CN106422816B - The preparation of grapheme foam-poly-dopamine composite membrane and its product and application - Google Patents
The preparation of grapheme foam-poly-dopamine composite membrane and its product and application Download PDFInfo
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- CN106422816B CN106422816B CN201610841373.0A CN201610841373A CN106422816B CN 106422816 B CN106422816 B CN 106422816B CN 201610841373 A CN201610841373 A CN 201610841373A CN 106422816 B CN106422816 B CN 106422816B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
Abstract
The invention discloses a kind of preparation of grapheme foam-poly-dopamine composite membrane and its product and applications, and wherein the preparation method includes the following steps：(1) grapheme foam-poly-dopamine is prepared：The pH value for adjusting graphene oxide solution adds Dopamine hydrochloride and obtains precursor solution, carries out hydro-thermal reaction and obtains grapheme foam-poly-dopamine；(2) grapheme foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is added to N, in N- bicine N-, and is mixed with temperature sensing polymer, stirred, be filtered by vacuum and obtain thermosensitive graphene foam-poly-dopamine composite membrane.The present invention is improved by integrated artistic design, the reaction condition of each step etc. to crucial preparation process, the grapheme foam being prepared-poly-dopamine composite membrane has good Thermo-sensitive, excellent Superhydrophilic and underwater superoleophobic property, are highly suitable for being applied to water-oil separating.
Description
Technical field
The invention belongs to functional composite material technical fields, multiple more particularly, to a kind of grapheme foam-poly-dopamine
The preparation of conjunction film and its product and application, the grapheme foam-poly-dopamine composite membrane have good Thermo-sensitive.
Background technique
In recent years, petroleum and organic liquid leakage accident cause catastrophic pollution to water resources such as ocean and rivers,
Irremediable economic loss is brought to the mankind, has seriously endangered the health and safety of the mankind and animals and plants.In petroleum and have
In the oil-water mixture that machine liquid leakage is formed, water and oil are not only to be simply mixed together, and it is very small to yet form size
Droplets of emulsified oil.This large-scale oil emulsion contaminant water is difficult to administer, and will lead to serious ecosystem problem.Currently,
Membrane technology can intelligently applied to various sizes lotion oil separation, and have can operate continuously, simple process with
High-efficient advantage.However, during using the processing contaminant water of membrane technology, there are still many problems urgently to be resolved and
Challenge.For example, the problem of dirt and clogging of pores of surfactant formation, can all cause membrane flux and efficiency to reduce.In addition,
There are also another great problem, low separation efficiency of most of films in the oil water mixture of high concentration.Therefore, for difference
The mechanism of material, water-oil separating still requires study.Now, the draw inspiration from natural phenomena produces height using new material
Durable seperation film is imitated, is a quantum jump mouth of water-oil separating problem.
In a variety of materials, graphene and its composite material due to its low cost, high durability and excellent physical characteristic,
And becomes and compare the candidate material for having application prospect.It is most of compound using three-dimensional structure graphene in water-oil separating application
Material, on the one hand, relative to the material of two-dimensional structure, three-dimensional structure material has bigger specific surface area, than pore volume and
Higher mechanical performance and conductivity；On the other hand, three-dimensional structure grapheme material oil-based liquid load with higher.This
Outside, novel surface wetability material role in oil water separation process is just being increasingly subject to the attention of people.The study found that
It is available a series of with such as super hydrophilic, super-hydrophobic, super oleophylic by control surface topography and chemical composition, it is superoleophobic
Etc. the material for having special wetability.If material mutually has different wetting characteristics with oil to water phase, this can be very big
Promote oil-water separation in degree.Therefore, the height that special this field of wetability material obtains rapidly academia is prepared to look steadily
Mesh obtains development and application there are many kinds of special wetability material.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of grapheme foams-
The preparation of poly-dopamine composite membrane and its product and application, wherein being designed by the integrated artistic to its crucial preparation process, being each
The reaction condition (proportion of such as reactant, hydrothermal temperature) of step improves, and compared with prior art, is prepared
Grapheme foam-poly-dopamine composite membrane have good Thermo-sensitive, can according to the change of temperature, realize grapheme foam
Regulation of the aperture in nanoscale；The composite membrane has excellent Superhydrophilic and underwater superoleophobic property, is highly suitable for applying
In water-oil separating, and the regulation for realizing membrane flux is controlled by temperature, can efficiently separate the emulsified oil droplet dispersed in water.
