CN109837545A - A kind of anti-rotten and antifouling capacity method in the ocean of NB-IOT information module encapsulation protection stainless steel substrates - Google Patents
A kind of anti-rotten and antifouling capacity method in the ocean of NB-IOT information module encapsulation protection stainless steel substrates Download PDFInfo
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Abstract
The present invention provides a kind of anti-rotten and antifouling capacity the methods in the ocean of NB-IOT information module encapsulation protection stainless steel substrates.This method is to be fixed on hyper-branched polymer brush by way of covalence graft to carry out antifouling and anti-corruption on stainless steel substrates substrate, dopamine carries out autohemagglutination on the surface SS first, and an alkyl bromide is subsequently introduced as atom transfer radical polymerization (ATRP) initiator.Vinyl chloride (VBC) occurs ATRP polymerization on the surface SS that bromine blocks and obtains hyperbranched polyvinylbenzylchloride brush, then purpurine is introduced in the polymer brush, it improves the concentration of quaternary ammonium salt in the system, enhances the anti-rotten and antifouling capacity in ocean of the stainless steel substrates.The method of the present invention has simple, it is nontoxic, Environmental Sustainability, commercial viability, durability and high-performance, and the advantages that can be prepared on a large scale, it is expected to the encapsulation protective materials as NB-IOT module, when it being made to work in marine environment, carry out wireless data transmission that can be stable, from module damage caused by marine corrosion and pollution, prolong its service life.
Description
Technical field
The antifouling and anti-biological corrosion field for using material is encapsulated the invention belongs to narrowband Internet of Things (NB-IOT) information module,
Modify stainless steel substrates more particularly to a kind of hyper-branched polymer using containing purpurine, thus reach it is antifouling in marine environment and
The method of antibiont corrosion.
Background technique
With the development of science and technology, human society has gradually stepped into the intelligent epoch.In recent years, such as Intelligent stop
The novel intelligents technology such as vehicle, intelligent medical treatment, smart home is grown rapidly like the mushrooms after rain, in order to meet the logical of intellectual technology
Letter demand, the building and development of Internet of Things of new generation also become the most important thing.Narrowband Internet of Things (NB-IOT) is Internet of Things neck
One emerging technology in domain.It is the whole world unified standard that the Internet of Things demands such as wide, low-power consumption, big connection are established towards covering.
Currently, the commercial test of NB-IOT has been completed, the globalization construction of NB-IOT will start.On the other hand, as ocean provides
The increasing of dynamics is developed in source, and the demand of ocean operation and deep-sea detecting to communication increases, and NB-IOT is as a kind of novel
The communication technology, has a wide covering, low-power consumption, can be standby for a long time etc. advantages, the communication being highly suitable in ocean development
Demand.However, when NB-IOT communication module works in marine environment, inevitably will receive seawater corrosion and
The pollution of marine microorganism, this is likely to result in the damage of communication module, influences its normal network connection and data transmission,
Therefore it in order to extend service life of the NB-IOT module in marine environment, just needs that suitable material is selected to come to NB-IOT
Module is packaged protection.
By stainless steel substrates (SS) the chromium-rich oxide skin(coating) institute band thin and dense with good durability and its surface
Come good corrosion resistance and be widely used as the construction material in marine environment.However, when stainless steel substrates exposure for a long time
When Yu Haiyang's environment, it also will receive the biological pollution of various microorganisms, this problem is not now yet by very good solution.Sea
Foreign biological pollution refers to the biology that microorganism and large ocean biology are formed in the underwater surface of ship and marine structure
Film, the detrimental effect in turn resulted in.
Based on tributyl tin, the self-polishing coating of copper, zinc and other antimicrobials has been widely used for preventing ocean raw
Object pollution.However, the release of antimicrobial has serious adverse effect to marine organisms in marine environment.Therefore, it designs
The antifouling anti-rotten coating that no biocides leach is necessary.
At the same time, material surface is modified with nontoxic functional polymer brush to reduce and resist marine organisms
Pollution is a kind of technology that comparison is efficient and environmental-friendly.The atom transfer radical polymerization (SI-ATRP) that surface is caused can
To be effectively used to prepare fine and close and stable polymer brush.Such as these surfaces characteristic such as surface wettability degree and charge,
It is extremely important during biofouling.By SI-ATRP technology, the polymer brush being grafted from material surface can possess narrow
Dispersion index, controllable structure and specific component.Since quaternary ammonium group possesses the ability of destruction bacterial cell membrane, season
The poly- purpurine of ammonium and poly- purpurine brush have good antibacterial ability, have had been reported for the modification surface SS to prevent from giving birth to
Object corrosion.
Summary of the invention
Based on above-mentioned, the present invention provides one kind to be grafted in the encapsulation protection of NB-IOT information module with surface of stainless steel
Hyper-branched polymer is modified, is further introduced into the method for quaternary ammoniated poly- purpurine then to improve the anti-rotten and anti-of stainless steel substrates
Dirty ability, this method have the advantages that safe and nontoxic, efficient and environmentally friendly.
Technical solution of the present invention is as follows:
A kind of anti-rotten and antifouling capacity method in the ocean of NB-IOT information module encapsulation protection stainless steel substrates, including with
Lower step:
(1) the hyper-branched polymer functionalization stainless steel substrates containing purpurine are prepared
Poly-dopamine layer is prepared in stainless steel substrates surface autohemagglutination first, ATRP initiation is further anchored on poly-dopamine layer
Agent then causes ATRP reaction on its surface and hyperbranched poly (vinyl chloride) polymer brush is prepared, finally polymerizeing
Purpurine unit is introduced in object brush, has obtained the dissaving polymer brush containing purpurine.
