CN103524755A - Preparation method of functionalized carbon nanometer tube/metal complex anti-fouling agent - Google Patents
Preparation method of functionalized carbon nanometer tube/metal complex anti-fouling agent Download PDFInfo
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Abstract
The invention discloses a preparation method of a functionalized carbon nanometer tube/metal complex anti-fouling agent with anti-bacterial and slow release performances, and belongs to the field of anti-fouling agents. The preparation method is characterized by comprising the following steps: grafting a chitosan derivative on the surface of a carboxylation carbon nanometer tube, then respectively introducing copper ions, zinc ions or silver ions on that basis, or further reducing the silver ions into nano-silver, and preparing the functionalized carbon nanometer tube/metal complex anti-fouling agent. The preparation method is simple and easy to operate; due to the preparation method, large-sized precious instruments and equipment are not needed, and the controllable preparation can be effectively realized; the prepared functionalized carbon nanometer tube/metal complex anti-fouling agent has the advantages of very good water solubility, stability, excellent dispersibility, long-acting antibacterial ability, very good application prospect and the like.
Description
Technical field
The present invention relates to the preparation method of carbon nano tube compound material, particularly relate to a kind of preparation method with functionalized carbon nano-tube/metal complexes stain control agent of antibacterial and sustained release performance.
Background technology
Miscellaneous marine organisms that living in the ocean of the length and breadth of land, and in these biologies, have thousands of kinds to there is stained property.Marine biofouling, the biology with stained property be arranged in hull surface under water and be applied to ocean various device surface attachment, growth, breed and cause equipment corrosion and the destruction that produces.The marine attaching organism that is attached to solid surface has been caused the destruction that is attached thing.The loss that marine biofouling brings to the mankind is huge, and research shows, marine microorganism adheres to the material damage causing and the number of resources of losing of losing efficacy accounts for and relates to 70% of extra large material unaccounted-for (MUF) total amount.Along with the mankind are to the further investigation of oceanic resources and exploitation, marine biofouling also becomes one of great difficult problem urgently to be resolved hurrily with protection.
At present, thus the most effective anti-pollution measure be alow or underwater facility brushing antifouling paint reach antifouling object.Organotin was once widely used in marine antifouling coating with its excellent antifouling properties and long-acting work-ing life, but in recent years, people find that it pollutes the marine eco-environment gradually, and serious harm marine organisms.So, can replace the Wuxi of organotin, the R and D of the environmentally friendly stain control agent of low toxicity just become research emphasis in recent years.At present, many antifouling paints that contain the metal-salts such as copper, zinc, silver rely on its excellent bacteriostasis property to be subject to paying close attention to widely, but its ubiquity the short problem of validity period, this has just affected its work-ing life greatly, and the slow-releasing that therefore how to improve stain control agent sterilization component just becomes an important research topic.
Summary of the invention
The problem existing for existing stain control agent technology, the object of this invention is to provide a kind of preparation method with functionalized carbon nano-tube/metal complexes stain control agent of good dispersiveness, long-acting bacteriostasis property.
First the present invention is grafted on chitosan derivatives carbon nanotube (CNT) surface, then introduces on this basis cupric ion, zine ion or silver ions, or by silver ion reduction, is further nanometer silver, prepares functionalized carbon nano-tube/metal complexes stain control agent.
The carbon nanotube adopting in the present invention is carboxylated Single Walled Carbon Nanotube (SWNT) or multi-walled carbon nano-tubes (MWNT), because it has very large specific surface area and nano level cylindrical cavity structure, adsorptive power is very strong, by chitosan functionalization, can improve the shortcomings such as it is easily reunited, hydrophobicity is poor, improve its dispersing property.Chitosan derivatives described in the present invention is cm-chitosan, chitinamine oligosaccharide or glucosamine.Chitosan (Cs), as the product of the de-part ethanoyl of chitin, has the advantages such as nontoxic, good biocompatibility and biodegradability, also has certain bacteriostasis property simultaneously.The basic structure of chitosan is glucosamine (Glucosamine), wherein contains a large amount of amino and hydroxyl, and contains lone-pair electron on amino nitrogen-atoms, and metal ion has unoccupied orbital, so the two can be in conjunction with forming metal complexes.But chitosan only can dissolve in acidic solution, and as the derivative of chitosan, cm-chitosan (cmCs) is having good solvability within the scope of pH value more widely, and there is equally biocidal property, its carboxyl containing can with metal ion Cheng Jian, thereby improve the charge capacity of metal ion, strengthening bacteriostasis property.
