CN105918319A - Functionalized graphene oxide bacteriostatic material and preparation method thereof - Google Patents
Functionalized graphene oxide bacteriostatic material and preparation method thereof Download PDFInfo
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- CN105918319A CN105918319A CN201610287213.6A CN201610287213A CN105918319A CN 105918319 A CN105918319 A CN 105918319A CN 201610287213 A CN201610287213 A CN 201610287213A CN 105918319 A CN105918319 A CN 105918319A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
Abstract
The invention discloses a functionalized graphene oxide bacteriostatic material and a preparation method thereof. The method comprises the following steps that 1, graphene oxide, ammonium halide and a catalyst beneficial for esterification are added into an organic solvent to fully react at the temperature of 50 DEG C to 100 DEG C under the stirring condition, then the reaction products are centrifuged, supernatant is discarded, solids are collected after subnatant is subjected to water washing and alcohol washing, and freeze drying is conducted to obtain substance A, wherein the oxygen content of graphene oxide is 20%-50%, and carboxyl accounts for 15% of the total oxygen content; 2, the substance A and a sodium hypochlorite solution are mixed to be uniform according to the mass ratio of 1:(2-100) and fully react at the temperature of 25 DEG C-50 DEG C under the stirring condition, and reaction products are subjected to water washing and freeze drying to obtain the functionalized graphene oxide bacteriostatic material. According to the method, a synergistic antibacterial agent is grafted onto graphene oxide by taking graphene oxide as a substrate, and the prepared product not only has the antibacterial property of graphene but also has the additional antibacterial property of ammonium halide.
Description
Technical field
The present invention relates to antibacterial material field, particularly relate to a kind of functional graphene oxide antibacterial material and preparation thereof
Method.
Background technology
Graphene is a kind of New Two Dimensional plane nano material with special monoatomic layer structure of discovered in recent years, tool
There are the characteristics such as chemical stability is high, conduct electricity very well, specific surface area is big.In recent years, people take in terms of the preparation of Graphene
Obtain remarkable break-throughs, develop the new technologies and methods such as mechanical stripping, crystal epitaxy, chemical gaseous phase deposition and organic synthesis.
2010, it is found that the anti-microbial property of grapheme material first, causes the extensive concern of academia at once.But Graphene is difficult to
It is dissolved in organic solvent, and bad dispersibility in the base, it is unfavorable for the further expansion of its research and application work.For fully
Play its good characteristic, Graphene is modified the most necessary.Introducing specific functional group is to carry out Graphene modification at present
One of main path.Patent CN104068058A is prepared for graphene oxide, improves its dispersibility, and by silver nanoparticle
Particle loading prepares anti-biotic material on graphene oxide.But this anti-biotic material is unstable, silver nano-grain cause easy to fall off
Make its anti-microbial property impacted, be unfavorable for using for a long time.
Graphene modification technology is the most common in Graphene application aspect, but, use Synergistic antimicrobial agent modification stone
Ink alkene is almost without report.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention provides a kind of functional graphene oxide antibacterial material and preparation side thereof
Method, Synergistic antimicrobial agent, with graphene oxide as base material, is grafted on graphene oxide by this preparation method, and prepared product not only has
There is the anti-microbial property of Graphene, and addition of the anti-microbial property of halogen ammonium salt.
To this end, technical scheme is as follows:
The preparation method of a kind of functional graphene oxide antibacterial material, comprises the steps:
(1) by graphene oxide, halogen ammonium salt be beneficial to the catalyst of esterification and add in organic solvent, 50～100 DEG C, stir
Under the conditions of mixing, fully react, then reactant is centrifuged, abandon supernatant, lower floor's liquid is collected after washing, alcohol are washed solid
Body, freeze-dried obtains substance A；Wherein, it is 20～50% that described graphene oxide meets oxygen content, and carboxyl accounts for total oxygen
15%；
(2) substance A is mixed homogeneously according to mass ratio 1:2～100 with liquor natrii hypochloritis, at 25～50 DEG C, stirring bar
Under part, fully react, then by product through washing, lyophilization, obtain described functional graphene oxide antibacterial material.