(2) hyper-branched polymer functionalization stainless steel substrates simulation application Yu Haiyang's environment containing purpurine
The stainless steel substrates of functional modification obtained in step (1) are subjected to Amphora coffeaeformis attachment, false list respectively
As a result the sedimentation experiment of born of the same parents bacterium and barnacle cyprid proves the stainless steel chip base of the dissaving polymer brush functionalization containing purpurine
Plate has better anti-pollution.On the other hand, the analysis result of antibacterial experiment and Tafel polarization curve also indicates that functionalization
Stainless steel substrates substrate also show good corrosion resistance.It is simulating ocean environment in bacterial corrosion experiment, simultaneously
Also for the antibiont corrosive effect of a certain bacterium of quantitative detection, culture solution used is all based on filtering sea.Experiment is selected thin
Bacterium is the typical bacteria strain for being widely present while being also corrosion hull in ocean.
The bacterial species of the antibiont corrosion experiment are unlimited, not only include the double eyebrow algaes of the coffee, barnacle cyprids
And pseudomonad, certain anticorrosive effect is all had to other marine bacterias.
The anti-rotten and antifouling energy in ocean of a kind of NB-IOT information module encapsulation protection stainless steel substrates according to the present invention
The method of power wherein prepares the method for the hyper-branched polymer functional modification stainless steel substrates containing purpurine in step (1) are as follows:
1) on stainless steel substrates covalence graft poly-dopamine process are as follows: prepare stainless steel substrates sheet metal specimens, clean stainless
Steel disc sheet surface is simultaneously dried up with argon gas, and stainless steel substrates thin slice is immersed in Piranha solution H2SO4(95%-97%): H2O2
(30%) after oxidation processes, clean stainless steel substrates sample is depressurized for the surface that stainless steel substrates thin slice is activated in=3: 1, v/v
It is dry；Dopamine is dissolved in and is equipped with the dopamine solution that concentration is 5mg/mL in Tris-HCl buffer (pH 8.5), and will
The steel disc of processing rear surface hydroxyl is immersed in solution, is stirred；After reaction, it cleans, it is dry；
2) process of ATRP initiator is introduced are as follows: the stainless steel substrates of poly-dopamine modification are immersed and contain TEA methylene chloride
In, under ice bath, the dichloromethane solution of 2- bromine isobutyl acylbromide is added drop-wise in reaction mixture, is stirred at room temperature, is obtained
The stainless steel substrates of ATRP initiator modification, are rinsed, dry；
3) cause the ATRP reaction process of vinyl chloride in the stainless steel substrates surface being prepared in step 2) are as follows: will draw
The stainless steel substrates immersion of hair agent modification contains VBC, CuBr ligand, N, N, N', N', N "-five methyl diethylentriamine and benzene first
In ether reaction mixture, so that carrying out the atom transition free radical polymerization reaction of 4- vinyl chloride on stainless steel substrates surface；
Then suspension argon-degassed seals the reaction tube；Reaction prepares the print of hyperbranched poly (vinyl chloride) grafting；
After polymerization, wash, it is dry；
4) process of the stainless steel substrates surface coupling purpurine for the hyper-branched polymer brush modification being prepared in step 3) are as follows:
The stainless steel substrates and equimolar α that step 3) is obtained, the chloro- paraxylene of α '-two and 4,4'- bipyridyl mixture are in diformazan
It is reacted in base formamide, and then obtains the stainless steel substrates of the hyper-branched polymer functionalization of purpurine coupling.
Further, the polymer is hyperbranched polyvinylbenzylchloride.
The present invention also provides a kind of anti-rotten and antifouling capacity the NB-IOT information modules in ocean to encapsulate protection stainless steel substrates
Preparation method, i.e., above-mentioned specific experiment step such as Fig. 1 for preparing functionalization of polymers stainless steel substrates:
1. the covalence graft poly-dopamine on SS substrate
The SS sheet metal specimens of 2cm × 2cm, and successively deionized water are prepared, acetone and EtOH Sonicate clean 5 minutes to clean
Surface.Then clean SS thin slice is cleaned again with deionized water and is dried up with argon gas.It is molten that SS thin slice is immersed in Piranha
Liquid (H2SO4(95%-97%): H2O2(30%)=3: 1, v/v) in activate the surface of SS thin slice within 30 minutes.Piranha solution
Original oxide can be removed and make stainless steel substrates surface rich in a large amount of hydroxyl, be expressed as the surface SS-OH.Oxidation processes
Afterwards, clean SS sample is dried under reduced pressure.In order to which dopamine to be fixed on stainless steel substrates, dopamine is dissolved in 10mM's
It is equipped with concentration in Tris-HCl buffer (pH8.5) and is the dopamine solution of 5mg/mL, and SS-OH substrate is immersed in solution
It is middle to be kept for 24 hours.Reaction mixture is sufficiently stirred to prevent from depositing unwanted particle on surface.After reaction, it takes out
Substrate, it is clear with deionized water and be dried under reduced pressure.Dopamine occurs autohemagglutination and generates poly-dopamine (PDA) layer and be firmly anchored
On substrate.The surface of poly-dopamine coating is expressed as the surface SS-PDA.
2. introducing ATRP initiator
In order to be introduced into alkyl bromide as ATRP initiator on substrate, the immersion of SS-PDA substrate is contained into 2.0mL
In the 20mL methylene chloride of (14.4mmol) TEA.Under ice bath, by 10mL2- bromine isobutyl acylbromide (1.8mL, 3.34g,
Dichloromethane solution 14.4mmol) is added drop-wise in reaction mixture.Then, reaction mixture is stirred at room temperature 24 hours.
Gained surface is expressed as the surface SS-PDA-Br, then successively uses 10mL acetone, ethyl alcohol and deionized water flush three times, and
Depressurize lower drying.