The present invention includes following steps:
(1) chloride of carbon nanotube
Carboxylic carbon nano-tube is joined to anhydrous N, in dinethylformamide (DMF), ultrasonic dispersion is after 10 ~ 30 minutes, slowly drip the chloride reagent that is equivalent to 20 ~ 40 times of carboxylic carbon nano-tube quality, under nitrogen protection, at 0 ~ 5 ℃, stir 2 ~ 4 hours, then stirring at room is 2 ~ 4 hours, is finally warmed up to 70 ~ 80 ℃, stirs 12 ~ 24 hours;
(2) preparation of carbon nanotube-cm-chitosan matrix material of covalence graft
Chitosan derivatives is dispersed in anhydrous DMF, stirs 10 ~ 20 hours, make its abundant swelling; Then obtained solution is added drop-wise in step (1) reaction solution, under nitrogen protection, in 100 ~ 130 ℃, reacts 45 ~ 60 hours; After above-mentioned reaction solution cool to room temperature, micropore suction filtration, the solid obtaining distilled water repetitive scrubbing, removes unreacted chitosan derivatives, then uses successively 80 ~ 85% ethanol, absolute ethanol washing dehydration, suction filtration; By vacuum-drying at 40 ~ 80 ℃ of gained solids 8 ~ 20 hours, obtain carbon nanotube-chitosan derivatives matrix material of covalence graft;
(3) preparation of carbon nanotube-cm-chitosan metal complexes stain control agent
Above-mentioned matrix material is joined in deionized water, after ultrasonic dispersion, splash into metal salt solution, stir 20 ~ 30 hours at 20 ~ 30 ℃; Or above-mentioned matrix material is added in well-mixed Silver Nitrate/polyvinylpyrrolidonesolution solution, under UV-irradiation, stir 3 ~ 6 hours at 20 ~ 30 ℃; Reaction finish rear centrifugal, with deionized water repetitive scrubbing until can't detect metal ion in supernatant liquor; Again by products therefrom 40 ~ 80 ℃ of vacuum-dryings 12 ~ 24 hours, obtain functionalized carbon nano-tube/metal complexes stain control agent.
Described carboxylated reagent is the chlorination reagents such as oxalyl chloride, benzene sulfonyl chloride or SULPHURYL CHLORIDE, requires to have suitable stability, and easily removes.
Described chitosan derivatives is cm-chitosan, chitinamine oligosaccharide or glucosamine, requires easily to form stable title complex with metal ion.
Described metal-salt, for soluble copper salt, soluble zinc salt or soluble silver salt etc. can provide the salt of the metal ion with sterilization, bacteriostasis property, requires easily molten, stable.
Compared with prior art, tool of the present invention has the following advantages:
(1) the present invention is by carboxymethyl chitosan grafted branch in carbon nano tube surface, and carbon nanotube-cm-chitosan matrix material of the covalence graft of preparation has good dispersiveness, long-acting bacteriostasis property;
(2) the present invention introduces metal ion, the metal complexes stain control agent of preparation, and its bacteriostasis property obtains strengthening and promotes;
(3) the present invention introduces nanometer silver, and the carbon nanotube grafting glucosamine of preparation carries silver-colored stain control agent, has the advantage such as broad spectrum antibacterial, long-acting bacteriostatic of nanometer silver.
Accompanying drawing explanation
Fig. 1 be carbon nanotube (MWCNT) (a) and carbon nanotube grafting cm-chitosan (MWCNT-cmCs) transmission electron microscope picture (b).
Fig. 2 be carbon nanotube-cm-chitosan-copper complex (MWNT-cmCs-Cu) (a), (b) the specific conductivity curve of solution of cm-chitosan-copper complex (cmCs-Cu).