To achieve the above object, according to one aspect of the present invention, it is compound to provide a kind of grapheme foam-poly-dopamine
The preparation method of film, which is characterized in that include the following steps：
(1) grapheme foam-poly-dopamine is prepared：
The pH value for adjusting graphene oxide solution keeps the graphene oxide solution alkaline, then molten to the graphene oxide
Liquid is ultrasonically treated；Then, Dopamine hydrochloride is added into the graphene oxide solution, and utilizes ultrasonic disperse again, obtains
To precursor solution；Then, hydro-thermal reaction is carried out to the precursor solution and obtains gel-like product, which is done
Grapheme foam-poly-dopamine is obtained after dry；
(2) grapheme foam-poly-dopamine composite membrane is prepared：
Grapheme foam-the poly-dopamine being prepared in the step (1) is ground, N is then added to,
Ultrasonic disperse is carried out in N- bicine N-, obtains grapheme foam-poly-dopamine/N, the dispersion of N- bicine N-
System；Then, by the grapheme foam-poly-dopamine/N, N- bicine N- disperse system and dissolved with temperature sensing polymer
N, N- bicine N- solution mixes, is stirred to react, and thermosensitive graphene bubble is then obtained by vacuum filtration
Foam-poly-dopamine composite membrane.
As present invention further optimization, in the step (2), the temperature sensing polymer is poly- (2- methyl -2- third
Olefin(e) acid -2- (2- methoxy ethoxy) ethyl ester), polyacrylamide, polyacrylic acid, poly(N-isopropylacrylamide), polyethylene
At least one of pyrrolidones.
As present invention further optimization, in the step (1), the pH value for adjusting graphene oxide solution makes this
Graphene oxide solution is alkalinity, is that Tris-HCl is added into the graphene oxide solution to make the pH of the graphene oxide solution
Value is adjusted to 7.5~9.5.
As present invention further optimization, in the precursor solution in the step (1), graphene oxide it is dense
Degree is 1mg/ml~12mg/ml, and the concentration of Dopamine hydrochloride is 0.1mg/ml~8mg/ml；Preferably, the graphene oxide
Mass ratio with the Dopamine hydrochloride is 10~1.
As present invention further optimization, the hydro-thermal reaction in the step (1) is reacted at 60~120 DEG C
6~32h；The drying is freeze-drying.
As present invention further optimization, in the step (2), the grapheme foam-poly-dopamine/N, N- dihydroxy
Ethyl glycine disperse system is alkalinity, it is preferred that the grapheme foam-poly-dopamine/N, N- bicine N- disperse system
PH value be 7.5~9.0.
As present invention further optimization, in the step (2), the stirring is carried out at 20 DEG C~40 DEG C,
Mixing time is 6~72h.
Above-mentioned grapheme foam-poly-dopamine composite membrane preparation side is utilized it is another aspect of this invention to provide that providing
The grapheme foam that method is prepared-poly-dopamine composite membrane.
Another aspect according to the invention provides and utilizes above-mentioned grapheme foam-poly-dopamine composite membrane preparation side
The grapheme foam that method is prepared-application of the poly-dopamine composite membrane in water-oil separating.