3. the ATRP reaction that vinyl chloride is caused on surface
SS-PDA-Br coupons are immersed and contain 1.4127mLVBC (10mmol), 14.4mgCuBr (0.1mmol) ligand,
20.84 μ L (0.1mmol) N, N, N', N', N "-five methyl diethylentriamines (PMDTA) and 30mL methyl phenyl ethers anisole reaction mixture
In, so that carrying out the ATRP reaction of 4- vinyl chloride (VBC) on the surface SS-PDA-Br.Suspension argon-degassed about 30
Minute to remove the oxygen of dissolution.Then the reaction tube is sealed.24 hours are reacted at 120 DEG C to prepare hyperbranched polyethylene
The print of base benzyl chloride grafting, is expressed as the surface SS-HPVBC.After polymerization, with THF, methanol and deionized water washing
The SS sample of HPVBC grafting is to remove unreacted monomer and remaining homopolymer.Then they are done in vacuum desiccator
It is dry.
4. being coupled purpurine on the surface SS-HPVBC
By the surface SS-HPVBV and equimolar α, the chloro- paraxylene of α '-two and 4,4'- bipyridyl (each 0.1M) mixture
It is reacted 48 hours at 70 DEG C in dimethylformamide (DMF), and then obtains the surface SS-HPVBC of purpurine coupling.Reaction knot
Shu Hou successively uses THF, and methanol and distilled water thoroughly wash functionalized stainless steel substrates substrate, to remove unreacted reagent.
Finally the stainless steel substrates substrate (SS-PViologen) that purpurine is coupled is dried under reduced pressure.
The present invention also provides a kind of hyper-branched polymer functionalization stainless steel substrates containing purpurine, by it is above-mentioned prepare it is hyperbranched
Prepared by the method for polymer functionalization stainless steel substrates.
Purpurine has sterilization and anti-corrosion property energy in the present invention, and the present invention is prepared for purpurine using 4,4'- bipyridyl.Then I
Attempt to introduce purpurine on stainless steel substrates surface, to improve its sterilization, antifouling and anticorrosive property.To achieve it,
Polymer precursor poly-dopamine is covalently fixed on to the stainless steel substrates surface of surface oxidation first, an alkyl is subsequently introduced
Halide ATRP initiator.Then, in the carry out ATRP polymerization on the surface SS-PDA-Br, hyperbranched polyethylene base benzyl has been obtained
Chlorine polymer brush.The covalent interaction being then based between the benzyl chloride and bipyridyl of metal substrate surface introducing, and be added
The dissaving polymer brush containing purpurine has been prepared in the chloro- paraxylene of α, α '-two, passes through fixed benzyl cl radical and connection
Purpurine part is introduced metal substrate surface by the covalent interaction between pyridine.In addition, sealing end pyridine groups by with benzyl
Chlorine is coupled and is quaternized.Stainless steel substrates after the method modification have good anti-rotten and antifouling capacity in marine environment.
Compared with prior art, provided by the invention to build and protect with stainless using the base station functionalization of polymers NB-IOT
Steel disc (SS) plate improves antibiont corrosion and resistant to pollution method has the following beneficial effects:
(1) stainless steel substrates can be effectively improved using the dissaving polymer brush functional modification stainless steel substrates containing purpurine to resist
Biological corrosion and antifouling capacity, while also there is nontoxic, Environmental Sustainability, commercial viability, durability and high-performance etc. are excellent
Point.
(2) method of modifying is simple and easy, Yi Jinhang large-scale production, is expected to anti-applied to the encapsulation of NB-IOT module
Shield.
Detailed description of the invention
Fig. 1 is that stainless steel substrates (SS) surface of the dissaving polymer functionalization containing purpurine prepares schematic diagram.
Fig. 2 is living cells (a, c, e, g) and dead cell (b, d, f, h) after exposing 4 hours in false unicellular bacterium culture medium
Be in (a, b) original ss, (c, d) SS-PDA, (e, f) SS-PDA-Br, (g, h) SS-HPVBC and (i, j) SS- respectively
Fluorescence micrograph on the surface PViologen.
Fig. 3 is to be immersed in 30 ‰ salinity, 24 in Amphora coffeaeformis filtering sea suspension (every milliliter of 105 bacterium cells)
(a) original ss, (b) SS-PDA-Br, (c) SS-HPVBC after hour, (d) fluorescence microscopy figure on the surface SS-PViologen
Picture.
After Fig. 4 impregnates 24 hours in algae suspension (every milliliter of 105 cells), on the original and functionalization surface SS
Double eyebrow algaes adhere to situation.Error line indicates duplicate standard deviation three times.Illustration is thin at double eyebrow frustule quantity and 690nm
The fluorescence intensity figure of born of the same parents and matched curve.
Fig. 5 is the barnacle Venus children adhere on the surface original and functionalized SS or dead after 24 hours sedimentation periods
Percentage of the body relative to total amount.
Fig. 6 is to have supported (a) 7 in false unicellular bacterium culture medium medium temperature, (b) 14, (c) 21 and (d) after 35 days, original SS, SS-
The Tafel polarization curve of PDA-Br, SS-HPVBC, SS-PViologen sample.
Specific embodiment
The following are a kind of anti-marine organisms of NB-IOT information module encapsulation protection stainless steel plate provided by the invention are rotten
The specific embodiment of erosion and pollution ameliorative way.
The stainless steel substrates preparation of specimen process for the functional modification being previously mentioned in following embodiments is as follows:
1) on SS substrate covalence graft poly-dopamine process are as follows: prepare the SS sheet metal specimens of 2cm × 2cm, and successively
Deionized water, acetone and EtOH Sonicate, which clean 5 minutes, carrys out clean surface.Then by clean SS thin slice with deionized water again
It cleans and is dried up with argon gas.SS thin slice is immersed in Piranha solution (H2SO4(95%-97%): H2O2(30%)=3: 1, v/
V) surface of SS thin slice is activated within 30 minutes in.Piranha solution can remove original oxide and make stainless steel substrates surface
Rich in a large amount of hydroxyl, it is expressed as the surface SS-OH.After oxidation processes, clean SS sample is dried under reduced pressure.In order to by DOPA
Amine is fixed on stainless steel substrates, and dopamine is dissolved in outfit concentration in the Tris-HCl buffer (pH 8.5) of 10mM and is
The dopamine solution of 5mg/mL, and SS-OH substrate is immersed in solution and is kept for 24 hours.Be sufficiently stirred reaction mixture with
It prevents from depositing unwanted particle on surface.After reaction, substrate is taken out, it is clear with deionized water and be dried under reduced pressure.DOPA
Amine occurs autohemagglutination and generates poly-dopamine (PDA) layer and be firmly anchored on substrate.The surface of poly-dopamine coating is expressed as
The surface SS-PDA.