Fig. 3 be carbon nanotube-cm-chitosan-Zn complex (MWNT-cmCs-Zn) (a), (b) the specific conductivity curve of solution of cm-chitosan-Zn complex (cmCs-Zn).
Fig. 4 is MWCNT-cmCs(a), MWCNT-cmCs-Cu(b) and infrared spectrogram MWCNT-cmCs-Zn(c).
Fig. 5 is MWCNT-cmCs(a), MWCNT-cmCs-Zn(b), MWCNT-cmCs-Cu(c) respectively to streptococcus aureus and intestinal bacteria MWCNT-cmCs(d), MWCNT-cmCs-Zn(e), MWCNT-cmCs-Cu(f) inhibition zone photo figure, every partial enlarged drawing that the photo upper right corner is this inhibition zone.
Fig. 6 is that MWNT-cmCs, MWNT-cmCs-Zn and MWNT-cmCs-Cu are to streptococcus aureus and colibacillary counting process fungistatic effect comparison diagram.
Fig. 7 is the infrared spectrogram of carbon nanotube-glucosamine (MWCNT-glucosamine) matrix material.
Fig. 8 is the XRD figure that carbon nanotube grafting glucosamine carries silver (MWCNT-glucosamine-Ag NPs) stain control agent.
Fig. 9 is that carbon nanotube grafting glucosamine carries the antibacterial loop graph of silver-colored stain control agent to streptococcus aureus (a) and intestinal bacteria (b).
Figure 10 is the reacting flow chart of carbon nanotube-cm-chitosan-copper complex stain control agent.
Figure 11 is the reacting flow chart that carbon nanotube-glucosamine carries silver-colored stain control agent.
Embodiment
Below in conjunction with accompanying drawing and by specific embodiment, further illustrate the present invention, but the invention is not restricted to following specific embodiment.
embodiment 1:the preparation of carbon nanotube-cm-chitosan-copper complex stain control agent.
Reaction raw materials is carboxylated multi-walled carbon nano-tubes, oxalyl chloride, cm-chitosan, copper sulfate, and reaction process is as Figure 10, and wherein carboxylated multi-walled carbon nano-tubes is purchased from Alfa Aesar company, and diameter is 30 ~ 50nm, and carboxylated degree is 0.73%.
The carboxylated multi-walled carbon nano-tubes of 30mg is joined in the anhydrous DMF of 20mL, and ultrasonic dispersion, after 10 minutes, slowly drips 1mL oxalyl chloride, wherein at N
2under protection, 0 ℃ is stirred 2 hours, and then stirring at room is 2 hours, is finally warmed up to 70 ℃, stirs 12 hours, to remove unnecessary oxalyl chloride, obtains solution A.Take cm-chitosan 300mg and be dispersed in the anhydrous DMF of 20mL, stir and after abundant swelling, obtain solution B in 12 hours.Added in solution A, at N
2under protection, in 110 ℃, react 48 hours; be cooled to after room temperature, by 0.2 μ m millipore filtration suction filtration, distilled water repetitive scrubbing, suction filtration for the solid obtaining; finally, by vacuum-drying at 50 ℃ of resulting solids 8 hours, obtain carbon nanotube-cm-chitosan matrix material of covalence graft.
Prepared matrix material is joined in deionized water, ultrasonic dispersion 20 minutes, slowly adding 50mL concentration is the copper-bath of 0.1mol/L, under room temperature, stir 24 hours, centrifugal, with deionized water repetitive scrubbing, until can't detect cupric ion with sodium sulphite in supernatant liquor, 50 ℃ of vacuum-drying 12 hours, obtains carbon nanotube-carboxymethyl chitosan copper title complex (MWCNT-cmCs-Cu).
Prepared matrix material is dispersed in deionized water, metal ion, along with time growth discharges in solution gradually, causes the specific conductivity of solution to rise, by the mensuration to electrical conductivity of solution, investigate the ion rate of release of sample, thereby contrast its sustained release performance.
