CN102432720A - Preparation method for graphene based compound hydrogel modified with poly (N-isopropylacrylamide) - Google Patents
Preparation method for graphene based compound hydrogel modified with poly (N-isopropylacrylamide) Download PDFInfo
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- CN102432720A CN102432720A CN2011102281580A CN201110228158A CN102432720A CN 102432720 A CN102432720 A CN 102432720A CN 2011102281580 A CN2011102281580 A CN 2011102281580A CN 201110228158 A CN201110228158 A CN 201110228158A CN 102432720 A CN102432720 A CN 102432720A
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Abstract
The invention relates to a preparation method for a graphene based compound hydrogel modified with poly (N-isopropylacrylamide). The preparation method comprises the following steps: (1) at room temperature, adding graphite oxide in water, ultrasonically dispersing so as to form a graphite oxide aqueous solution, and then adding monomer N-isopropylacrylamide and trigger potassium peroxydisulfate, and ultrasonically dispersing under a nitrogen atmosphere, thereby forming a precursor solution; and (2) performing hydro-thermal reaction on the precursor solution, after the reaction, cooling the precursor solution to room temperature, and taking out a product. The preparation method is simple in process and short in reaction time, thereby being suitable for industrial production. The graphene based compound hydrogel prepared according to the preparation method has the advantages that the graphene is served as a three-dimensional network skeleton, the mechanical strength is high, the chemical stability is excellent, the conductivity is high, the reversible swelling/ deswelling response to ambient temperature is achieved, the change in conductivity is triggered, and the application prospect in the fields of electronics, biomedicine, and the like is wide.
Description
Technical field
The invention belongs to the preparation field of Graphene hydrogel, particularly a kind of preparation method of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel.
Background technology
The two dimension grapheme material has characteristics such as ultra-thin, ultra firm and superpower conductivity, has obtained widespread use in fields such as nano electron device, matrix material, energy storage and biomedicines.In recent years, scientist finds to use several different methods to prepare the three-dimensional grapheme material of graphene film assembling.This material has kept the excellent conductivity of graphene film, and the three-dimensional framework construction machine intensity that assembles through the π key is high, chemicalstability is good, has a large amount of nano levels to micron-sized hole thereby has high specific surface area.Based on above characteristics, this type novel three-dimensional grapheme material is regarded as good energy storage material.People such as Y.Zhu have prepared three-dimensional porous grapheme material at the last graphite oxide that utilizes KOH activation microwave to peel off of having reported of Science (2011) DOI:10.1126/science.1200770, and this material has 3100m
2The specific surface area of/g, its energy density of ultracapacitor that is assembled into as electrode can reach the lead-acid cell level, the charge velocities that also keeps the output of ultracapacitor inherent superpower simultaneously and be exceedingly fast.This three-dimensional porous cancellated carbon material is regarded as the optimum electrode material of ultracapacitor.People such as X.Zhang are at the last Graphene hydrogel that utilizes xitix reduction-oxidation graphite solution to obtain the three-dimensional framework structure of having reported of Journal ofMaterials Chemistry 21 (2011) 6494-6497; And its lyophilize obtained the Graphene gas gel as electrode material for super capacitor, it can reach 128F/g than electric capacity.People such as Y.Xu make graphite oxide be self-assembled into the Graphene hydrogel material in the last method of utilizing hydro-thermal of also once reporting of ACS Nano 4 (2010) 4323-4330, and it reaches 172F/g than electric capacity.
Yet the three-dimensional grapheme material purposes of preparation is single at present, and its gel network skeleton structure is not fully utilized.For example, than the polymer gel material, three-dimensional grapheme material does not possess the reversible volumetric change performance of environmental response.This is because in graphene-based material, because stronger pi-pi bond effect graphene film is spontaneous easily and irreversibly pile up again.For two-dimentional graphene film, can utilize the method for surface-treated effectively to address this problem, thereby and make in this way and also can suppress simultaneously the effect of π key and can't constitute the Graphene skeleton structure and obtain three-dimensional grapheme material.