2) process of ATRP initiator is introduced are as follows: on poly-dopamine layer in order to introduce alkyl bromide as ATRP initiator
Onto substrate, SS-PDA substrate is immersed in the 20mL methylene chloride containing 2.0mL (14.4mmol) TEA.It, will under ice bath
The dichloromethane solution of 10mL2- bromine isobutyl acylbromide (1.8mL, 3.34g, 14.4mmol) is added drop-wise in reaction mixture.Then,
Reaction mixture is stirred at room temperature 24 hours.Gained surface is expressed as the surface SS-PDA-Br, then successively uses 10mL third
Ketone, ethyl alcohol and deionized water flush three times, and are dried under reduced pressure.
3) cause the ATRP reaction process of vinyl chloride in the stainless steel substrates surface being prepared in step 2) are as follows: will
SS-PDA-Br coupons, which immerse, contains 1.4127mLVBC (10mmol), 14.4mg CuBr (0.1mmol) ligand, 20.84 μ L
In (0.1mmol) N, N, N', N', N "-five methyl diethylentriamine (PMDTA) and 30mL methyl phenyl ethers anisole reaction mixture, so that
The ATRP reaction of 4- vinyl chloride (VBC) is carried out on the surface SS-PDA-Br.Suspension with argon-degassed about 30 minutes with
Remove the oxygen of dissolution.Then the reaction tube is sealed.24 hours are reacted at 120 DEG C to prepare hyperbranched polyethylene base benzyl
The print of chlorine grafting, is expressed as the surface SS-HPVBC.After polymerization, with THF, methanol and deionized water washing HPVBC grafting
SS sample to remove unreacted monomer and remaining homopolymer.Then they are dry in vacuum desiccator.
4) process of the stainless steel substrates surface coupling purpurine for the hyper-branched polymer brush modification being prepared in step 3)
Are as follows: by the surface SS-HPVBV and equimolar α, the chloro- paraxylene of α '-two and 4,4'- bipyridyl (each 0.1M) mixture are two
It is reacted 48 hours at 70 DEG C in methylformamide (DMF), and then obtains the surface SS-HPVBC of purpurine coupling.After reaction,
THF is successively used, methanol and distilled water thoroughly wash functionalized stainless steel substrates substrate, to remove unreacted reagent.Finally will
The stainless steel substrates substrate (SS-PViologen) of purpurine coupling is dried under reduced pressure.
Embodiment 1:
In the present embodiment, bacterial adhesion analysis is carried out to the stainless steel substrates template of functional modification.
Implementation steps:
Using marine bacteria, the NCIMB2021 of false unicellular Pseudomonas come assess polymer coating bacterial adhesion characteristic and
Bactericidal potency.False unicellular bacterium is cultivated in simulated seawater full of nutrition.Every liter of culture medium rich in nutrition by
23.476gNaCl；3.917gNa2SO4； 0.192gNaHCO3；0.664gKCl；0.096gKBr；10.61gMgCl2·6H2O；
1.469gCaCl2·2H2O；0.026gH3BO3； 0.04gSrCl2·6H2O, 3g bacto peptone and 1.5g yeast extract group
At.The pH of culture medium is adjusted to 7.2 ± 0.1, and the high pressure sterilization 20min under 121 DEG C and 15psi using 5MNaOH solution.
After 37 DEG C are cultivated 3 days, by each bacterial suspension with 2700rpm centrifugation 10 minutes.Supernatant is removed, it is false slender
Born of the same parents' bacterium deposit washes twice with simulated seawater and re-starts suspension, concentration 107A cell/mL.By each sample substrate
It is cut into 1cm × 1cm sample, is put into 24 orifice plates (Nalge, NuncInt., Rochester, NY), and in 37 DEG C of static item
4h is immersed in 1mL bacterial suspension under part.The bacterial suspension in each hole is gently removed by suction using pipette,
And 1mL ultrapure water is slowly added to each hole along wall.Subsequent gentle aspiration simulated seawater.
With milli-Q water three times to remove nonadherent bacterium after, with LIVE/DEADBacLight bacterial action reagent
Box dyes every kind of sample substrate 15 minutes.The bacterial cell for being fixed on sample surfaces can have a green filter (to swash
Hair/transmitting: 450-490 nm/500-550nm) and red filter (excitation/emission: 510-560nm/605-685nm)
Told under NikonECLIPSETi-U fluorescence microscope (Tokyo) bacterial cell life or death (living cells present green, extremely
Cell presents red).
Each substrate sample is immersed in 1mL3% (v/v) glutaraldehyde water solution at 4 DEG C, and is kept for 24 hours, with
Afterwards successively 20,40,60,80 and 100% the unicellular bacterium of vacation for carrying out secure attachment for ethyl alcohol continuous dehydration 5 minutes.Then by sample
Product are dried at reduced pressure conditions, are then sputtering one layer thin platinum layer (JFC-1300AutoFineCoater) above.With scanning electricity
(SEM, model JSM-5600LV, JEOLCo., Tokyo) is imaged in sub- microscope.