Contemplated above technical scheme through the invention, compared with prior art, due to the poly- DOPA of grapheme foam-
The preparation process of amine composite membrane improves, first that Graphene gel and hydrophilic poly-dopamine is compound, not only can
The microcellular structure for increasing Graphene gel, can also enhance the hydrophily of grapheme material；Then, then by the poly- DOPA of graphene-
Amine further modifies thermally sensitive polymeric and is modified and thermal response film is prepared；It in practical applications, can be by grinding
Study carefully the influence of the variation of temperature to the seperation film separative efficiency of the hydrophilic/oleophobic, reach intelligent control seperation film water flux and
The purpose of membrane channels size.The seperation film that preparation method is prepared through the invention helps to separate various different rulers in water phase
Very little oil liquid carries out intellectual monitoring to seperation film by the response of thermally sensitive polymeric, and then realizes to water-oil emulsion high throughput
Quick separating.Also, the characteristic of hydrophilic/oleophobic of the material makes it have antipollution, rapid cleaning regeneration, energy repetitive cycling benefit
With the characteristics of, therefore lid seperation film have longer service life and higher oil recovery rate.Furthermore.The preparation method is simple
Efficiently, raw material is easy to get, is cheap, is energy-efficient, is environmentally friendly, and stable operation safety, is expected to realize large-scale industrial production.
The present invention is anti-by the pH environment, dispersion degree, hydro-thermal of reactant ratio, reaction solution to each reaction step
Condition etc. is answered to be controlled, by molten with graphene oxide to Tris-HCl in preparing grapheme foam-poly-dopamine step
The mixed solution of both liquid carries out the graphite that ultrasonic treatment is dispersed graphene oxide layer with monolithic form, and will be prepared
Alkene foam-poly-dopamine is ground into fractionlet for the preparation of grapheme foam-poly-dopamine composite membrane, is finally prepared
Thermosensitive graphene foam-poly-dopamine composite membrane has excellent Superhydrophilic and underwater superoleophobic property, is highly suitable for answering
For water-oil separating, and is controlled by temperature and realize that the regulation of membrane flux (i.e. according to the change of temperature, realizes graphene bubble
Regulation of the foam aperture in nanoscale), the emulsified oil droplet dispersed in water can be efficiently separated.
Grapheme foam in the present invention is that kind has mushy graphene stacked structure, graphene film from inside to outside
Layer constitutes the porous foam shape material of a three-dimensional netted full-mesh, the porous structure of grapheme foam in a seamless fashion
It is that overlapped accumulation is formed under the action of hydrogen bond and π-pi-conjugated key due to graphene sheet layer, which not only has extremely low
Density, high porosity and high-specific surface area, but also inherit the excellent chemistry of graphene, calorifics, mechanical stability
Can, expand physical property and the application space of graphene, and simple production process, cost is relatively low.Since grapheme foam has gently
The stable feature low with production cost of soft, bigger serface, chemical characteristic, in addition being repaired using dopamine to grapheme foam
Decorations can substantially increase the hydrophily and porosity of grapheme foam；Further, grapheme foam-poly-dopamine can be with high score
Sub (especially temperature-sensitive macromolecular) is compound, and obtained thermosensitive graphene foam-this thermal response of poly-dopamine composite membrane is thin
Film, the response polymer in the composite membrane are able to achieve regulation of the grapheme foam aperture in nanoscale (that is, with environment temperature
The variation of degree, the pore size in grapheme foam can flexibly change；Since the hole aperture in grapheme foam is in nanoscale,
Therefore, it can be realized grapheme foam aperture in the regulation of nanoscale).
Although being mostly that graphene oxide is molten at present also about other reports of thermosensitive graphene foam
Liquid directly directly reacts with temperature-sensitive macromolecular, and phase occurs by the oxygen-containing functional group and macromolecule of surface of graphene oxide
The addition reaction answered generates thermosensitive graphene foam.And the present invention is first passed through and is carried out using poly-dopamine to grapheme foam
Functionalization, Dopamine hydrochloride have certain reduction while aoxidizing autohemagglutination, to the oxygen-containing functional group of surface of graphene oxide
Effect, and the grapheme foam of poly-dopamine modification has superior hydrophilic and oleophobic property, porosity and mechanical strength.This
Outside, since in generating grapheme foam-poly-dopamine hydrothermal reaction process, graphene oxide loses most surface
Oxygenated functional group, thermally sensitive polymeric later are obtained with grapheme foam-poly-dopamine by Michael addition reaction thermo-responsive
Compound is the active site provided by poly-dopamine, and reaction can be gone on smoothly at normal temperature, and preparation process is simple, production
It is high-efficient.Grapheme foam-poly-dopamine prepared by the present invention has had both heat sensitivity energy, higher porosity and superior
Hydrophilic and oleophobic characteristic.