The antibacterial test of prepared stain control agent is as follows:
(1) preparation of bacteria suspension
Respectively the bacterial classification of intestinal bacteria (E.coli) and streptococcus aureus (S.aureus) is linked on LB broth culture and is activated, by bacterium in constant incubator 37 ℃ cultivate 24 hours, then the activated good bacterial classification of picking 1 ring is dispersed in 9mL stroke-physiological saline solution it respectively, concussion shakes up, and makes bacteria suspension.
(2) qualitative antibacterial test
To after the circular filter paper sheet sterilizing of diameter 9mm, be immersed in the sample aqueous solution of 5mg/mL, drawing 0.2mL bacteria suspension drips on nutrient agar, coating evenly, with the tweezers gripping filter paper after sterilizing, be attached to nutrient agar central authorities, in constant incubator, cultivate 24 hours for 37 ℃, the size of observing antibacterial circle diameter, diameter shows that more greatly its fungistatic effect is better.
(3) the antibacterial test of counting process
Respectively the sample of certain mass is joined in LB broth culture, the solution 20mL that preparation sample concentration is 1mg/mL, accurately adds 0.2mL bacteria suspension, in earthquake incubator, cultivates 12 hours for 37 ℃.By 10 times of the solution dilutions after cultivating, get one after another drop ofly on blood counting chamber, examine under a microscope counting indoor bacteria.
The transmission electron microscope picture of carbon nanotube-cm-chitosan matrix material of preparation is referring to Fig. 1.In Fig. 1, (a) be original carbon nanotube; (b) be carbon nanotube grafting cm-chitosan.From Fig. 1 (b) figure, it is large that the carbon nanotube caliber after cm-chitosan modification obviously becomes, and its tube wall exterior and pipe end are all wrapped up by cm-chitosan, have formed the structure of similar core-shell.
The MWNT-cmCs-Cu of preparation and the specific conductivity curve of cmCs-Cu are referring to Fig. 2.In Fig. 2, (a) be MWNT-cmCs-Cu; (b) be cmCs-Cu.As seen from Figure 2, carboxymethyl chitosan copper title complex was at initial several days, and ion release rate is very fast; Since the 5th day, the burst size of ion just sharply reduced, and conductivity variations is afterwards extremely slow, and in illustrative material, most metal ion has discharged at initial several days.Compare with the cmCs-Cu that does not add carbon nanotube, the MWNT-cmCs-Cu that contains carbon nanotube is relatively slow at initial several days ion release rate, and along with the prolongation of soak time, the specific conductivity of its solution presents the trend of steady rising, illustrates that metal ion slowly and constantly discharges from sample.
embodiment 2:the preparation of carboxylic carbon nanotube-cm-chitosan-Zn complex stain control agent.
The preparation process of carbon nanotube-cm-chitosan matrix material is as embodiment 1, prepared matrix material is joined in deionized water, ultrasonic dispersion 20 minutes, slowly adding 50mL concentration is the solution of zinc sulfate of 0.1mol/L, under room temperature, stir 24 hours, centrifugal, with deionized water repetitive scrubbing until can't detect zine ion with sodium sulphite in supernatant liquor, 50 ℃ of vacuum-drying 12 hours, obtains carbon nanotube-cm-chitosan-Zn complex (MWCNT-cmCs-Zn).To the antibacterial testing method of the measuring method of sample solution specific conductivity with embodiment 1.
The MWNT-cmCs-Zn of preparation and the specific conductivity curve of cmCs-Zn are referring to Fig. 3.In Fig. 3, (a) be MWNT-cmCs-Zn; (b) be cmCs-Zn.As seen from Figure 3, releasing trend and Fig. 2 of metal ion are similar, and its metal ion of the MWNT-cmCs-Zn that contains carbon nanotube slowly and constantly discharges in the middle of sample.The interpolation of carbon nanotube has delayed the release rate of metal ion, and metal ion is had to slow release effect, and has extended its effective deenergized period.