Polyalcohol hydrogel has obtained effective application because of the performance acquisition scientist that reversible volumetric change (swelling/deswelling phenomenon) takes place down its unique external stimulus (temperature, pH value, light, electricity, magnetic etc.) pays close attention to widely at pharmaceutical engineering and biological technical field.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel; This method technology is simple, and the reaction times is short, is suitable for suitability for industrialized production; The graphene-based composite aquogel of gained with Graphene as the three-dimensional network skeleton; Physical strength is high, and chemicalstability is good, and specific conductivity is high;
The preparation method of a kind of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel of the present invention comprises:
(1) preparation of precursor solution:
At room temperature, graphite oxide is added in the entry, ultra-sonic dispersion forms the graphite oxide aqueous solution, adds then monomer N-NSC 11448 and initiator potassium persulfate, and ultra-sonic dispersion forms precursor solution under nitrogen atmosphere;
(2) compound water congealing composes:
Above-mentioned precursor solution is carried out hydro-thermal reaction, and reaction is cooled to room temperature after finishing, and takes out product and gets final product.
The mass volume ratio of graphite oxide described in the step (1) and water is 1～4mg: 1ml.
Ultra-sonic dispersion described in the step (1) forms in the graphite oxide aqueous solution, and ultrasonic power is 200～400W, and the time is 1～2h.
The mass ratio of N-NSC 11448 described in the step (1) and graphite oxide is 10: 1～50: 1, and the mass ratio of N-NSC 11448 and Potassium Persulphate is 10: 1～100: 1.
Ultra-sonic dispersion described in the step (1) forms in the precursor solution, and ultrasonic power is 200～400W, and the time is 30～60min.
Hydro-thermal reaction described in the step (2) is for to carry out in reaction kettle, and the temperature of reaction of hydro-thermal reaction is 100～200 ℃, and the reaction times is 8～16h.
Beneficial effect
(1) this method technology is simple, and the reaction times is short, is suitable for suitability for industrialized production;
(2) as the three-dimensional network skeleton, physical strength is high with Graphene for the graphene-based composite aquogel of this method preparation, and chemicalstability is good, and specific conductivity is high;
(3) prepared graphene base composite aquogel of the present invention has reversible swelling/deswelling response to envrionment temperature, and can cause conductivity variations, the more wide application space of developing in fields such as electron device, biomedicines.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the composite aquogel of embodiment 1 preparation;
Fig. 2 is Fourier's infared spectrum of the composite aquogel of embodiment 1 preparation;
Fig. 3 is the electron scanning micrograph of the composite aquogel of embodiment 1 preparation;
Fig. 4 is the temperature response photo of the composite aquogel of embodiment 1 preparation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Take by weighing the 50mg graphite oxide and add the 50ml deionized water; Ultra-sonic dispersion 2h under 200W power; After waiting to be uniformly dispersed, take by weighing the 2.5gN-NSC 11448 again, the 250mg Potassium Persulphate adds in the above-mentioned graphite oxide aqueous solution, at nitrogen atmosphere protection continuation ultra-sonic dispersion 60min (200W) down.Above-mentioned precursor solution is put into reaction kettle, be warming up to 100 ℃, reaction 12h.Reaction finishes back taking-up hydrogel product and gets final product.
Fig. 1 is the X ray diffracting spectrum of product, and the diffraction peak among the figure shows that graphite oxide is reduced into and is Graphene.Fig. 2 is Fourier's infared spectrum of product, can find out to contain poly N-isopropyl acrylamide in the composite aquogel.Fig. 3 is the electron scanning micrograph of product, can find out that the hydrogel product constitutes the network skeleton structure by the multi-layer graphene sheet, and poly N-isopropyl acrylamide is distributed in the graphene film intercalation and between the skeleton structure.The ultimate compression strength that measuring mechanical property obtains hydrogel is 3.11MPa.The specific conductivity that electrical performance testing obtains hydrogel is 4 * 10
-3S/cm.Fig. 4 is the swelling/deswelling experiment photo of product, in experiment along with the rising of envrionment temperature with to reduce the volume change of hydrogel obvious and reversible.And find the contraction along with volume through electrical performance testing, the specific conductivity of hydrogel is from 4 * 10
-3S/cm is reduced to 4 * 10
-4S/cm; Along with gel volume expands its specific conductivity rise to 4 * 10
-3About S/cm.In swelling/deswelling experiment, find that hydrogel has good chemicalstability.