Further, the molecule of described halogen ammonium salt contains hydroxyl and secondary amine simultaneously；Preferably, halogen ammonium salt is 1-methylol-5,
5-dimethyl hydantoin or 3-vinyl-5,5-dimethyl hydantoin or both mixture.
Further, the described catalyst being beneficial to esterification is dicyclohexylcarbodiimide (DCC) or dimethyl aminopyridine
Or both mixture (DMAP).
Preferably, in step (1), the time of reaction is 4～72h；In step (2), the time of reaction is 2～6h.
Further, the mass ratio of graphene oxide, halogen ammonium salt and organic solvent described in step (1) be 1:1～3:200～
500。
Described organic solvent selects according to similar compatibility principle, preferably dichloromethane, DMF
Or oxolane.
Further, graphene oxide described in step (1) prepares through following steps:
1. adding concentrated sulphuric acid, potassium peroxydisulfate and phosphorus pentoxide in reaction vessel, under the conditions of 70～100 DEG C, mixing is all
Even, be subsequently adding graphite, 60～90 DEG C, react under stirring condition, make that graphite is fully oxidized, peel off；Solid is collected by filtration, will
Described solid is through washing, obtaining product I after drying；Wherein, the matter of described graphite, concentrated sulphuric acid, potassium peroxydisulfate and phosphorus pentoxide
Amount ratio is 5:40～60:3～8:3～8；
2., under conditions of 0～10 DEG C, described product I, sodium nitrate are added mix homogeneously in concentrated sulphuric acid, the most slowly adds
Enter potassium permanganate, after potassium permanganate adds, continue reaction 0.5～2h；Subsequently 30～50 DEG C, under stirring condition, dropwise add
Enter deionized water, it is ensured that the response time maintains 1～2h；After deionized water is added completely into 80～100 DEG C, stirring condition anti-
Answer 10～30min；Then be added dropwise to hydrogen peroxide, filtered while hot, collect solid, by it through pickling, be washed to after pH value is neutrality,
It is dried, obtains described graphene oxide；Wherein, the mass ratio of described product I, concentrated sulphuric acid, sodium nitrate, potassium permanganate and hydrogen peroxide
For 1:15～20:0.3～1:2～5:5～10.
(1) structure of anti-biotic material that present invention reaction obtains is shown in formula 1 or formula 2 or formula 3,
Formula 1,2 is satisfied by n ∈ [1,1000000000].
The invention provides a kind of new function graphene oxide antibacterial material and preparation method thereof, this composite with
Graphene oxide is base material, Synergistic antimicrobial agent is grafted on graphene oxide, and graphene oxide substrate and halogen ammonium salt have been all
The main material layer of function, for anti-bacterial attachment and sterilization, when antibacterial touches material surface, more than 99% thin
Bacterium can be killed,.Not only make use of the anti-microbial property of graphene oxide, and addition of the anti-microbial property that halogen ammonium salt is excellent.Greatly
The big raising antibacterial efficiency of functional graphene oxide, adds broad spectrum antibacterial performance, reaches long-acting sustained anti-microbial effect simultaneously.With
Time, this material structure is simple, easy to implement, can be widely applied to the various product having antibacterial demand, as medical material, apparatus and
Textile etc..
Detailed description of the invention
By the following examples technical scheme is described in detail.
Embodiment 1
The preparation method of a kind of graphite oxide thiazolinyl anti-biotic material, comprises the steps:
1) in the three-neck flask of 250ml, add 40ml concentrated sulphuric acid and be heated to 90 DEG C, then carry out mechanical agitation, add respectively
Enter 4g potassium peroxydisulfate and 4g phosphorus pentoxide, be cooled to 80 DEG C, add 5g graphite, water bath with thermostatic control reaction 4.5h, stopped reaction,
After being cooled to room temperature, use 200ml distilled water diluting, filter, and with distilled water repeated washing three times, drying, pre-oxidized
Graphite.