The infrared spectrogram of carbon nanotube-cm-chitosan metal complexes stain control agent of preparation is referring to Fig. 4.In Fig. 4, (a) be MWCNT-cmCs; (b) be MWCNT-cmCs-Cu; (c) be MWCNT-cmCs-Zn.As seen from Figure 4, in MWCNT-cmCs, after the contained carboxyl and metal ion salify of cm-chitosan ,-COO-is at 1640cm
-1the antisymmetric stretching vibration peak at place is moved to respectively 1653cm
-1and 1648cm (MWCNT-cmCs-Cu)
-1(MWCNT-cmCs-Zn) locate; Correspondingly ,-COO-is at 1400cm
-1the symmetrical stretching vibration peak at place is moved to respectively 1406cm
-1and 1403cm (MWCNT-cmCs-Cu)
-1(MWCNT-cmCs-Zn) locate, this is to be combined the covalency of rear O-M with metal ion and to strengthen due to carboxyl, thereby cause two of carboxyl C=O to absorb peak-to-peak distance, becomes large.Meanwhile, MWCNT-cmCs-Cu and MWCNT-cmCs-Zn are respectively at 624cm
-1, 620cm
-1having there is new absorption peak in place, represents the formation of O-Cu, O-Zn key.In addition, cmCs is at 3424cm
-1n-H, O-H vibration peak that place's corresponding part has neither part nor lot in carbon nanotube graft reaction have moved to respectively 3434cm
-1and 3449cm
-1place, has also illustrated that part amino has participated in reacting with hydroxyl.Result shows that carboxyl, amino and hydroxyl have all participated in and the reacting of metal ion, Formed nanotube grafting cm-chitosan metal complexes.
Carbon nanotube-cm-chitosan metal complexes stain control agent of preparation to streptococcus aureus and colibacillary antibacterial loop graph referring to Fig. 5.In Fig. 5, (a) MWCNT-cmCs, (b) MWCNT-cmCs-Zn, (c) MWCNT-cmCs-Cu are the antibacterial loop graph of stain control agent to streptococcus aureus; (d) MWCNT-cmCs, (e) MWCNT-cmCs-Zn, (f) MWCNT-cmCs-Cu be stain control agent to colibacillary antibacterial loop graph, every partial enlarged drawing that the photo upper right corner is this inhibition zone.As seen from Figure 5, relatively three kinds of carbon nanotube-cm-chitosan metal complexes stain control agents are known to the size of inhibition zone in streptococcus aureus and colibacillary inhibition zone photo figure, three kinds of carbon nanotube-cm-chitosan metal complexes stain control agents have all shown biocidal property to streptococcus aureus and intestinal bacteria, its biocidal property MWCNT-cmCs-Cu > MWCNT-cmCs-Zn > MWCNT-cmCs, in two kinds of tested bacteriums, sample is greater than intestinal bacteria to the biocidal property of streptococcus aureus.
Carbon nanotube-cm-chitosan metal complexes stain control agent of preparation to streptococcus aureus and colibacillary counting process fungistatic effect comparison diagram referring to Fig. 6.The bacteria suspension that does not add any antibacterial material of take is blank, has investigated after interpolation MWNT-cmCs, MWNT-cmCs-Zn, MWNT-cmCs-Cu, and 37 ℃ of isothermal vibrations are cultivated the bacteria suspension bacterial concentration of 12 hours.As Fig. 6, the bacteria suspension bacterial concentration that has added carbon nanotube-cm-chitosan metal complexes stain control agent has reduced only about half of than check sample, shown certain biocidal property, and the fungistatic effect of MWNT-cmCs-Zn, MWNT-cmCs-Cu is more remarkable, its bacteria suspension bacterial concentration has reduced an order of magnitude than check sample, has shown excellent bacteriostatic activity.Wherein more obvious than intestinal bacteria to the biocidal property of streptococcus aureus, the biocidal property MWNT-cmCs-Cu > MWNT-cmCs-Zn > MWNT-cmCs of sample, consistent with the result of Bactericidal test.
embodiment 3:multi-walled carbon nano-tubes-glucosamine carries the preparation of silver-colored stain control agent.
Reaction process is as Figure 11.
