CN104945636A - Composite material as well as preparation method and use of composite material - Google Patents
Composite material as well as preparation method and use of composite material Download PDFInfo
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- CN104945636A CN104945636A CN201510242938.9A CN201510242938A CN104945636A CN 104945636 A CN104945636 A CN 104945636A CN 201510242938 A CN201510242938 A CN 201510242938A CN 104945636 A CN104945636 A CN 104945636A
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- graphene oxide
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Abstract
The invention discloses a composite material. The composite material is a graphene oxide composite material the surface of which is modified with polypyrazole; the graphene oxide composite material is obtained by performing an esterification reaction on the carboxyl of the graphene oxide and the secondary ammonia of the polypyrazole in the presence of a catalyst. The preparation method of the composite material comprises the following steps: (1) dissolving the graphene oxide, the polypyrazole and the catalyst together in an organic solvent and heating in oil bath within the range from 60 to 90 DEG C for reacting for 6-24 hours; (2) cooling the product obtained in the step (1) to a room temperature, washing away the organic solvent, and drying to obtain the composite material. According to the method, the composite material can be prepared only by virtue of one step of reaction; the method is simple and convenient, and easy to operate; the obtained material has hydrophobicity and remarkable antibacterial property, and can be widely applied to preparing antibacterial materials.
Description
Technical field
The present invention relates to a kind of matrix material, Its Preparation Method And Use, particularly finishing has the graphene oxide composite material of poly-pyrazoles, its preparation method and is preparing the application on anti-biotic material.
Background technology
Graphene oxide is a kind of carbon material with two-dirnentional structure, and is considered to the basic structural unit constructing soccerballene, carbon nanotube and graphite.Graphene has chemistry and the physical propertiess such as good electroconductibility, thermal conductivity, hardness and intensity, receives the attention of Material Field and demonstrates excellent prospect of the application.Chemically structure is said, surface of graphene oxide has a large amount of epoxy group(ing), carboxyl, hydroxyl etc., can carry out to chemically easy, modify fast, obtain the material that can be widely used in electronics, energy storage, sensor field.In recent years, the graphene oxide composite material of biocompatibility receives to be paid close attention to widely and studied, and was applied to the field such as pharmaceutical carrier and cell proliferation.2010, the people such as Fan reported the anti-biotic material based on graphene oxide in the world for the first time.Afterwards, based on the anti-biotic material of graphene oxide by large quantifier elimination and report.Wherein, the material based on graphene oxide and nano metal particles obtains investigation and application widely.Such as, the matrix material based on graphene oxide and silver nano-grain has outstanding antibacterial ability.An other class is then the matrix material based on graphene oxide and polymkeric substance, also shows good antibacterial ability.Such as, the matrix material of graphene oxide and polyethylene/polyoxyethylene glycol composition, it has significantly active the suppression to intestinal bacteria etc.
But the composite material preparation process formed based on graphene oxide and metal nanoparticle is complicated, and need through polystep reaction, metal ion involves great expense, reaction process condition is comparatively strict, and preparation process pollutes the environment.At present, based on graphene oxide and Macroscopic single crystal antimicrobial composite material kind little, generally also need polystep reaction, synthesis technique is complicated, and reaction conditions is comparatively strict.
Summary of the invention
The object of the present invention is to provide a kind of matrix material, Its Preparation Method And Use.
The technical solution used in the present invention is:
A kind of matrix material, the graphene oxide composite material of its poly-pyrazoles for finishing has.
As the further improvement of invention, described matrix material is by parahelium generation esterification gained on carboxyl on graphene oxide and poly-pyrazoles.
As the further improvement of invention, described esterification occurs in the presence of a catalyst, and described catalyzer is dicyclohexylcarbodiimide.
As the further improvement of invention, the mass ratio of poly-pyrazoles and graphene oxide is 1:1-20.
A preparation method for matrix material, comprises the following steps:
(1) get graphene oxide, poly-pyrazoles, catalyzer, mixed dissolution in organic solvent, 60-90 DEG C of reacting by heating 6-24 hour;
(2) product that step (1) obtains is cooled to room temperature, and washing removing organic solvent, is drying to obtain matrix material.
As the further improvement of invention, in step (1), the interpolation mass ratio of graphene oxide and poly-pyrazoles is 1:1-20.
As the further improvement of invention, in step (1), described catalyzer is dicyclohexylcarbodiimide.
As the further improvement of invention, in step (1), described organic solvent can be at least one in dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone.