2) in the three-neck flask of 250ml, add 60ml concentrated sulphuric acid (in ice-water bath), mechanical agitation 30min, be subsequently adding
2.5g pre-oxidation graphite flake and 0.5g sodium nitrate, treat that solid is completely dissolved, and reacts 30min after being slowly added to 5g potassium permanganate；So
After temperature is increased to 35 DEG C, with constant pressure funnel dropping 230ml distilled water, the maintenance response time is 90min；Drip
Reaction 15min it is immediately transferred in the oil bath of 95 DEG C after Biing, then the mixture in three-neck flask down in the beaker of 2000ml
And drip 30% hydrogen peroxide 12.5ml filtered while hot, obtain withered yellow solid, add 10% dilute hydrochloric acid 10ml washing centrifugal,
It is washed with distilled water to neutrality, lyophilization, obtains graphene oxide, stand-by.
3) in graphene oxide, add the ultrasonic 1h of dry DMF, be subsequently adding 3-vinyl-5 of mass ratio 1:1,5-bis-
Methyl hydantoin, under conditions of DCC and DMAP is as catalyst, 60 DEG C of stirring reaction 6h, centrifugal, collection lower floor liquid,
Washed, after alcohol washes, collected solid, freeze-dried obtained functional graphene oxide；
4) by 1g step 3) functional graphene oxide that obtains is distributed to mix homogeneously in 20ml liquor natrii hypochloritis,
Stir 6h at 50 DEG C, then by product through washing, lyophilization, obtain functional graphene oxide antibacterial material, i.e. oxygen
Functionalized graphene is combined 3-vinyl-5,5-dimethyl hydantoin anti-biotic material.
Cultivate antibacterial according to the way surveying growth curve, take the nothing of bacteria suspension respectively with the 100 μ L of 1mLO.D.600=0.1
After the mixing of bacterium water (blank group), antibacterial, it is then transferred in the test tube of 15mL, adds the fluid medium of 10mL afterwards
In.At 37.5 DEG C, after shaking 2h under the conditions of 140rpm.Bacteria suspension after diluting 100,000 times of process with 100 μ L paves plate, is placed on
Clump count after cultivating 24 hours in 37.5 DEG C of constant incubators.Antibacterial in this experiment is the product that this enforcement finally prepares
The aqueous solution of (100 μ g/mL).Blank experiment is the sterilized water adding 100 μ L.
The present embodiment obtains graphene oxide and is combined 3-vinyl-5, the sterilizing rate of 5-dimethyl hydantoin anti-biotic material
＞ 98% (experimental strain: escherichia coli, staphylococcus aureus etc.).
Sterilizing rate computing formula: (1-experimental group material bacterium number/matched group material bacterium number) × 100%
Embodiment 2
The preparation method of a kind of graphite oxide thiazolinyl anti-biotic material, comprises the steps:
1) in the three-neck flask of 250ml, add 40ml concentrated sulphuric acid and be heated to 90 DEG C, then carry out mechanical agitation, add simultaneously
Enter 4g potassium peroxydisulfate and 4g phosphorus pentoxide, be cooled to 80 DEG C, add 5g graphite, water bath with thermostatic control reaction 4.5h, stopped reaction,
After being cooled to room temperature, use 200ml distilled water diluting, filter, and with distilled water repeated washing three times, drying, pre-oxidized
Graphite.
2) in the three-neck flask of 250ml, add 60ml concentrated sulphuric acid (in ice-water bath), mechanical agitation 30min, be subsequently adding
2.5g pre-oxidation graphite flake and 0.5g sodium nitrate, treat that solid is completely dissolved, and reacts 30min after being slowly added to 7.5g potassium permanganate.
Then temperature being increased to 35 DEG C, with the distilled water of constant pressure funnel dropping 230ml, the maintenance response time is 90min；Dropping
After be immediately transferred in the oil bath of 95 DEG C reaction 20min, then mixture down in the beaker of 2000ml and drip 30%
Hydrogen peroxide 12.5ml filtered while hot, obtain withered yellow solid, add 10% dilute hydrochloric acid 10ml washing centrifugal, with distillation washing
Wash to neutrality, lyophilization, obtain graphene oxide, stand-by.
3) in graphene oxide, add the ultrasonic 1h of dry DMF, be subsequently adding 3-vinyl-5 of mass ratio 1:2,5-bis-
Methyl hydantoin, under conditions of DCC and DMAP is as catalyst, 60 DEG C of stirring reaction 6h, centrifugal, collection lower floor liquid,
Washed, after alcohol washes, collected solid, freeze-dried obtained functional graphene oxide；
4) by 1g step 3) functional graphene oxide that obtains is distributed to mix homogeneously in 40ml liquor natrii hypochloritis, and 60
Stir 6h at DEG C, then by product through washing, lyophilization, obtain described functional graphene oxide antibacterial material.