Filter membrane is prepared using thermosensitive graphene foam-poly-dopamine in the present invention, at room temperature (such as 20 DEG C~
40 DEG C) with excellent Superhydrophilic and underwater superoleophobic property, and there is good response to temperature；The response film is applied to
Water-oil separating can be controlled the regulation for realizing membrane flux by temperature, be dispersed so that the membrane material be enable to efficiently separate in water
Emulsified oil droplet, be a kind intelligentized response film；Also, the superoleophobic characteristic of the intelligence grapheme material is conducive to material
Cleaning regeneration and repeated recycling utilize (for example, by the temperature of intelligent control film, adjust the size of membrane pores, Neng Goushi
The cleaning of dirt in existing membrane pores, consequently facilitating the regeneration and recycling of film), it can be widely applied to for example have exhibiting high surface living
The petroleum industry that property agent uses.
Particularly have the following advantages that：
1, graphene nano material is assembled to the three-dimensional porous graphene macroscopic material to be formed and inherits graphene nano material
Expect excellent light, heat, electricity, mechanical property, its scale application is also realized by its macrostructure.
2, temperature-sensitive macromolecular is modified to porous graphene assembly surface, there is excellent Superhydrophilic at normal temperature
With underwater superoleophobic property, it can realize that high efficiency oil-water separates in dynamic fluid.
3, the superoleophobic characteristic of the seperation film can antipollution, regeneration convenient for cleaning, realize repeated recycling utilize, should
Method efficiently, green, cheap, energy-saving and environmental protection.
The present invention is prepared by the methods of MOLECULE DESIGN and surface modification can change its surface profit under given conditions
Moist material controls material surface wetting characteristics by the variation of temperature to obtain the effect that intelligence is separated and discharged；
Also, due to surface of graphene oxide functional group rich in, can be relatively easy to that it is modified and is modified, to make
The standby functional material for obtaining having special wetability and energy intelligent control, the preparation method are simple and easy to do.
Detailed description of the invention
Fig. 1 a, Fig. 1 b are micropore grapheme foam-poly-dopamine pictorial diagram and scanning electron microscope (SEM) figure respectively in Fig. 1；
Fig. 2 is grapheme foam-poly-dopamine composite membrane pictorial diagram, the grapheme foam-poly-dopamine composite membrane tool
There is good Thermo-sensitive；
In Fig. 3 Fig. 3 a, Fig. 3 b be respectively film with the contact angle of water (state, the right figure that the corresponding 0s of left figure has just been contacted are corresponding
State after contacting 5s), in water film with oily contact angle (after the corresponding contact 5s of state, the right figure that the corresponding 0s of left figure has just been contacted
State)；As it can be seen that the hydrophilic and oleophobic characteristic of thermosensitive graphene foam-poly-dopamine composite membrane；
Fig. 4 is the device process and separating effect schematic diagram of water-oil separating test；
Fig. 5 is the pictorial diagram that grapheme foam-poly-dopamine filters film.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
N- bicine N- solution (can be well prepared in advance) mixing, is stirred to react, and finally by being filtered by vacuum, obtained thermal response is thin
Film.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 8.5.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 2mg/ml, salt
The concentration of sour dopamine is 1mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 2.Preferably, hydro-thermal reaction temperature
Degree is 80 DEG C.Preferably, the hydro-thermal reaction time is 12h.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 8.5.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 23 DEG C.