The carboxylated multi-walled carbon nano-tubes of 90mg is joined in the anhydrous DMF of 60mL, after ultrasonic dispersion 10min, slowly drip wherein 3mL oxalyl chloride, at N
2under protection, 0 ℃ is stirred 2 hours, and then stirring at room is 2 hours, is finally warmed up to 70 ℃, stirs 12 hours, to remove unnecessary oxalyl chloride, obtains solution A.Take 900mg glucosamine and be dispersed in the anhydrous DMF of 40mL, after fully dissolving, obtain solution B.Added in solution A, at N
2under protection, in 90 ℃, react 48 hours; be cooled to after room temperature; by 0.2 μ m millipore filtration suction filtration, remove N; dinethylformamide; distilled water repetitive scrubbing, suction filtration for the solid obtaining; by vacuum-drying at 50 ℃ of resulting solids 8 hours, obtain multi-walled carbon nano-tubes-glucosamine (MWCNT-glucosamine) matrix material of covalence graft.
Get respectively the silver nitrate aqueous solution that 10mL concentration is 10mmol/L, polyvinylpyrrolidone (PVP) solution that 5mL concentration is 5mmol/L stirs half an hour under room temperature in beaker, and silver ions can be scattered in polyvinylpyrrolidone template fully.Then add the prepared carbon nanotube-glucosamine matrix material of 20mg, under UV-irradiation, stirring at room 4 hours.Then suction filtration, by deionized water repetitive scrubbing suction filtration for the black solid obtaining, again successively with 85% ethanol, absolute ethanol washing dehydration, suction filtration, finally, by vacuum-drying at 50 ℃ of resulting solids 8 hours, obtain multi-walled carbon nano-tubes-glucosamine and carry ag material (MWCNT-glucosamine-Ag NPs).Antibacterial testing method is with embodiment 1.
The infrared spectrogram of carbon nanotube-glucosamine matrix material of preparation is referring to Fig. 7.As seen from Figure 7,1628cm
-1the peak at place is the C=O stretching vibration peak of amido linkage in MWCNT-glucosamine (CONH-), has proved that the carboxyl of carbon nanotube and the amino in glucosamine react, and has generated amido linkage, between the two with-CONH-combination.At 2923cm
-1place represents the C-H vibration peak of glucosamine molecular skeleton, 1385cm
-1the C-N vibration peak at place, 1095cm
-1the C-O vibration peak at place, has all illustrated the introducing of glucosamine molecule.
The X-ray diffraction spectrogram that the carbon nanotube-glucosamine of preparation carries ag material is referring to Fig. 8.In Fig. 8,38.0 °, 44.2 °, 64.4 °, 77.5 ° four diffraction peaks locating corresponding respectively (111), (200), (220), (311) crystal face of silver, illustrate that prepared multi-walled carbon nano-tubes-glucosamine carries in ag material, silver is that the form with metal simple-substance exists, and its sharp-pointed diffraction peak has shown that Nano silver grain has good face-centred cubic structure; Meanwhile, appear at 26.0 ° and 42.5 ° diffraction peak correspondence the characteristic diffraction peak of carbon nanotube in material, proved the existence of carbon nanotube in material.
Preparation carbon nanotube-glucosamine carry ag material to the antibacterial loop graph of streptococcus aureus (a) and intestinal bacteria (b) referring to Fig. 9.As seen from Figure 9, MWCNT-glucosamine-Ag NPs has shown the biocidal property of highly significant to two kinds of bacteriums, illustrate that the introducing of nanometer silver has improved the biocidal property of material significantly, and it is more obvious to the biocidal property of streptococcus aureus.