It is finally made graphene oxide and is combined 3-vinyl-5,5-dimethyl hydantoin anti-biotic material finished product, utilize same
Method of testing in embodiment 1, records the present embodiment and obtains the sterilizing rate ＞ 99% (experimental strain: escherichia coli, golden yellow of product
Staphylococcus etc.).
Embodiment 3
The preparation method of a kind of graphite oxide thiazolinyl anti-biotic material, comprises the steps:
1) in the three-neck flask of 250ml, add 50ml concentrated sulphuric acid and be heated to 95 DEG C, then carry out mechanical agitation, add simultaneously
Enter 4g potassium peroxydisulfate and 4g phosphorus pentoxide, be cooled to 75 DEG C, add 5g graphite, water bath with thermostatic control reaction 4.5h, stopped reaction,
After being cooled to room temperature, use 200ml distilled water diluting, filter, and with distilled water repeated washing three times, drying, pre-oxidized
Graphite.
2) in the three-neck flask of 250ml, add 70ml concentrated sulphuric acid (in ice-water bath), mechanical agitation 30min, be subsequently adding
2.5g pre-oxidation graphite flake and 0.5g sodium nitrate, treat that solid is completely dissolved, and reacts 30min after being slowly added to 7.5g potassium permanganate.
Then temperature being increased to 35 DEG C, with the distilled water of constant pressure funnel dropping 230ml, the maintenance response time is 90min；Dropping
After be immediately transferred in the oil bath of 95 DEG C reaction 20min, then mixture down in the beaker of 2000ml and drip 30%
Hydrogen peroxide 20ml filtered while hot, obtain withered yellow solid, add 10% dilute hydrochloric acid 10ml washing centrifugal, use distilled water wash
To neutral, lyophilization, obtain graphene oxide, stand-by.
3) add graphene oxide into the ultrasonic 1h of dry DMF, be subsequently adding 1-methylol-5 of mass ratio 1:1,5-diformazan
Base hydantoin, under conditions of DMAP is as catalyst, 70 DEG C of stirring reaction 6h, centrifugal, collection lower floor liquid, Jiang Qishui
Wash, after alcohol washes, collect solid, freeze-dried obtain functional graphene oxide；
4) by 0.5g step 3) functional graphene oxide that obtains is distributed to mix homogeneously in 30ml liquor natrii hypochloritis,
Stir 8h at 50 DEG C, then by product through washing, lyophilization, obtain described functional graphene oxide antibacterial material.
It is finally made graphene oxide and is combined 1-methylol-5,5-dimethyl hydantoin anti-biotic material finished product, utilize same
Method of testing in embodiment 1, records the present embodiment and obtains the sterilizing rate ＞ 99% (experimental strain: escherichia coli, golden yellow of product
Staphylococcus etc.).
Embodiment 4
The preparation method of a kind of graphite oxide thiazolinyl anti-biotic material, comprises the steps:
1) in the solid oxide Graphene being commercially available, add the ultrasonic 3h of dry DMF, be subsequently adding the 1-of mass ratio 1:2
Methylol-5,5-dimethyl hydantoin, under conditions of DCC and DMAP is as catalyst, 80 DEG C of stirring reaction 5h, centrifugal water
Wash three times, obtain product and dry.
2) by 0.5g step 1) functional graphene oxide that obtains is distributed to mix homogeneously in 50ml liquor natrii hypochloritis,
8h is stirred at 50 DEG C, centrifugal, collect lower floor's liquid, wash, after alcohol washes, collection solid, freeze-dried obtained functionalization
Graphene oxide；
It is finally made graphene oxide and is combined 1-methylol-5,5-dimethyl hydantoin anti-biotic material finished product, utilize same
Method of testing in embodiment 1, records the present embodiment and obtains the sterilizing rate ＞ 98% (experimental strain: escherichia coli, golden yellow of product
Staphylococcus etc.).