Grapheme foam-poly-dopamine and temperature sensing polymer reacts at 25 DEG C of room temperature in step (2)
Lower progress, preferably, the reaction time is 48h.
Embodiment 2
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 7.5.
In step (1), the mixed liquor of graphene oxide and poly-dopamine, the concentration of graphene oxide is 1mg/ml, hydrochloric acid
The concentration of dopamine is 0.1mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 10.Preferably, hydro-thermal reaction temperature
Degree is 60.Preferably, the hydro-thermal reaction time is 6h.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 7.5.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 26 DEG C.
Grapheme foam-poly-dopamine carries out at 27 DEG C of room temperature with reacting for temperature sensing polymer in step (2), as
It is preferred that reaction time 6h.
Embodiment 3
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 8.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 4mg/ml, salt
The concentration of sour dopamine is 1mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 14.Preferably, hydro-thermal reaction temperature
Degree is 70 DEG C.Preferably, the hydro-thermal reaction time is 8h.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 8.0.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 35 DEG C.
Grapheme foam-poly-dopamine carries out at 37 DEG C of room temperature with reacting for temperature sensing polymer in step (2), as
It is preferred that reaction time 10h.
Embodiment 4
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 8.5.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 8mg/ml, salt
The concentration of sour dopamine is 8mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 1.Preferably, hydro-thermal reaction temperature
Degree is 60~120 DEG C.Preferably, the hydro-thermal reaction time is 16h.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 8.5.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 25 DEG C.
Grapheme foam-poly-dopamine carries out at 25 DEG C of room temperature with reacting for temperature sensing polymer in step (2), as
It is preferred that the reaction time is for 24 hours.
Embodiment 5
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 8.5.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 6mg/ml, salt
The concentration of sour dopamine is 1mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 6.Preferably, hydro-thermal reaction temperature
Degree is 80 DEG C.Preferably, the hydro-thermal reaction time is for 24 hours.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 8.0.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 23 DEG C.
Grapheme foam-poly-dopamine carries out at 30 DEG C of room temperature with reacting for temperature sensing polymer in step (2), as
It is preferred that reaction time 36h.
Embodiment 6
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 9.0.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 10mg/ml, salt
The concentration of sour dopamine is 2mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 5.Preferably, hydro-thermal reaction temperature
Degree is 90 DEG C.Preferably, the hydro-thermal reaction time is for 24 hours.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 9.0.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 20 DEG C.
Grapheme foam-poly-dopamine carries out at 27 DEG C of room temperature with reacting for temperature sensing polymer in step (2), as
It is preferred that reaction time 48h.
Embodiment 7
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 9.5.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 12mg/ml, salt
The concentration of sour dopamine is 6mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 2.Preferably, hydro-thermal reaction temperature
Degree is 100 DEG C.Preferably, the hydro-thermal reaction time is 28h.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 9.0.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 26 DEG C.
Grapheme foam-poly-dopamine is carried out with reacting for temperature sensing polymer at 28 DEG C of room temperature in step (2), as excellent
Choosing, reaction time 60h.
Embodiment 8
Include the following steps：
(1) grapheme foam-poly-dopamine is prepared：Tris-HCl is mixed with graphene oxide solution, adjusts pH, then
Ultrasound disperses graphene oxide layer with monolithic form.Dopamine hydrochloride ultrasonic disperse is added, graphene oxide is configured to
With the mixed liquor of Dopamine hydrochloride, hydro-thermal reaction is carried out.Cooled to room temperature after reaction coagulates the black circle of generation
Rubber column gel column is clean with deionized water washing by soaking, and finally freeze-drying obtains grapheme foam-poly-dopamine.
(2) thermosensitive graphene foam-poly-dopamine composite membrane is prepared：Grapheme foam-poly-dopamine is ground into small
Fragment is then added to N, carries out ultrasonic disperse in N- bicine N-.Later with the N that has dissolved temperature sensing polymer,
The mixing of N- bicine N- solution, is stirred to react, and thermal response film is made finally by being filtered by vacuum.
