CN108675683A - Graphene oxide is composite porous - Google Patents
Graphene oxide is composite porous Download PDFInfo
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- CN108675683A CN108675683A CN201810649660.0A CN201810649660A CN108675683A CN 108675683 A CN108675683 A CN 108675683A CN 201810649660 A CN201810649660 A CN 201810649660A CN 108675683 A CN108675683 A CN 108675683A
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- graphene oxide
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- composite porous
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- polyethyleneimine
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The present invention provides a kind of graphene oxide is composite porous, include the component of following parts by weight：5~10 parts of graphene oxide porous material；Copolymer 1~2 part of glucose dicarboxylic acid dimethyl ester and polyethyleneimine；2~5 parts of diatomite；4~8 parts of gelatin.The composite porous specific surface area of the graphene oxide is 500~1000m2/g, and porosity is 85~99%.The present invention is by graphene oxide porous material, the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine, diatomite and gelatin-compounded to prepare graphene oxide composite porous, the material can optimize each component advantageous combination, realize the desired combination of each material, so that the composite material machinery intensity is good, and there is outstanding adsorptivity, biocidal property, biocompatibility and biodegradability.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of graphene oxide is composite porous.
Background technology
Carbon material is element most magical in nature, is not only the composition most important element of nature material base, and
And play extremely important role in the development process of the mankind, there is inseparable contact with us.Due to carbon
Quite extensive in distributed in nature, carbon nanomaterial receives always the favor of scientist, graphene technical research in the past 30 years
In science frontier field.The fullerenes found in 1985 and the carbon nanotube found in 1991 cause tremendous influence,
Liao Tan families research boom is started in worldwide.2004, Univ Manchester UK physicist Geim et al. was utilized
The graphene of single layer structure has been prepared in " band such as a few tool power partition methods "（Grephene）." micromechanical forces partition method " is exactly to use
Adhesive tape is removed repeatedly on the graphite of highly directional pyrolysis, has finally obtained graphene.The discovery of graphene makes carbon material family again
It is added to a newcomer, completes the carbon nanotube dilute, one-dimensional by zero dimension fowler, two-dimensional graphene to three-dimensional graphite and gold
The integral framework of hard rock.
Nano-porous materials are as a kind of new material, with high porosity, high-specific surface area, unique mechanics, light
The characteristics such as and electricity, and these characteristics make nano-porous materials in numerous necks such as material science research and the development of the national economy
Domain plays huge effect.
In numerous nano-porous materials, carbon-based material is most widely used and mostly important polyporous materials.Stone
Black alkene possesses excellent mechanics, calorifics and electric property as novel nano-carbon material, before having very wide application
Scape.Common graphene is existed in the form of the graphene powder of micron order lamellar structure.Simultaneously because graphene film interlayer holds
Easily assemble, be difficult to manipulate in practical applications, it is difficult to obtain larger specific surface to lead to the assembly based on graphene
Product, it is more difficult to which the theoretical specific surface area value 2630m2/g for reaching graphene greatly hinders graphene as sorbing material
Using.Therefore microcosmic graphene is assembled into the graphene macroform with three-dimensional network shape porous structure, makes it microcosmic
In the proper property for macroscopically showing porous material again while the upper substantive characteristics with nano material, will have very heavy
The meaning wanted.
The present invention is by graphene oxide porous material, the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine, silicon
Diatomaceous earth and the gelatin-compounded graphene oxide for preparing are composite porous, which can optimize each component advantageous combination, realize
The desired combination of each material so that the good mechanical strength of the composite material, outstanding adsorptivity, biocidal property, bio-compatible
Property and biodegradability.
Invention content
The technical purpose of the present invention be to provide a kind of graphene oxide it is composite porous, it is strong with good machinery
Degree, outstanding adsorptivity, biocidal property, biocompatibility and biodegradability.
To realize the above-mentioned technical purpose, technical solution provided by the present invention is：
A kind of graphene oxide is composite porous, including following components by weight percent：
5~10 parts of graphene oxide porous material；
Copolymer 1~2 part of glucose dicarboxylic acid dimethyl ester and polyethyleneimine；
2~5 parts of diatomite；
4~8 parts of gelatin.
Further, the composite porous specific surface area of graphene oxide be 500~1000m2/g, porosity be 85~
99%.
Further, the synthesis step of the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine is as follows：It weighs
The polyethyleneimine and glucose dicarboxylic acid dimethyl ester of quality are molten in ethanol, and 1% triethylamine is added, and are stirred at room temperature 3~4 days,
Obtain the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine.