Sterilizing rate computing formula: (1-experimental group material bacterium number/matched group material bacterium number) × 100%
Embodiment 5
The preparation method of a kind of graphite oxide thiazolinyl anti-biotic material, comprises the steps:
1) in the solid oxide Graphene being commercially available, add the ultrasonic 3h of dry DMF, be subsequently adding the 1-of mass ratio 1:3
Methylol-5,5-dimethyl hydantoin, under conditions of DCC is as catalyst, 60 DEG C of stirring reaction 6h, centrifugal, collect under
Layer liquid, wash, after alcohol washes, collection solid, freeze-dried obtains functional graphene oxide；
2) by 1g step 1) functional graphene oxide that obtains is distributed to mix homogeneously in 50ml liquor natrii hypochloritis, and 60
Stir 6h at DEG C, then by product through washing, lyophilization, obtain described functional graphene oxide antibacterial material.
It is finally made graphene oxide and is combined 1-methylol-5,5-dimethyl hydantoin anti-biotic material finished product, utilize same
Method of testing in embodiment 1, records the present embodiment and obtains the sterilizing rate ＞ 98% (experimental strain: escherichia coli, golden yellow of product
Staphylococcus etc.).
Sterilizing rate computing formula: (1-experimental group material bacterium number/matched group material bacterium number) × 100%.
Claims (9)
1. the preparation method of a functional graphene oxide antibacterial material, it is characterised in that comprise the steps:
(1) by graphene oxide, halogen ammonium salt and the catalyst addition organic solvent being beneficial to esterification, at 50～100 DEG C, stirring bar
Under part, fully react, then reactant is centrifuged, abandon supernatant, lower floor's liquid is collected after washing, alcohol are washed solid, warp
Lyophilization obtains substance A；Wherein, it is 20～50% that described graphene oxide meets oxygen content, and carboxyl accounts for total oxygen
15%；
(2) described substance A is mixed homogeneously according to mass ratio 1:2～100 with liquor natrii hypochloritis, at 25～50 DEG C, stirring bar
Under part, fully react, then by product through washing, lyophilization, obtain described functional graphene oxide antibacterial material.
2. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that: described halogen ammonium salt
Molecule on contain hydroxyl and secondary amine simultaneously.
3. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that: described halogen ammonium salt
For 1-methylol-5,5-dimethyl hydantoin or 3-vinyl-5,5-dimethyl hydantoin or both mixture.
4. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that: described beneficially ester
The catalyst changed is dicyclohexylcarbodiimide or dimethyl aminopyridine or both mixture.
5. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that: in step (1)
The mass ratio of described graphene oxide, halogen ammonium salt and organic solvent is 1:1～3:200～500.
6. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that: in step (1)
The time of reaction is 4～72h；In step (2), the time of reaction is 2～6h.
7. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that: described organic molten
Agent is dichloromethane, N,N-dimethylformamide or oxolane.
8. the preparation method of functional graphene oxide antibacterial material as claimed in claim 1, it is characterised in that institute in step (1)
State graphene oxide to prepare through following steps:
1. addition concentrated sulphuric acid, potassium peroxydisulfate and phosphorus pentoxide in reaction vessel, mix homogeneously under the conditions of 70～100 DEG C,
Be subsequently adding graphite, 60～90 DEG C, react under stirring condition, make that graphite is fully oxidized, peel off；Solid is collected by filtration, by institute
State solid through washing, obtaining product I after drying；Wherein, the quality of described graphite, concentrated sulphuric acid, potassium peroxydisulfate and phosphorus pentoxide
Ratio is 5:40～60:3～8:3～8；
2., under conditions of 0～10 DEG C, described product I, sodium nitrate are added mix homogeneously in concentrated sulphuric acid, is then slowly added into height
Potassium manganate, after potassium permanganate adds, continues reaction 0.5～2h；Subsequently 30～50 DEG C, under stirring condition, be added dropwise over
Ionized water, it is ensured that the response time maintains 1～2h；80～100 DEG C, stirring condition reaction 10 after deionized water is added completely into
～30min；Then be added dropwise to hydrogen peroxide, filtered while hot, collect solid, by it through pickling, be washed to after pH value is neutrality, dry
Dry, obtain described graphene oxide；Wherein, described product I, concentrated sulphuric acid, sodium nitrate, potassium permanganate with the mass ratio of hydrogen peroxide are
1:15～20:0.3～1:2～5:5～10.