(3) in terms of grapheme foam made from-poly-dopamine composite membrane is applied to water-oil separating.
In step (1), the pH value of Tris-HCl and graphene oxide mixed solution is 9.5.
In step (1), the mixed liquor of graphene oxide and Dopamine hydrochloride, the concentration of graphene oxide is 12mg/ml, salt
The concentration of sour dopamine is 8mg/ml, and the concentration ratio of graphene oxide and Dopamine hydrochloride is 1.5.Preferably, hydro-thermal reaction
Temperature is 120 DEG C.Preferably, the hydro-thermal reaction time is 32h.
After grapheme foam-poly-dopamine fragment carries out ultrasonic disperse in N, N- bicine N- in step (2),
The dispersion liquid is alkalescent, preferably, pH value is 9.0.
Temperature sensing polymer be added is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) second in step (2)
Ester P (OEMO2- MA), preferably, the lower critical solution temperature (LCST) of the polymer is 23 DEG C.
Grapheme foam-poly-dopamine carries out at 24 DEG C of room temperature with reacting for temperature sensing polymer in step (2), as
It is preferred that reaction time 72h.
Temperature sensing polymer in the present invention can also use poly- 2- first other than the specific substance in above-described embodiment
(No. CAS is 9003- for base -2- acrylic acid -2- (2- methoxy ethoxy) ethyl ester (CAS 45103-58-0), polyacrylamide
05-8), polyacrylic acid (No. CAS is 9003-01-4), poly-N-isopropyl acrylamide (No. CAS is 25189-55-3), polyethylene
Pyrrolidones (No. CAS be 9003-39-8) etc. or the temperature sensing polymer similar with them, as long as its is low for used polymer
Critical solution temperature (LCST) is not higher than the temperature being stirred to react can be (that is, the temperature sensing polymer that selection is different, needs
The temperature for being stirred to react progress is adjusted according to the LCST of the temperature sensing polymer；Certainly, since the LCST of polymer can be adjusted
Monomer ratio is saved to adjust, therefore the progress of reaction can also be controlled by adjusting LCST).
The above specific embodiment is the selection when specific operation in the condition range of choice of scheme provided by the invention
Data, and above raw material that the present invention enumerates, reaction condition such as temperature, solution concentration, the citing in the reaction time with
And high-low limit value can realize the preparation to seperation film proposed by the present invention, therefore just no longer repeat one by one.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of grapheme foam-poly-dopamine composite membrane preparation method, which is characterized in that include the following steps：
(1) grapheme foam-poly-dopamine is prepared：
Adjust graphene oxide solution pH value make the graphene oxide solution alkalinity, then to the graphene oxide solution into
Row ultrasonic treatment；Then, Dopamine hydrochloride is added into the graphene oxide solution, and utilizes ultrasonic disperse again, before obtaining
Drive liquid solution；Then, hydro-thermal reaction is carried out to the precursor solution and obtains gel-like product, after gel-like product drying
Obtain grapheme foam-poly-dopamine；
(2) grapheme foam-poly-dopamine composite membrane is prepared：
Grapheme foam-the poly-dopamine being prepared in the step (1) is ground, N, N- bis- are then added to
Ultrasonic disperse is carried out in hydroxyethyl glycine, obtains grapheme foam-poly-dopamine/N, N- bicine N- disperse system；
Then, by the grapheme foam-poly-dopamine/N, N- bicine N- disperse system and the N for being dissolved with temperature sensing polymer,
N- bicine N- solution mixes, and is stirred to react, and it is poly- that thermosensitive graphene foam-is then obtained by vacuum filtration
Dopamine composite membrane.
2. grapheme foam as described in claim 1-poly-dopamine composite membrane preparation method, which is characterized in that the step
(2) in, the temperature sensing polymer is poly- (2- methyl -2- acrylic acid -2- (2- methoxy ethoxy) ethyl ester), polyacrylamide
At least one of amine, polyacrylic acid, poly(N-isopropylacrylamide), polyvinylpyrrolidone.