Further, the K values of the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine are 110~130.
Further, the preparation process of graphene oxide porous material is as follows：
（1）It is ultrasonically treated graphene oxide and is made into aqueous solution；
（2）It is freeze-dried step（1）Obtained treatment fluid obtains graphene oxide porous material；
（3）Heat-treat step（2）Obtained graphene oxide porous material obtains the graphene porous material.
Further, step（1）A concentration of 10~15g/L of graphene oxide, the ultrasonic time be 45~
60min, supersonic frequency are 20~25kHz.
Still further, step（2）Described in freeze-drying be vacuum freeze drying, temperature be -60 DEG C~-40 DEG C,
The time of vacuum degree ＜ 10Pa, freeze-drying are 36~120 hours.
Still further, step（3）Described in thermal reduction be that atmosphere furnace heat-treats, temperature is 600~700 DEG C, and atmosphere is
Argon gas or nitrogen, processing time are 5~6h.
Further, the composite porous preparation process of graphene oxide is as follows：
1) copolymer of graphene porous material and glucose dicarboxylic acid dimethyl ester and polyethyleneimine is weighed by number, is added
Condensing agent EDCI and dimethyl sulfoxide react 12~48 hours, and centrifugation is precipitated；
2) precipitation and the diatomite and gelatin that are weighed by number are configured to aqueous solution, ultrasound 1~2 hour, then
It is transferred to mold and stands crosslinking；
3) it after the blending colloidal sol after step 2) cross-linking reaction being transformed into gel, then is freeze-dried, graphene oxide is made
It is composite porous.
Further, graphene oxide is obtained by modified Hummers methods, and the oxidant that this method uses is persulfuric acid
It is one or more in potassium, phosphorus pentoxide, sodium nitrate, the concentrated sulfuric acid, phosphoric acid and potassium permanganate.
The present invention is by graphene oxide porous material, the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine, silicon
Diatomaceous earth and the gelatin-compounded graphene oxide for preparing are composite porous, which can optimize each component advantageous combination, realize
The desired combination of each material so that the good mechanical strength of the composite material, outstanding adsorptivity, biocidal property, bio-compatible
Property and biodegradability.
Specific implementation mode
With reference to specific embodiment, present invention is further described in detail.It should be understood that following embodiment is only used
In illustrating the present invention, and it is not construed as limiting scope.
Embodiment 1
The synthesis of the copolymer of glucose dicarboxylic acid dimethyl ester and polyethyleneimine
Polyethyleneimine and the glucose dicarboxylic acid dimethyl ester for the quality such as weighing are molten in ethanol, and 1% triethylamine, room temperature is added
Stirring 3~4 days, centrifuges to obtain sediment, and glucose dicarboxylic acid dimethyl ester and polyethylene are obtained after washing the sediment 5 times with ether
The copolymer of imines.Between the K values for measuring the copolymer are 110~130.
Embodiment 2
A kind of graphene oxide is composite porous, including following components by weight percent：5 parts of graphene oxide porous material, glucose
4 parts of copolymer 1 part of dicarboxylic acid dimethyl ester and polyethyleneimine, 2 parts of diatomite and gelatin.
The preparation process of graphene oxide porous material is as follows：
（1）It is ultrasonically treated graphene oxide and is made into aqueous solution, a concentration of 10g/L of graphene oxide, ultrasonic time 45min,
Supersonic frequency is 20kHz；
（2）It is freeze-dried step（1）Obtained treatment fluid, temperature are -60 DEG C~-40 DEG C, vacuum degree ＜ 10Pa, freeze-drying
Time is to obtain graphene oxide porous material in 48 hours；
（3）Heat-treat step（2）Obtained graphene oxide porous material, temperature are 600~700 DEG C, and atmosphere is nitrogen, processing
Time is 5h, obtains the graphene porous material.
The composite porous preparation process of graphene oxide is as follows：
1) copolymer 1 of 5 parts of above-mentioned graphene oxide porous material and glucose dicarboxylic acid dimethyl ester and polyethyleneimine is weighed
Part, condensing agent EDCI and dimethyl sulfoxide is added, reacts 12 hours, centrifugation is precipitated；
2) 4 parts of 2 parts of the diatomite weighed and gelatin are configured to aqueous solution, then ultrasound 1 hour is transferred to mold and stands crosslinking；
3) it after the blending colloidal sol after step 2) cross-linking reaction being transformed into gel, then is freeze-dried, graphene oxide is made
It is composite porous.