9. the functional graphene oxide antibacterial material as obtained by any one preparation method in claim 1～8, its feature
Being: base material is graphene oxide, halogen amine salt is grafted on described graphene oxide.
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| CN106435819A (en) * | 2016-09-12 | 2017-02-22 | 天津工业大学 | Novel high-performance composite porous nanometer antibacterial fiber material adopting functionalized graphene and preparation method of novel high-performance composite porous nanometer antibacterial fiber material |
| CN106675390A (en) * | 2016-12-16 | 2017-05-17 | 安徽荣玖智能装备科技有限公司 | Graphene oxygen fluoride and polyimide composite powder coating and preparation method thereof |
| CN107384281A (en) * | 2017-09-26 | 2017-11-24 | 安徽大松树脂有限公司 | A kind of antibiotic property epoxy resin adhesive |
| CN107418490A (en) * | 2017-09-26 | 2017-12-01 | 安徽大松树脂有限公司 | A kind of epoxy resin adhesive containing graphene oxide |
| CN108042809A (en) * | 2018-02-01 | 2018-05-18 | 南京林业大学 | A kind of preparation method of bacteria resistance function graphene oxide |
| CN109097988A (en) * | 2017-06-20 | 2018-12-28 | 常州三心堂康复护理用品有限公司 | Antibiotic fabric and its manufacturing method |
| CN109247329A (en) * | 2018-09-25 | 2019-01-22 | 广西中医药大学 | A kind of novel antibacterial active material and its preparation method and application |
| CN112970761A (en) * | 2021-02-03 | 2021-06-18 | 长春工业大学 | Quaternized halamine modified graphene oxide antibacterial nanoparticles and preparation method thereof |
| CN113712038A (en) * | 2021-08-27 | 2021-11-30 | 安徽新虹新材料科技有限公司 | Graphene-based composite antibacterial material and preparation method thereof |
| CN115821420A (en) * | 2022-11-24 | 2023-03-21 | 江苏江山红化纤有限责任公司 | Graphene modified polyamide 6 composite fiber and preparation method thereof |
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| CN106435819A (en) * | 2016-09-12 | 2017-02-22 | 天津工业大学 | Novel high-performance composite porous nanometer antibacterial fiber material adopting functionalized graphene and preparation method of novel high-performance composite porous nanometer antibacterial fiber material |
| CN106675390A (en) * | 2016-12-16 | 2017-05-17 | 安徽荣玖智能装备科技有限公司 | Graphene oxygen fluoride and polyimide composite powder coating and preparation method thereof |
| CN109097988A (en) * | 2017-06-20 | 2018-12-28 | 常州三心堂康复护理用品有限公司 | Antibiotic fabric and its manufacturing method |
| CN107384281A (en) * | 2017-09-26 | 2017-11-24 | 安徽大松树脂有限公司 | A kind of antibiotic property epoxy resin adhesive |
| CN107418490A (en) * | 2017-09-26 | 2017-12-01 | 安徽大松树脂有限公司 | A kind of epoxy resin adhesive containing graphene oxide |
| CN108042809A (en) * | 2018-02-01 | 2018-05-18 | 南京林业大学 | A kind of preparation method of bacteria resistance function graphene oxide |
| CN109247329A (en) * | 2018-09-25 | 2019-01-22 | 广西中医药大学 | A kind of novel antibacterial active material and its preparation method and application |
| CN112970761A (en) * | 2021-02-03 | 2021-06-18 | 长春工业大学 | Quaternized halamine modified graphene oxide antibacterial nanoparticles and preparation method thereof |
| CN113712038A (en) * | 2021-08-27 | 2021-11-30 | 安徽新虹新材料科技有限公司 | Graphene-based composite antibacterial material and preparation method thereof |
| CN115821420A (en) * | 2022-11-24 | 2023-03-21 | 江苏江山红化纤有限责任公司 | Graphene modified polyamide 6 composite fiber and preparation method thereof |
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