As the further improvement of invention, be dissolved as ultrasonic dissolution described in step (1), the time is 10-60min.
As the further improvement of invention, being operating as of step (2): after the product that step (1) obtains is cooled to room temperature, add at least one in acetone, tetrahydrofuran (THF), chloroform, methylene dichloride, stir, filter, get precipitation, repeated washing is to organic solvent Ex-all.
As the further improvement of invention, the drying described in step (2) is vacuum-drying, and time of drying is 12-24 hour.
Above-mentioned arbitrary described matrix material, the application on anti-biotic material prepared by the matrix material that the preparation method of above-mentioned arbitrary described matrix material prepares.
The invention has the beneficial effects as follows:
Must through polystep reaction in order to overcome the existing material prepared based on graphene oxide, synthesis technique is complicated, the problem that reaction conditions is harsh, the present invention proposes a kind of matrix material, in the presence of a catalyst, by parahelium generation esterification gained on carboxyl on graphene oxide and poly-pyrazoles, single stage method is adopted to obtain, simple and convenient, easy handling, and this material all has hydrophobicity and significant germ resistance, can be widely used in preparing anti-biotic material.
Accompanying drawing explanation
Fig. 1 is the route map of graphene oxide and poly-pyrazoles synthesising complex.
Fig. 2 is the static contact angle test pattern of anti-biotic material.
Fig. 3 is antibacterial experiment detailed maps.
Fig. 4 is antibacterial experiment bacteria live rate figure.
Embodiment
1, the preparation of anti-biotic material
embodiment 1:
1.take 20 milligrams of graphene oxides, 10 milligrams of poly-pyrazoles and 10 milligrams of dicyclohexylcarbodiimide, be placed in the round-bottomed flask of 50 milliliters, measure 20 milliliters of dimethyl sulfoxide (DMSO), add in flask, ultrasonic dissolution 20 minutes; Oil bath round-bottomed flask being placed in 80 DEG C is reacted 12 hours; Cooling reaction system is to room temperature, and joined in 150 milliliters of acetone by mixture after reaction, vigorous stirring for some time, by sedimentation and filtration; 200 milliliters of washing with acetones are adopted to filter gained throw out 2-5 time, remove dimethyl sulfoxide (DMSO), again by gained throw out vacuum-drying 24 hours, obtain the graphene oxide composite material that finishing has poly-pyrazoles, described matrix material is that the route map of concrete graphene oxide and poly-pyrazoles synthesising complex is as Fig. 1 by parahelium generation esterification gained on carboxyl on graphene oxide and poly-pyrazoles.
embodiment 2:
Take 200 milligrams of graphene oxides, 10 milligrams of poly-pyrazoles and 10 milligrams of dicyclohexylcarbodiimide, be placed in the round-bottomed flask of 100 milliliters, measure 50 milliliters of DMFs, add in flask, ultrasonic dissolution 60 minutes; Oil bath round-bottomed flask being placed in 60 DEG C is reacted 24 hours; Cooling reaction system is to room temperature, and joined in 150 milliliters of tetrahydrofuran (THF)s by mixture after reaction, vigorous stirring for some time, by sedimentation and filtration; Adopt 200 milliliters of tetrahydrofuran (THF) washing and filtering gained throw outs 2-5 time, remove DMF, then by gained throw out vacuum-drying 24 hours, obtain the graphene oxide composite material that finishing has poly-pyrazoles.
embodiment 3:
Acetone, tetrahydrofuran (THF), chloroform, methylene dichloride
Take 100 milligrams of graphene oxides, 10 milligrams of poly-pyrazoles and 10 milligrams of dicyclohexylcarbodiimide, be placed in the round-bottomed flask of 100 milliliters, measure 50 milliliters of N-Methyl pyrrolidone, add in flask, ultrasonic dissolution 10 minutes; Oil bath round-bottomed flask being placed in 90 DEG C is reacted 6 hours; Cooling reaction system is to room temperature, and joined in 150 milliliters of chloroforms by mixture after reaction, vigorous stirring for some time, by sedimentation and filtration; Adopt 200 milliliters of chloroform to filter gained throw out 2-5 time, remove N-Methyl pyrrolidone, then by gained throw out vacuum-drying 12 hours, obtain the graphene oxide composite material that finishing has poly-pyrazoles.
