 | 齐鲁工业大学 | Antibacterial and anti-protein coating and preparation method thereof |
| CN115806686B (en) * | 2021-09-15 | 2023-09-15 | 齐鲁工业大学 | Antibacterial protein-resistant coating and preparation method thereof |
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