Interpretation of result:
Fig. 2 is the fluorescence microscope images on the surface SS before and after functionalization after being exposed to pseudomonad inoculation medium 4 hours,
After with combination dyeing, green is presented in living cells under fluorescence microscope, and red is presented in dead cell.In pure SS
Surface is observed that the bacterium cell (separately distributed or with tuftlet formal distribution) of the high concentration with green fluorescence phenomenon
(Fig. 2 a), only a small number of separate cells (Fig. 2 b) with red fluorescence phenomenon, this shows that the bacterium of most of pseudomonads is thin
Born of the same parents are intact on the original surface SS, and the original surface SS is highly sensitive to false unicellular bacterium adherency.
On the surface SS-PDA and SS-PDA-Br it has also been discovered that the living unicellular bacterium of vacation of high concentration presence (Fig. 2 c and
Fig. 2 e), although the quantity of the unicellular bacterium of vacation on the surface SS-PDA and SS-PDA-Br is than opposite on the original surface SS
It is less.Compared with the original surface SS and SS-PDA, more recognizable dead cell numbers are observed on the surface SS-PDA-Br
Mesh, this may be attributed to bactericidal effect of the bromide to the surface SS-PDA-Br.
It is compared on surface with original SS, SS-PDA with SS-PDA-Br, the vacation for being attached to the work on the surface SS-HPVBC is unicellular
The quantity (Fig. 2 g) of bacterium is declined slightly, and most bacterium cells are all dead cells.It is whole for the surface SS-PViologen
Only a small number of living cells sparse distributions (Fig. 2 i) on a surface, and compared with the surface SS-HPVBC, dead bacterial cell (Fig. 2 j)
Greatly reduce.The surface SS-PViologen has better antibacterial and anti-pollution, because of the hydrophilic surface SS-PViologen
The interface energy of (contact angle is 17 ± 1 °) with lower polymer-water.The aquation of height increases biological foulant attachment
When the energy that is dehydrated, cause a small amount of particle-bound bacteria cell.Bactericidal activity and positively charged pyridine (N+) cation surface
Concentration is associated.Known pyridine polycation chain can cause the destruction of cell membrane, cause the loss of intracellular matter.SS-
The hydrophilic component on the surface PViologen can prevent biological fouling, and the quaternary ammonium component on the surface SS-PViologen plays antibacterial agent
Effect.
Therefore, it is found through experiments that, purpurine is as the pyridine type polymer with polycation group, for being functionalized
After the test button of modification of surfaces oxidation, there is good antibacterial and anti-pollution.
Embodiment 2:
In the present embodiment, the analysis of Amphora coffeaeformis adhiesion test is carried out to the stainless steel substrates template of functional modification.
Implementation steps:
Amphora coffeaeformis (UTEX reference number B2080) need to be cultivated before use in tissue culture flasks.It, will at 24 DEG C
It is placed in F/2 medium, and is in 12 hours/12 hours light dark alternate environments, maintains at least one week.When coffee shape
Double eyebrow phycomycetes acquire cell when Flasks surface converges, and are gently scraped alga cells by using cell scraper from tissue
It gently takes out on the surface of culture bottle.Double eyebrow algaes are destroyed by using 35 μm of continuous liquid reliefs of Nitex strainer and filtering.Make
The cell number of double eyebrow algaes of harvest is measured with hemacytometer, and further preparing concentration is 105The seawater of a cell/mL
Solution, seawater contains 30% salinity, and is filtered using 0.22 μm of filter.
Sedimentation is tested, each sample substrate is cut into the sample of 1cm × 1cm size and is immersed in 1mL24 orifice plate
In double eyebrow algae suspension.Infall process carries out 24 hours at 24 DEG C, and wherein illumination 12 hours, are protected from light 12 hours.It is tied in sedimentation
Shu Hou, with 30% salinity, lightly cleaning base plate is three times, any loose and unstable to remove for 0.22 μm of filtered seawater
Diatom.The cleaning procedure of double eyebrow algae adherence tests is similar to the cleaning procedure that bacterial adhesion is tested, and all ultrapure waters are all by sea
Water replaces.
For qualitative determination, using Nikon ECLIPSE Ti-U fluorescence microscope (Tokyo) in red filter
The double eyebrow frustules of sedimentation on 1cm × 1cm sample are observed under (excitation/emission: 510-560nm/605-685nm).For quantitative
The substrate of each sedimentation is transferred to 2mL30% salinity, in 0.22 μm of filtered seawater by measurement.It is immersed into ultrasonic wave
In 10 minutes to remove the diatom of sedimentation.Then, this sample is divided into 200 μ L and is transferred to 96 hole microtest plates
In.In the excitation wavelength (λ equipped with 440nmexS) Tecan Infinite M200 microplate reader (It is auspicious
Scholar) on measurement launch wavelength be 690nm each hole fluorescence intensity.By 30% salinity, 0.22 μm of filtered seawater it is glimmering
Luminous intensity is set as blank.Each measurement is in triplicate to obtain average value.
Interpretation of result:
In this example, double eyebrow algae adhesion detections are used to the anti-pollution on the surface SS of Study Polymer Melts grafting.It is shown in Fig. 3
The fluorescence microscope image for being immersed in the double eyebrow frustules adhered on the sample in algae suspension after 24 hours is shown.It is double
Eyebrow algae all seriously polluted the original surface SS and SS-PDA-Br (Fig. 3 a, b) either in the form of discrete or cluster, however
Fouling caused by the double eyebrow algaes observed on the surface SS-HPVBC slightly reduces (Fig. 3 c).In contrast, SS-PViologen
Only adhere to a small amount of frustule (Fig. 3 d) on surface.The high-hydrophilic polymer brush on the surface SS-PViologen keeps seawater continuously dilute
Microalgae quantity is released, to reduce its adherency on modified surface.
