CN108212118A - A kind of hydrophilic material - Google Patents
A kind of hydrophilic material Download PDFInfo
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- CN108212118A CN108212118A CN201711240578.4A CN201711240578A CN108212118A CN 108212118 A CN108212118 A CN 108212118A CN 201711240578 A CN201711240578 A CN 201711240578A CN 108212118 A CN108212118 A CN 108212118A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3285—Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
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Abstract
This disclosure relates to a kind of hydrophilic material, including graphite material, has a surface and the polymer adjacent with the surface, wherein polymer is made of PEG or PEO polymer.Graphite material in the present invention can be a kind of carbon nano-tube film compared with traditional membrane material with excellent chemistry, mechanics and electrical property.The hydrophilic graphite ink material contains PEG/PEO polymer coatings, and this coating increases the hydrophily of graphite material.
Description
Technical field
This disclosure relates to hydrophilic material, more specifically, this disclosure relates to which novel hydrophilic graphite material, passes through polymerization
Object or molecule are modified the surface of graphite material.Polymer or molecule can help at adjacent graphite material surface be formed
One orderly water layer, so as to significantly improve the hydrophily of graphite material.
Background technology
Pure water is an important resource.Population increases and the expansion of industrial or agricultural activity, just so that fresh water is more and more diluter
It lacks.At the same time, the generation of waste water, the pollution of surface water and groundwater are in rising trend.Therefore, it needs and removes water in industry
In pollutant effective method for treating water and technology.
Membrane filtration technique provides effective solution for removal water pollutant, but realizes high osmosis, high selection
Property and contamination resistance are still the significant challenge that existing membrane filtration technique faces.By microbe deposition and growth, chemical attack, day
Fouling membrane caused by right organic material and inorganic matter fouling, has a negative impact to the performance of film so that filtration flux decline,
Energy consumption increases, maintenance and operation cost rise.At present, in water treatment technology most there is an urgent need to be exploitation pollutant retention
The filter membrane that rate is high, productivity is high, transmembrane pressure is low and antifouling property is excellent.
Most of commercial filter films are made of hydrophobic polymer material.It is usually used in micro-filtration (MF) film and ultrafiltration (UF)
The material of film has cellulose acetate, Kynoar (PVDF), polyacrylonitrile (PAN), polypropylene, polysulfones and polyether sulfone (PES).
Cellulose acetate and polyamide material are mainly used for nanofiltration (NF) and reverse osmosis membrane (RO).Each polymer in surface charge, hate
Water degree and hydrophilicrty, the tolerance degree to pH value and oxidant, mechanical strength and flexibility all show different
Property.For example, cellulose acetate film is easy to be degraded by microorganisms, operation pH value range is narrow, and between 4~8, and polyamide is anti-
Permeable membrane can use in the range of wider pH, be not easy to be degraded by microorganisms.
Membrane material is the core of micro-filtration, ultrafiltration, nanofiltration and reverse osmosis process flow.However, the hydrophobicity of polymer material
So that commodity filter membrane is easily contaminated.Pollution is probably derived from inorganic compound, particulate matter, microorganism or organic matter.Cause
This, the strainability of polymer film inevitably declines over time.Therefore, the new filtering of necessary exploitation
Membrane material, the shortcomings that overcome polymer film.
Carbon nanotube (CNT) powder is added in polymer and prepares composite membrane, has been found that the hydrophily of film can be improved
And filtration flux.However, in CNT powder polymer composite membranes, CNT loses over time or a key is asked
Topic.Further, since with hydrophobicity, carbon nanotube easily aggregation and conglomeration so that the carbon nanometer when preparing composite material in itself
Pipe is difficult to be evenly dispersed into polymer.Therefore, it is necessary to CNT is chemically treated with strong acid at high temperature, for example, with
Concentrated nitric acid and the concentrated sulfuric acid flow back for a long time, hydrophilic-OH and-COOH group are introduced on CNT so that CNT becomes more
It is hydrophilic.However,-OH and-COOH group are introduced into CNT surface using corrosive strong acid, it is unfavorable for reducing the shadow to environment
It rings, batch production is also relatively difficult.Furthermore it is also challenging to control the introduction volume of-OH and-COOH group in carbon nanotube
's.Basically, covalent introducing-OH and-COOH group can only occur in CNT it is destructurized when, therefore, covalent official
The CNT surface of energyization has the defects of in more structure, the electronics and mechanical property that these defects will change CNT.These change
Performance and fault of construction usually promote rather than prevent the pollution of CNT surface.