3. grapheme foam as described in claim 1-poly-dopamine composite membrane preparation method, which is characterized in that the step
(1) in, it is molten to the graphene oxide that the pH value for adjusting graphene oxide solution, which keeps the graphene oxide solution alkaline,
Tris-HCl is added in liquid makes the pH value of the graphene oxide solution be adjusted to 7.5~9.5.
4. grapheme foam as described in claim 1-poly-dopamine composite membrane preparation method, which is characterized in that the step
(1) in the precursor solution in, the concentration of graphene oxide is 1mg/ml~12mg/ml, and the concentration of Dopamine hydrochloride is
0.1mg/ml~8mg/ml；The mass ratio of the graphene oxide and the Dopamine hydrochloride is 10~1.
5. grapheme foam as described in claim 1-poly-dopamine composite membrane preparation method, which is characterized in that the step
(1) hydro-thermal reaction in is 6~32h of reaction at 60~120 DEG C；The drying is freeze-drying.
6. grapheme foam as described in claim 1-poly-dopamine composite membrane preparation method, which is characterized in that the step
(2) in, the grapheme foam-poly-dopamine/N, N- bicine N- disperse system is alkalinity.
7. grapheme foam as claimed in claim 6-poly-dopamine composite membrane preparation method, which is characterized in that the graphene
Foam-poly-dopamine/N, the pH value of N- bicine N- disperse system are 7.5~9.0.
8. grapheme foam as described in claim 1-poly-dopamine composite membrane preparation method, which is characterized in that the step
(2) in, the stirring is carried out at 20 DEG C~40 DEG C, and mixing time is 6~72h.
9. being prepared into using grapheme foam-poly-dopamine composite membrane preparation method as described in claim 1-8 any one
The grapheme foam arrived-poly-dopamine composite membrane.
10. being prepared using grapheme foam-poly-dopamine composite membrane preparation method as described in claim 1-8 any one
Obtained grapheme foam-application of the poly-dopamine composite membrane in water-oil separating.
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| CN106943896A (en) * | 2017-03-29 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation of three-dimensional porous graphene functionalized assembly membrane material and application process |
| CN108148224B (en) * | 2017-12-12 | 2021-05-28 | 明基材料有限公司 | Graphene/cellulose composite aerogel and manufacturing method thereof |
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| CN108548480A (en) * | 2018-05-09 | 2018-09-18 | 电子科技大学 | Three layers of selfreparing flexibility strain transducer of one kind and preparation method thereof |
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| CN111318172B (en) * | 2018-12-17 | 2022-01-25 | 中国石油化工股份有限公司 | Preparation method of polymer-modified graphene filtering membrane |
| CN111318190B (en) * | 2018-12-17 | 2022-04-05 | 中国石油化工股份有限公司 | Graphene composite material filtering membrane |
| CN111318171B (en) * | 2018-12-17 | 2022-06-24 | 中国石油化工股份有限公司 | Processing and coating process of three-dimensional porous graphene filtering membrane |
| CN109627004B (en) * | 2018-12-19 | 2022-01-07 | 重庆大学 | Heat-conducting and electric-conducting graphene film and preparation method thereof |
| CN109736022B (en) * | 2019-03-07 | 2020-06-30 | 浙江理工大学 | Preparation method of oil-water separation material with photo-thermal responsiveness |
| CN112755805B (en) * | 2020-12-09 | 2022-10-25 | 山东大学 | Underwater super-oleophobic two-dimensional nanoscale mica sheet oil-water separation membrane and preparation method and application thereof |
| CN113372608B (en) * | 2021-05-18 | 2022-05-10 | 暨南大学 | PNIPAAm (AM)/DA composite imprinted gel and preparation method and application thereof |
| CN115155536B (en) * | 2022-07-12 | 2023-04-07 | 湖北大学 | Preparation method of super-hydrophobic flame-retardant sponge for selective adsorption |
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