Fluorescence microscopy images provide only qualitative comparison of the surface SS of polymer grafting to double eyebrow algae adherency are influenced.It is logical
It crosses supersonic cell disengaging and the detection of chlorophyll autofluorescence further adheres to pair eyebrow frustules and is quantitatively evaluated.In 440nm
Excitation wavelength (λex) under, the chlorophyll of Amphora coffeaeformis cell shows autofluorescence, and the wavelength of emission peak is on the left side 690nm
It is right.Therefore, as shown in calibration curve (Fig. 4 illustration), the fluorescence intensity of planktonic algae suspension is directly proportional to its cell density.
Therefore, be functionalized the surface SS on double eyebrow frustules quantity than can from be functionalized SS and the original surface SS fluorescence intensity
Than being derived from, this quantization method is true and reliable for the whole fouling area for evaluating surface.Fig. 4 is shown in original
The quantitative determination begun with double eyebrow algaes adherency on the surface SS of polymer-coated.Compared with the original surface SS, SS-PDA and SS-
Still there is 87% and 81% area serious scale on the surface PDA-Br respectively, and the surface SS-HPVBC and SS-PViologen is divided
Double eyebrow algae adherency are not made to reduce by 46% and 12% respectively.These results are kissed very much with the Qualitative observations under fluorescence microscope
It closes, SS-PViologen surface exhibits go out best anti-pollution.
The anti-pollution on the surface SS-PViologen is attributable to quaternized viologen polymer brush with high-hydrophilic.Season
The viologen polymer brush of ammonium have preferable antifouling efficacy because they can more strongly with water molecules so that SS-
PViologen polymer, which more " is liked " contacting rather than biological substance (such as double eyebrow algae microalgae cell) with water, to be contacted.SS-
Therefore the surface PViologen shows to fight the best anti-pollution of double eyebrow algae adherency.
Therefore, it is found through experiments that, purpurine is as the pyridine type polymer with polycation group, for being functionalized
After the test button of modification of surfaces oxidation, there is good antibacterial and anti-pollution.
Embodiment 3:
In the present embodiment, the analysis of cypris larva sedimentation experiment is carried out to the stainless steel substrates template of functional modification.
Implementation steps:
The adult barnacle (line barnacle) collected from Singapore Kranji mangrove supports the open cycle aquarium at 25 DEG C
In, it is used at 25 DEG C daily, with the microalgae feed mixtures of the planktonic organism of 1:1 (v/v) and Chaetoceros muelleri, concentration is every
Milliliter 5 × 105A boiled shrimps with shell in salt water young feeds.The algae media of replacement in every 2 days.The young enters gland Jie's stage after 5 days.
Before the assay, the cypris larva of harvest 4 DEG C further growth 2 days, and at room temperature adapt to 30 minutes.
The analysis by sedimentation of cypris larva is carried out with sessile drop method.About 500 μ L are contained to the filtering of about 40 barnacle cyprids
Seawater be respectively added to 2cm × 2cm before modified after SS substrate sample in.Each sample is placed in culture dish and is covered,
To reduce drop evaporation rate.Culture dish is placed in the black plastic case of sealing, dark and moist ring is kept with wet cloth
Border is kept for 24 hours.After 24 hours, sample is taken out, and the quantity for counting oriented cyprids under the microscope is total with it
Number.Each sedimentation test carries out three repeated experiments to obtain reliable average result.
Interpretation of result:
In instances, the cypris larva of adult barnacle (line barnacle) is selected to study functionalization of polymers SS under static conditions
The external anti-fouling effect on surface.Sedimentation measurement carried out to about 40 young using sessile drop method, Shi Changwei 24 hours.Fig. 5 is shown
Exposure duration is the percentage of sedimentation and dead cypris larva on original and functionalization SS surface after 24 hours.About
84%, 72% and 63% barnacle cypris larva respectively falls in the original surface SS, SS-PDA and SS-PDA-Br, shows them
To the high susceptibility of large-scale fouling.It is different from the surface SS-HPVBC and SS-PViologen, original SS, SS-PDA and SS-
The surface PDA-Br has oxygen-containing polar functional group abundant, allows to directly mutual with protein by ionic bond and hydrogen bond
Effect, causes more barnacle cypris larvas to be deposited in the original surface SS, SS-PDA and SS-PDA-Br.On the original surface SS
More barnacle cypris larva is settled, this may be because hydroxyl has the initial elicitation procedure of underwater attachment
Great influence, the glue protein of barnacle need access to the firm surface SS with water molecules and replace water, so with the surface SS
Coupling.
The sedimentation ratio on the surface of polymer grafting greatly reduces, and the cypris larva sedimentation rate of SS-HPVBC is lower, is
26%.Although cypris larva sedimentation ratio greatly reduces on the surface SS-HPVBC, relatively large amount of barnacle sedimentation can attribution
In the hydrophobic interaction of protein molecule and hyperbranched poly (VBC) layer.On the contrary, the quaternized surface SS-PViologen
Barnacle adherency (0%) is not observed.Highly hydrophilic quaternized viologen polymer brush eliminates barnacle in infall process
The attachment of the glycoprotein glue of cypris larva, and the effect of facilitate the low pollution on the surface SS-PViologen.
After the surface of cypris larva type corresponding with its contacts 24 hours, in addition to the barnacle cypris larva secured
Except, the Mortality Ratio of cypris larva on original SS, SS-PDA, SS-PDA-Br, the surface SS-HPVBC and SS-PViologen
Example is respectively 4%, 5%, 6%, 13% and 7%.In addition to the surface SS-HPVBC, be functionalized the surface SS death rate with it is original
The surface SS is close.The surface SS of VBC functionalization have slight toxicity, but by with purpurine part on the surface SS-HPVBC
Coupling toxicity can be reduced to non-toxic level.Other than the surface SS-HPVBC, the death rate under every kind of experiment is lower than 11%
Show that there is no toxic residuas on most of sample substrates.
Therefore, the sedimentation measurement of barnacle cypris larva shows that the surface SS-PViologen has good anti-pollution.