embodiment 4:
Take 200 milligrams of graphene oxides, 10 milligrams of poly-pyrazoles and 10 milligrams of dicyclohexylcarbodiimide, be placed in the round-bottomed flask of 100 milliliters, measure 50 milliliters of dimethyl sulfoxide (DMSO), add in flask, ultrasonic dissolution 60 minutes; Oil bath round-bottomed flask being placed in 60 DEG C is reacted 24 hours; Cooling reaction system is to room temperature, and joined in 150 milliliters of methylene dichloride by mixture after reaction, vigorous stirring for some time, by sedimentation and filtration; Adopt 200 milliliters of washed with dichloromethane to filter gained throw out 2-5 time, remove dimethyl sulfoxide (DMSO), then by gained throw out vacuum-drying 24 hours, obtain the graphene oxide composite material that finishing has poly-pyrazoles.
2, hydrophobic performance
By water droplet on the surface of anti-biotic material of preparing gained according to the method for the invention, the contact angle utilizing Static Contact angle measuring instrument to record this anti-biotic material is 104 °, contact angle θ > 90 °, illustrate that this anti-biotic material is nonwetting for hydrophobic material, experimental detail figure is as Fig. 2.In daily life, most bacterium is by water as communication media, and this hydrophobic material can reduce the infection rate of bacterium to a certain extent.
3, antibacterial experiment
Get 30 lli be 0.9% sodium chloride solution and concentration be 10
7the colibacillary mixing solutions of individual/mL, is divided into three groups, is added drop-wise to the blank agar plate being of a size of 4 square centimeters of sizes, poly-pyrazoles material respectively and prepares the anti-biotic material surface of gained according to the method for the invention, often organize 8 samples.It is 90% that three groups of samples are all placed on relative humidity, and temperature is cultivate 4 hours under the condition of 37 DEG C, more respectively the material of three groups is placed in 200 ml beakers, adds 100 ml deionized water vigorous stirring.After stirring, get solution 30 microlitre in each beaker to be respectively added drop-wise to and to be rich on the agar plate of nutritive medium, cultivate 24 hours under the condition of 37 DEG C, the bacterium of each health all can form a bacterium colony, under the microscope bacterium colony is counted, and calculating the survival rate of bacterium, experiment detailed maps, as Fig. 3, obtains experimental result as Fig. 4.
Result is known as shown in Figure 4, and poly-pyrazoles has certain promoter action to bacterial growth, and has remarkable and stable antibacterial effect according to the anti-biotic material based on poly-pyrazoles and graphene oxide that the method for the invention prepares gained, may be used for preparing anti-biotic material.
Claims (10)
1. a matrix material, the graphene oxide composite material of its poly-pyrazoles for finishing has.
2. matrix material according to claim 1, is characterized in that, described matrix material is by parahelium generation esterification gained on carboxyl on graphene oxide and poly-pyrazoles.
3. matrix material according to claim 2, is characterized in that, described esterification occurs in the presence of a catalyst, and described catalyzer is dicyclohexylcarbodiimide.
4. the matrix material according to any one of claim 1-3, is characterized in that, the mass ratio of poly-pyrazoles and graphene oxide is 1:1-20.
5. a preparation method for matrix material, is characterized in that, comprises the following steps:
(1) get graphene oxide, poly-pyrazoles, catalyzer, mixed dissolution in organic solvent, 60-90 DEG C of reacting by heating 6-24 hour;
(2) product that step (1) obtains is cooled to room temperature, and washing removing organic solvent, is drying to obtain matrix material.
6. the preparation method of matrix material according to claim 5, is characterized in that, in step (1), the interpolation mass ratio of graphene oxide and poly-pyrazoles is 1:1-20.
7. the preparation method of matrix material according to claim 5, is characterized in that, in step (1), described catalyzer is dicyclohexylcarbodiimide.
8. the preparation method of matrix material according to claim 5, is characterized in that, in step (1), described organic solvent is at least one in dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone.
9. the preparation method of matrix material according to claim 5, it is characterized in that, being operating as of step (2): after the product that step (1) obtains is cooled to room temperature, add at least one in acetone, tetrahydrofuran (THF), chloroform, methylene dichloride, stir, filter, get precipitation, repeated washing is to organic solvent Ex-all.
10. the matrix material described in any one of claim 1-4, the application on anti-biotic material prepared by the matrix material that the preparation method of the matrix material described in any one of claim 5-9 prepares.
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| CN106744826A (en) * | 2016-11-22 | 2017-05-31 | 长春工业大学 | A kind of method that the few layer graphene oxide film of large area is prepared based on esterification |
| 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 |
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| 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 |
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