Embodiment 2
Take by weighing the 100mg graphite oxide and add the 50ml deionized water; Ultra-sonic dispersion 1.5h under 300W power; After waiting to be uniformly dispersed, take by weighing the 3gN-NSC 11448 again, the 60mg Potassium Persulphate adds in the above-mentioned graphite oxide aqueous solution, at nitrogen atmosphere protection continuation ultra-sonic dispersion 45min (300W) down.Above-mentioned precursor solution is put into reaction kettle, be warming up to 150 ℃, reaction 16h.Reaction finishes back taking-up hydrogel product and gets final product.
X-ray diffraction and Fourier's infrared test show respectively and contain Graphene and poly N-isopropyl acrylamide component in the composite aquogel.Constitute network skeleton structure to the hydrogel product by the multi-layer graphene sheet through sem observation, poly N-isopropyl acrylamide is distributed in the graphene film intercalation and between the skeleton structure.Graphene-based composite aquogel product physical strength is high, and chemicalstability is good, and specific conductivity is high, and temperature is had reversible swelling/deswelling response and causes conductivity variations.
Embodiment 3
Take by weighing the 200mg graphite oxide and add the 50ml deionized water; Ultra-sonic dispersion 1h under 400W power; After waiting to be uniformly dispersed, take by weighing the 2gN-NSC 11448 again, the 20mg Potassium Persulphate adds in the above-mentioned graphite oxide aqueous solution, at nitrogen atmosphere protection continuation ultra-sonic dispersion 30min (400W) down.Above-mentioned precursor solution is put into reaction kettle, be warming up to 200 ℃, reaction 8h.Reaction finishes back taking-up hydrogel product and gets final product.
X-ray diffraction and Fourier's infrared test show respectively and contain Graphene and poly N-isopropyl acrylamide component in the composite aquogel.Constitute network skeleton structure to the hydrogel product by the multi-layer graphene sheet through sem observation, poly N-isopropyl acrylamide is distributed in the graphene film intercalation and between the skeleton structure.Graphene-based composite aquogel product physical strength is high, and chemicalstability is good, and specific conductivity is high, and temperature is had reversible swelling/deswelling response and causes conductivity variations.
Claims (6)
1. the preparation method of a poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel comprises:
(1) at room temperature, graphite oxide is added in the entry, ultra-sonic dispersion forms the graphite oxide aqueous solution, adds monomer N-NSC 11448 and initiator potassium persulfate then, and ultra-sonic dispersion forms precursor solution under nitrogen atmosphere;
(2) above-mentioned precursor solution is carried out hydro-thermal reaction, reaction is cooled to room temperature after finishing, and takes out product and gets final product.
2. the preparation method of a kind of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel according to claim 1 is characterized in that: the mass volume ratio of graphite oxide described in the step (1) and water is 1～4mg: 1ml.
3. the preparation method of a kind of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel according to claim 1; It is characterized in that: the ultra-sonic dispersion described in the step (1) forms in the graphite oxide aqueous solution; Ultrasonic power is 200～400W, and the time is 1～2h.
4. the preparation method of a kind of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel according to claim 1; It is characterized in that: the mass ratio of N-NSC 11448 described in the step (1) and graphite oxide is 10: 1～50: 1, and the mass ratio of N-NSC 11448 and Potassium Persulphate is 10: 1～100: 1.
5. the preparation method of a kind of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel according to claim 1; It is characterized in that: the ultra-sonic dispersion described in the step (1) forms in the precursor solution; Ultrasonic power is 200～400W, and the time is 30～60min.
6. the preparation method of a kind of poly N-isopropyl acrylamide modified graphite thiazolinyl composite aquogel according to claim 1; It is characterized in that: the hydro-thermal reaction described in the step (2) is for to carry out in reaction kettle; The temperature of reaction of hydro-thermal reaction is 100～200 ℃, and the reaction times is 8～16h.