Claims (6)
1. a preparation method for functionalized carbon nano-tube/metal complexes stain control agent, is characterized in that it comprises the following steps:
(1) carboxylic carbon nano-tube is joined to anhydrous N, in dinethylformamide, ultrasonic dispersion is after 10 minutes, slowly drip the chloride reagent that is equivalent to 20 ~ 40 times of carboxylic carbon nano-tube quality, under nitrogen protection, at 0 ~ 5 ℃, stir 2 ~ 4 hours, then 20 ~ 25 ℃ are stirred 2 ~ 4 hours, are finally warmed up to 70 ~ 80 ℃, stir 12 ~ 24 hours;
(2) chitosan derivatives is dispersed in anhydrous DMF, stirs 10 ~ 20 hours, make its abundant swelling; Then obtained solution is added drop-wise in step (1) reaction solution, under nitrogen protection, in 100 ~ 130 ℃, reacts 45 ~ 60 hours;
(3) after above-mentioned reaction solution cool to room temperature, micropore suction filtration, the solid obtaining distilled water repetitive scrubbing, removes unreacted chitosan derivatives, then uses successively 80 ~ 85% ethanol, absolute ethanol washing dehydration, suction filtration;
(4), by vacuum-drying at 40 ~ 80 ℃ of gained solids in step (3) 8 ~ 20 hours, obtain carbon nanotube-chitosan derivatives matrix material of covalence graft;
(5) above-mentioned matrix material is joined in deionized water, after ultrasonic dispersion, splash into metal salt solution, stir 20 ~ 30 hours at 20 ~ 30 ℃; Or above-mentioned matrix material is added in well-mixed Silver Nitrate/polyvinylpyrrolidonesolution solution, under UV-irradiation, stir 3 ~ 6 hours at 20 ~ 30 ℃;
(6) reaction finish rear centrifugal, with deionized water repetitive scrubbing until can't detect metal ion in supernatant liquor; Again by products therefrom 40 ~ 80 ℃ of vacuum-dryings 12 ~ 24 hours, obtain functionalized carbon nano-tube/metal complexes stain control agent.
2. preparation method as claimed in claim 1, the mass ratio that it is characterized in that described carboxylic carbon nano-tube, chitosan derivatives and metal-salt is 1:(5 ~ 15): (10 ~ 20).
3. preparation method as claimed in claim 1, is characterized in that described carboxylic carbon nano-tube is carboxylated Single Walled Carbon Nanotube or carboxylated multi-walled carbon nano-tubes.
4. preparation method as claimed in claim 1, the chloride reagent that it is characterized in that described carboxylic carbon nano-tube is oxalyl chloride, benzene sulfonyl chloride or SULPHURYL CHLORIDE.
5. preparation method as claimed in claim 1, is characterized in that described chitosan derivatives is cm-chitosan, chitinamine oligosaccharide or glucosamine.
6. preparation method as claimed in claim 1, is characterized in that described metal-salt is soluble copper salt, soluble zinc salt or soluble silver salt.
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| CN104004391A (en) * | 2014-06-11 | 2014-08-27 | 太原理工大学 | Manufacturing method of silver-loaded carbon nano-tube in marine antifouling agent |
| CN104525136A (en) * | 2014-10-27 | 2015-04-22 | 湖北工程学院 | Composite material, and preparation method and application thereof |
| CN104525136B (en) * | 2014-10-27 | 2016-08-17 | 湖北工程学院 | A kind of composite and its production and use |
| CN107987690A (en) * | 2017-11-16 | 2018-05-04 | 江山海维科技有限公司 | A kind of environmentally-friendly coating method of timber |
| CN109651912A (en) * | 2018-12-31 | 2019-04-19 | 方少章 | A kind of polymer light coating and preparation method thereof |
| CN111410888A (en) * | 2019-01-08 | 2020-07-14 | 上海先着点光电科技有限公司 | Preparation process of nano-silver coated zinc composite coating resistant to marine organism adhesion |
| CN110903488A (en) * | 2019-11-18 | 2020-03-24 | 广西大学 | Preparation method of chitosan @ metal organic framework antibacterial material |
| CN111799479A (en) * | 2020-07-20 | 2020-10-20 | 中国海洋大学 | Chitosan-transition metal ion composite modified cathode material and preparation method and application thereof |
| CN111808425A (en) * | 2020-07-31 | 2020-10-23 | 西北师范大学 | Preparation and application of chitosan/carboxylated polyphenylene sulfide composite material |
| CN111808425B (en) * | 2020-07-31 | 2023-06-06 | 西北师范大学 | Preparation and application of chitosan/carboxylated polyphenylene sulfide composite material |
| CN113277498A (en) * | 2021-05-19 | 2021-08-20 | 西北工业大学 | Transition metal-based hybrid material nanotube and preparation method and application thereof |
| CN113277498B (en) * | 2021-05-19 | 2023-10-27 | 西北工业大学 | Transition metal-based hybrid material nanotube and preparation method and application thereof |
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