Experiment measure the composite porous specific surface area of graphene oxide be 500~650m2/g, porosity be 86~
91%.
Embodiment 3
A kind of graphene oxide is composite porous, including following components by weight percent：10 parts of graphene oxide porous material, glucose
8 parts of 2 parts of the copolymer of dicarboxylic acid dimethyl ester and polyethyleneimine, 5 parts of diatomite and gelatin.
The preparation process of graphene oxide porous material is as follows：
（1）It is ultrasonically treated graphene oxide and is made into aqueous solution, a concentration of 15g/L of graphene oxide, ultrasonic time 60min,
Supersonic frequency is 25kHz；
（2）It is freeze-dried step（1）Obtained treatment fluid, temperature are -60 DEG C~-40 DEG C, vacuum degree ＜ 10Pa, freeze-drying
Time is to obtain graphene oxide porous material in 120 hours；
（3）Heat-treat step（2）Obtained graphene oxide porous material, temperature are 600~700 DEG C, and atmosphere is nitrogen, processing
Time is 6h, obtains the graphene porous material.
The composite porous preparation process of graphene oxide is as follows：
1) 2 parts of the copolymer of 10 parts of above-mentioned graphene porous material and glucose dicarboxylic acid dimethyl ester and polyethyleneimine is weighed,
Condensing agent EDCI and dimethyl sulfoxide is added, reacts 48 hours, centrifugation is precipitated；
2) 8 parts of 5 parts of the diatomite weighed and gelatin are configured to aqueous solution, then ultrasound 2 hours is transferred to mold and stands crosslinking；
3) it after the blending colloidal sol after step 2) cross-linking reaction being transformed into gel, then is freeze-dried, graphene oxide is made
It is composite porous.
Experiment measure the composite porous specific surface area of graphene oxide be 580~820m2/g, porosity be 90~
95%.
Embodiment 4
A kind of graphene oxide is composite porous, including following components by weight percent：8 parts of graphene oxide porous material, glucose
5 parts of 2 parts of the copolymer of dicarboxylic acid dimethyl ester and polyethyleneimine, 3 parts of diatomite and gelatin.
The preparation process of graphene oxide porous material is as follows：
（1）It is ultrasonically treated graphene oxide and is made into aqueous solution, a concentration of 15g/L of graphene oxide, ultrasonic time 60min,
Supersonic frequency is 25kHz；
（2）It is freeze-dried step（1）Obtained treatment fluid, temperature are -60 DEG C~-40 DEG C, vacuum degree ＜ 10Pa, freeze-drying
Time is to obtain graphene oxide porous material in 120 hours；
（3）Heat-treat step（2）Obtained graphene oxide porous material, temperature are 600~700 DEG C, and atmosphere is nitrogen, processing
Time is 5h, obtains the graphene porous material.
The composite porous preparation process of graphene oxide is as follows：
1) 2 parts of the copolymer of 8 parts of above-mentioned graphene porous material and glucose dicarboxylic acid dimethyl ester and polyethyleneimine is weighed,
Condensing agent EDCI and dimethyl sulfoxide is added, reacts 48 hours, centrifugation is precipitated；
2) 5 parts of 3 parts of the diatomite weighed and gelatin are configured to aqueous solution, then ultrasound 2 hours is transferred to mold and stands crosslinking；
3) it after the blending colloidal sol after step 2) cross-linking reaction being transformed into gel, then is freeze-dried, graphene oxide is made
It is composite porous.
Experiment measure the composite porous specific surface area of graphene oxide be 750~1000m2/g, porosity be 93~
99%.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of graphene oxide is composite porous, which is characterized in that including following components by weight percent：
5~10 parts of graphene oxide porous material,
Copolymer 1~2 part of glucose dicarboxylic acid dimethyl ester and polyethyleneimine,
2~5 parts of diatomite,
4~8 parts of gelatin,
Wherein, the composite porous specific surface area of the graphene oxide be 500~1000m2/g, porosity be 85~
99%.
2. graphene oxide according to claim 1 is composite porous, which is characterized in that the glucose dioctyl phthalate two
The synthesis step of the copolymer of methyl esters and polyethyleneimine is as follows：The polyethyleneimine and glucose dioctyl phthalate two of quality such as weigh
Methyl esters is molten in ethanol, and 1% triethylamine is added, and is stirred at room temperature 3~4 days, obtains glucose dicarboxylic acid dimethyl ester and polyethyleneimine
Copolymer.