Embodiment 4:
In the present embodiment, electrochemical analysis is carried out to the stainless steel substrates template of functional modification.
Implementation steps:
By using Autolab PGSTAT 30 (EcoChemie, Utrecht, Holland) electrochemical workstation measurement
Tafel polarization curve assesses the corrosion resistance of surface functionalization sample.It will before modified using Semi-continuous cultivation growth pattern
Sample afterwards is exposed in pseudomonad inoculation medium, is kept respectively 7,14,21 and 35 days.Terminate in the defined time
Afterwards, sample is promptly removed from culture medium, and be embedded into the fixator of a polyvinylidene fluoride (PVDF), stayed
A 1.0cm out2Border circular areas as working electrode, carry out electrochemical analysis in three electrode glass etching tanks.Platinum filament electricity
Pole is used as to electrode, and Ag/AgCl electrode is as reference electrode.With 1 mv s sweep speed in -250 to+250 millivolts of models
Enclose it is interior scanning come obtain Tafel curve [18].Use the inhibition efficiency (IE) of following formula gauging surface functionalization sample:
Wherein ioAnd icorrIt is the corrosion current for the functionalization front and back sample analyzed based on Tafel polarization curve respectively
Density.
Interpretation of result:
Polarization curve, which can be used to measure test button, an inhibitor, mushroom, antimicrobial and coating there are when
Instantaneous corrosion rate, and appropriate means of the electrochemical reaction for monitoring functionalized surfaces.Fig. 6, which is shown, to be exposed to
The Tafel polarization for being vaccinated in the culture medium of pseudomonad the original and surface functionalization sample after 7,14,21 and 35 days is bent
Line.As having described by research, the crosspoint that the linear segment of anode and cathode branch is extrapolated to them can be obtained
Obtain Tafel slope (βcAnd βa), corrosion potential (Ecorr) and corrosion electric current density (icorr) value.The analysis result of Tafel figure
It is summarised in shown in table 1.From the Tafel polarization curve in Fig. 6 can from obtain, when being exposed to the training for being vaccinated with pseudomonad
When supporting in base, the corrosion potential E of functionalization samplecorrPast negative direction that can be slight compared to original sample is mobile.According to mixing
Potential theory, this phenomenon may be attributed to the reduction of the cathodic process of the modified sample in surface.
For given exposure period, the i of the modified sample of purpurinecorrValue is much smaller than the i of corresponding original samplecorrValue, table
It is bright in the medium for being vaccinated with pseudomonad, the surface SS of the coupling of organic layer has preferably corrosion compared with the original surface SS
Inhibitory activity.The inhibition efficiency (IE) on the surface SS-PViologen is up to about 84.60% after 7 days of contact, and is incubating 35
Still there are the data close to 78.20% after it.There is relatively high inhibition efficiency to confirm purple during entirely exposing to the open air
Essence functionalization sample has good corrosion inhibitory activity, can protect following metal base and invades from microorganism with other
The invasion of corrosion substance.
For the original SS sample being exposed in false unicellular bacterium inoculation medium, corrosion rate with exposure duration increasing
It grows and accelerates, and reach 0.219mmy after incubating 35 days-1, the oxide layer on metal surface is shown in pseudomonad
In gramnegative bacterium bacterial strain attack under gradually lose its protective value.However, the surface SS-PViologen is in difference
Exposure period after corrosion rate be still significantly less than the original surface SS, this demonstrate show on the surface SS-PViologen
There is viologen polymer thin layer good protective value, quaternary ammonium salt and pyridine moiety to rise in the corrosion to SS sample inhibits
Important function.It increases greatly than the inhibition efficiency (IE) on the original surface SS-PDA-Br and SS-HPVBC on the surface SS-PViologen
Add, this further supports this point, shows that the surface SS of purpurine grafting has good corrosion resistance.
Table 1 exposes original and surface functionalization sample Tafel after different time in the culture medium of inoculation pseudomonad
Polarization curve calculated result is summarized
aβcIt is the Tafel slope of cathodic polarization curve
bβaIt is the Tafel slope of anodic polarization curves
cEcorrRefer to potential when electric current reaches zero under polarization
dCR indicates corrosion rate
eIE indicates to inhibit efficiency
The above results explanation modifies stainless steel plate using polymer functionalization, it is rotten can be effectively improved stainless steel antibiont
Erosion and antifouling capacity, and it with environmentally friendly, Environmental Sustainability, commercial viability, durability and high-performance etc. are excellent
The technology, is applied to the modification of stainless steel plate by point, and further applies the encapsulation protection of NB-IOT information module, can be had
Effect extends service life when NB-IOT information module works in marine environment, reduces maintenance cost.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to limit the present invention, all any modifications made in spirit of the invention, benefit
Fill or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of anti-rotten and antifouling capacity method in the ocean of NB-IOT information module encapsulation protection stainless steel substrates, feature exist
In, comprising the following steps:
(1) stainless steel substrates of the hyper-branched polymer functional modification containing purpurine are prepared
First in stainless steel substrates material surface covalence graft poly-dopamine layer, ATRP initiator 2- is then introduced in poly-dopamine
Bromine isobutyl acylbromide obtains the stainless steel of hyperbranched polyvinylbenzylchloride brush modification for causing vinyl chloride polymerization
Piece, and it is further introduced into purpurine unit, the hyperbranched chain containing viologen polymer has been prepared to get the hyperbranched height containing purpurine is arrived
The stainless steel substrates of molecular functionization modification；
(2) by stainless steel substrates simulation application Yu Haiyang's environment of the functional modification of hyper-branched polymer containing purpurine, carry out it is antifouling and
Anti-corrosion property can be evaluated and tested.