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| CN105645403A (en) * | 2016-03-28 | 2016-06-08 | 南京邮电大学 | Preparation method of high-performance nitrogen-doped three-dimensional graphene |
| CN106749923A (en) * | 2016-12-14 | 2017-05-31 | 青岛科技大学 | A kind of supernet structure graphene oxide hydrogel and preparation method thereof |
| CN106773143A (en) * | 2016-12-06 | 2017-05-31 | 东华大学 | A kind of near infrared light mutagens shape Graphene/NIPAAm laminated films and its preparation and application |
| CN108586774A (en) * | 2018-03-14 | 2018-09-28 | 西南科技大学 | A kind of preparation method of poly-N-isopropyl acrylamide/konjaku glucomannan/graphene oxide composite hydrogel |
| CN109232916A (en) * | 2018-08-17 | 2019-01-18 | 东华大学 | A kind of compound thermal response-type hydrogel of Mxene/PNIPAM/ alginate and its preparation and application |
| CN110002433A (en) * | 2019-03-13 | 2019-07-12 | 太原理工大学 | A kind of preparation method of high-specific surface area high compression-strength graphene aerogel |
| CN110341248A (en) * | 2019-07-05 | 2019-10-18 | 吴勇 | A kind of glued board that bonding strength is high |
| CN111944586A (en) * | 2020-08-26 | 2020-11-17 | 合肥工业大学 | Metal processing water lubricating nano additive and preparation method thereof |
| CN114446672A (en) * | 2021-12-17 | 2022-05-06 | 晋江瑞碧科技有限公司 | Preparation method of temperature-responsive graphene-based hydrogel electrode |
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| CN105618087B (en) * | 2016-01-03 | 2018-10-16 | 复旦大学 | A kind of two chalcogen compound nanoscale twins compound of transition metal and preparation method thereof |
| CN105618087A (en) * | 2016-01-03 | 2016-06-01 | 复旦大学 | Transition metal dithio compound nanometer sheet layer compound and preparation method thereof |
| CN105645403A (en) * | 2016-03-28 | 2016-06-08 | 南京邮电大学 | Preparation method of high-performance nitrogen-doped three-dimensional graphene |
| CN105645403B (en) * | 2016-03-28 | 2018-06-22 | 南京邮电大学 | A kind of preparation method of high-performance N doping three-dimensional grapheme |
| CN106773143A (en) * | 2016-12-06 | 2017-05-31 | 东华大学 | A kind of near infrared light mutagens shape Graphene/NIPAAm laminated films and its preparation and application |
| CN106749923A (en) * | 2016-12-14 | 2017-05-31 | 青岛科技大学 | A kind of supernet structure graphene oxide hydrogel and preparation method thereof |
| CN106749923B (en) * | 2016-12-14 | 2018-09-28 | 青岛科技大学 | A kind of supernet structure graphene oxide hydrogel and preparation method thereof |
| CN108586774A (en) * | 2018-03-14 | 2018-09-28 | 西南科技大学 | A kind of preparation method of poly-N-isopropyl acrylamide/konjaku glucomannan/graphene oxide composite hydrogel |
| CN109232916A (en) * | 2018-08-17 | 2019-01-18 | 东华大学 | A kind of compound thermal response-type hydrogel of Mxene/PNIPAM/ alginate and its preparation and application |
| CN110002433A (en) * | 2019-03-13 | 2019-07-12 | 太原理工大学 | A kind of preparation method of high-specific surface area high compression-strength graphene aerogel |
| CN110002433B (en) * | 2019-03-13 | 2022-09-06 | 太原理工大学 | Preparation method of graphene aerogel with high specific surface area and high compressive strength |
| CN110341248A (en) * | 2019-07-05 | 2019-10-18 | 吴勇 | A kind of glued board that bonding strength is high |
| CN111944586A (en) * | 2020-08-26 | 2020-11-17 | 合肥工业大学 | Metal processing water lubricating nano additive and preparation method thereof |
| CN114446672A (en) * | 2021-12-17 | 2022-05-06 | 晋江瑞碧科技有限公司 | Preparation method of temperature-responsive graphene-based hydrogel electrode |
| CN114446672B (en) * | 2021-12-17 | 2023-07-28 | 武夷学院 | Preparation method of temperature-responsive graphene-based hydrogel electrode |
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