3. graphene oxide according to claim 1 or 2 is composite porous, which is characterized in that the glucose diformazan
The K values of the copolymer of dimethyl phthalate and polyethyleneimine are 110~130.
4. graphene oxide according to claim 1 is composite porous, which is characterized in that the graphene oxide is porous
The preparation process of material is as follows：
（1）It is ultrasonically treated graphene oxide and is made into aqueous solution；
（2）It is freeze-dried step（1）Obtained treatment fluid, obtains porous material；
（3）Heat-treat step（2）Obtained porous material obtains the graphene oxide porous material.
5. graphene oxide according to claim 4 is composite porous, which is characterized in that step（1）Described in aoxidize
A concentration of 10~15g/L of graphene, the ultrasonic time are 45~60min, and supersonic frequency is 20~25kHz.
6. graphene oxide according to claim 4 is composite porous, which is characterized in that step（2）Described in it is cold
It is vacuum freeze drying to be lyophilized dry, and temperature is -60 DEG C~-40 DEG C, vacuum degree ＜ 10Pa, and the time of freeze-drying is 36~120
Hour.
7. graphene oxide according to claim 4 is composite porous, which is characterized in that step（3）Described in heat also
Originally it was atmosphere furnace thermal reduction, temperature is 600~700 DEG C, and atmosphere is argon gas or nitrogen, and processing time is 5~6h.
8. graphene oxide according to claim 1 is composite porous, which is characterized in that the graphene oxide is porous
The preparation process of composite material is as follows：
1）The copolymer that graphene oxide porous material and glucose dicarboxylic acid dimethyl ester and polyethyleneimine are weighed by number, adds
Enter condensing agent EDCI and dimethyl sulfoxide, react 12~48 hours, centrifugation is precipitated；
2）The precipitation and the diatomite and gelatin that are weighed by number are configured to aqueous solution, ultrasound 1~2 hour, then
It is transferred to mold and stands crosslinking；
3）It after blending colloidal sol after step 2) cross-linking reaction is transformed into gel, then is freeze-dried, graphene oxide is made
It is composite porous.
9. graphene oxide according to claim 1 is composite porous, which is characterized in that the graphene oxide is by changing
It is obtained into type Hummers methods, the oxidant that this method uses is potassium peroxydisulfate, phosphorus pentoxide, sodium nitrate, the concentrated sulfuric acid, phosphoric acid
With it is one or more in potassium permanganate.
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| CN103483617A (en) * | 2013-10-16 | 2014-01-01 | 苏州大学 | Method for preparing medical bacteriostasis type graphene oxide porous composite material |
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| CN104118873A (en) * | 2014-08-13 | 2014-10-29 | 济南圣泉集团股份有限公司 | Method for preparing active porous graphene |
| CN104275164A (en) * | 2014-09-29 | 2015-01-14 | 镇江华域环保设备制造有限公司 | Graphene oxide porous composite material for wastewater treatment, and preparation method thereof |
| JP2016158680A (en) * | 2015-02-27 | 2016-09-05 | 国立大学法人北海道大学 | Scaffold for osteoanagenesis or for skin regeneration using graphene oxide |
| WO2017217832A1 (en) * | 2016-06-17 | 2017-12-21 | 한국기계연구원 | Method for producing carbon aerogel precursor, and carbon aerogel precursor and carbon aerogel produced thereby |
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2018
- 2018-06-22 CN CN201810649660.0A patent/CN108675683A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483617A (en) * | 2013-10-16 | 2014-01-01 | 苏州大学 | Method for preparing medical bacteriostasis type graphene oxide porous composite material |
| CN103663438A (en) * | 2013-11-18 | 2014-03-26 | 南京久和纳米科技有限公司 | Preparation method of porous graphene |
| CN104118873A (en) * | 2014-08-13 | 2014-10-29 | 济南圣泉集团股份有限公司 | Method for preparing active porous graphene |
| CN104275164A (en) * | 2014-09-29 | 2015-01-14 | 镇江华域环保设备制造有限公司 | Graphene oxide porous composite material for wastewater treatment, and preparation method thereof |
| JP2016158680A (en) * | 2015-02-27 | 2016-09-05 | 国立大学法人北海道大学 | Scaffold for osteoanagenesis or for skin regeneration using graphene oxide |
| WO2017217832A1 (en) * | 2016-06-17 | 2017-12-21 | 한국기계연구원 | Method for producing carbon aerogel precursor, and carbon aerogel precursor and carbon aerogel produced thereby |
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Application publication date: 20181019 |