2. the anti-rotten and antifouling energy in ocean of a kind of NB-IOT information module encapsulation protection stainless steel substrates according to claim 1
The method of power, which is characterized in that pass through ATRP reactive grafting hyperbranched polyethylene base benzyl on stainless steel substrates surface in step (1)
After chlorine brush, purpurine further is introduced in the polymer brush, to improve the concentration of quaternary ammonium salt in the system.
3. the anti-rotten and antifouling energy in ocean of a kind of NB-IOT information module encapsulation protection stainless steel substrates according to claim 1
The method of power, which is characterized in that the method for hyper-branched polymer functional modification stainless steel substrates of the preparation containing purpurine in step (1)
Are as follows:
1) on stainless steel substrates covalence graft poly-dopamine process are as follows: preparation stainless steel thin slice sample, clean stainless steel thin slice
Surface is simultaneously dried up with argon gas, and stainless steel substrates thin slice is immersed in Piranha solution H2SO4(95%-97%): H2O2(30%)=3:
The surface that stainless steel substrates thin slice is activated in 1, v/v, after oxidation processes, clean stainless steel substrates sample is dried under reduced pressure；By DOPA
Amine is dissolved in the dopamine solution for being equipped with that concentration is 5mg/mL in Tris-HCl pH of buffer 8.5, and processing rear surface is contained hydroxyl
The steel disc of base is immersed in solution, stirring；After reaction, it cleans, it is dry；
2) process of ATRP initiator is introduced are as follows: the stainless steel substrates of poly-dopamine modification are immersed and are contained in TEA methylene chloride,
Under ice bath, the dichloromethane solution of 2- bromine isobutyl acylbromide is added drop-wise in reaction mixture, is stirred at room temperature, obtains ATRP initiation
The stainless steel substrates of agent modification, are rinsed, dry；
3) cause the ATRP reaction process of vinyl chloride in the stainless steel substrates surface being prepared in step 2) are as follows: by initiator
The stainless steel substrates immersion of modification contains VBC, and CuBr ligand, N, N, N', N', N "-five methyl diethylentriamine and methyl phenyl ethers anisole are anti-
It answers in mixture, so that carrying out the atom transition free radical polymerization reaction of 4- vinyl chloride on stainless steel substrates surface；It suspends
Then liquid argon-degassed seals the reaction tube；The print of reaction preparation hyperbranched polyethylene base benzyl chloride grafting；Polymerization terminates
Afterwards, it washs, it is dry；
4) process of the stainless steel substrates surface coupling purpurine for the hyper-branched polymer brush modification being prepared in step 3) are as follows: will walk
The rapid stainless steel substrates 3) obtained and equimolar α, the chloro- paraxylene of α '-two and 4,4'- bipyridyl mixture are in dimethyl formyl
It is reacted in amine, and then obtains the stainless steel substrates of the hyper-branched polymer functionalization of purpurine coupling.
4. the anti-rotten and antifouling energy in ocean of a kind of NB-IOT information module encapsulation protection stainless steel substrates according to claim 1
The method of power, which is characterized in that the polymer is hyperbranched polyvinylbenzylchloride.
5. the anti-rotten and antifouling energy in ocean of a kind of NB-IOT information module encapsulation protection stainless steel substrates according to claim 1
The method of power, which is characterized in that the bacterial species of the anticorrosive experiment are unlimited, not only include the double eyebrow algaes of the coffee, barnacle
Cyprids and pseudomonad all have certain anticorrosive effect to other marine bacterias.
6. a kind of method of the hyper-branched polymer functionalization stainless steel substrates prepared containing purpurine, which is characterized in that including walking as follows
It is rapid:
1) on stainless steel substrates covalence graft poly-dopamine process are as follows: prepare stainless steel substrates sheet metal specimens, clean stainless steel substrates
Sheet surface is simultaneously dried up with argon gas, and stainless steel substrates thin slice is immersed in Piranha solution H2SO4 (95%-97%): H2O2
(30%) surface that stainless steel substrates thin slice is activated in=3:1, v/v after oxidation processes, clean stainless steel substrates sample is depressurized dry
It is dry；Dopamine is dissolved in and is equipped with the dopamine solution that concentration is 5mg/mL in Tris-HCl pH of buffer 8.5, and will processing
The steel disc of rear surface hydroxyl is immersed in solution, stirring；After reaction, it cleans, it is dry；
2) process of ATRP initiator is introduced are as follows: the stainless steel substrates of poly-dopamine modification are immersed and are contained in TEA methylene chloride,
Under ice bath, the dichloromethane solution of 2- bromine isobutyl acylbromide is added drop-wise in reaction mixture, is stirred at room temperature, obtains ATRP initiation
The stainless steel substrates of agent modification, are rinsed, dry；
3) cause the ATRP reaction process of vinyl chloride in the stainless steel substrates surface being prepared in step 2) are as follows: by initiator
The stainless steel substrates immersion of modification contains VBC, and CuBr ligand, N, N, N', N', N "-five methyl diethylentriamine and methyl phenyl ethers anisole are anti-
It answers in mixture, so that carrying out the atom transition free radical polymerization reaction of 4- vinyl chloride on stainless steel substrates surface；It suspends
Then liquid argon-degassed seals the reaction tube；The print of reaction preparation hyperbranched polyethylene base benzyl chloride grafting；Polymerization terminates
Afterwards, it washs, it is dry；
4) process of the stainless steel substrates surface coupling purpurine for the hyper-branched polymer brush modification being prepared in step 3) are as follows: will walk
The rapid stainless steel substrates 3) obtained and equimolar α, the chloro- paraxylene of α '-two and 4,4'- bipyridyl mixture are in dimethyl formyl
It is reacted in amine, and then obtains the stainless steel substrates of the hyper-branched polymer functionalization of purpurine coupling.
7. a kind of hyper-branched polymer functionalization stainless steel substrates containing purpurine, prepare hyperbranched high score as described in claim 6
Prepared by the method for subfunction stainless steel substrates.
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