Non-covalent bond method is developed at present come in the presence of solving the problems, such as covalent modification carbon nanotube.Have
A kind of method is to use polyalkylene glycol monoalkyl ether.It is believed that hydrophobic alkyl preferentially occurs with hydrophobicity carbon nano tube surface
Interaction so that hydrophilic polyethylene glycol segment is close to the surface of CNT.Due to depositing for hydrophilic polyethylene glycol segment
So that obtained CNT becomes hydrophilic.Free hydroxyl group in polyethylene glycol polymer chain can be crosslinked further instead
Should, so as to form more stable hydrophilic layer.However, the long-term chemical durability or one of polyethylene glycol alkyl ether and cross-linking system
A the problem of meriting attention.When crosslinked polyethylene glycol is degraded in filter membrane, organic degradation product can penetrate into
In penetrating fluid.In addition, the carbon nanotube of polyalkylene glycol monoalkyl ether modification may lack enough hydrophilies to prevent surface dirty
Dye.
Another method is to use surfactant such as nonionic surface active agent Triton X-100 and ionic table
CNT powder is disperseed and CNT composite membrane of polymer is made by face activating agent lauryl sodium sulfate (SDS).With surfactant point
Son now has become technology well known to people to disperse CNT powder.It is generally believed hydrophobic in surfactant molecule
Alkyl can preferentially interact with hydrophobic CNT surface, so as to be arranged in hydrophilic group in surfactant
The surface of CNT.Due to the presence of the hydrophilic radical of surfactant, obtained this carbon nanotube becomes more hydrophilic.So
And in the long-time stability of surfactant molecule of CNT surface, there are still queries.Surfactant molecule is dissolved in water and many
Polar organic solvent.In filter process, the surfactant molecule adsorbed in CNT surface may be penetrated into filtered fluid.
Due to CNT powder polymers composite membrane there are it is many potential the problem of, CNT films are it is therefore more likely that as than composite membrane
The superior water filtration film of performance.Recently, flowing catalytic chemical vapor deposition technique (FCCVD) is so that prepare large area (such as 1m
× 1m) CNT films are possibly realized, and the CNT films of this large area can be assembled into for micro-filtration, ultrafiltration, nanofiltration and reverse osmosis process
In helical filter.The CNT films generated from reactor, be by long long nanotube bundle it is interlaced, mutual knit
Network-like structure, and the CNT in CNT powder polymer composite membranes is deposited in the form of single or tiny aggregation
Size other nanotube particles in the micron-scale.Therefore, CNT films have structural intergrity, compared with CNT powder composite membranes,
Significantly improve chemical stability and mechanical strength.For example, CNT films are acidproof, alkaline-resisting, and insoluble in organic solvent.In water
In filter process, the carbon nanotube in CNT films is also less likely to lose at any time.
However, original CNT films are hydrophobic, thus with low-down water penetration.Hydrophobicity also makes carbon nanotube
Film easily generates surface smut in water filtration.The existing hydrophilic method for improving CNT powder (live by such as strong acid treatment, surface
Property agent use) all also have some problems.In order to which CNT films is made to become useful water filtration new material, still having in industry at present must
Developing improves the hydrophilic new method of CNT films.
Invention content
Goal of the invention：In order to solve the deficiencies in the prior art, the present invention provides a kind of hydrophilic materials.
Technical solution：A kind of hydrophilic material, including graphite material, have a surface and with adjacent poly- in the surface
Object is closed, wherein polymer is made of PEG or PEO polymer.
In some embodiments, the weight average molecular weight of the PEG or PEO polymer or viscosity average molecular weigh are about 35000
To between about 8000000Da.
In some embodiments, PEG the or PEO polymer is adjacent with the water layer of the structuring on graphite material surface
It connects.
In some embodiments, the graphite material is carbon nanotube thin film, and polymer is PEG or PEO.
In some embodiments, the carbon nanotube thin film is by random orientation, partly or entirely orienting, horizontal or vertical
The carbon nanotube composition directly oriented.
In some embodiments, the graphite material be carbon nanotube (CNT) film, CNT cloth, CNT films, CNT powder,
Any combinations of graphene film, graphene powder or these materials.
In some embodiments, the surface of the PEG or PEO polymer and graphite material is non-covalently bound.
The film formed according to the hydrophilic material.
Advantageous effect：Graphite material in the present invention can be it is a kind of compared with traditional membrane material have excellent change
The carbon nano-tube film of, mechanics and electrical property.The hydrophilic graphite ink material contains PEG/PEO polymer coatings, this painting
Layer increases the hydrophily of graphite material.
The feature and technological merit of the disclosure are substantially outlined above, to more fully understand following detailed description.
It hereinafter will be illustrated that the other feature and advantage of the disclosure, these feature and advantage will by the right for forming present patent application
Seek the content of book.It should be appreciated by those skilled in the art that concept and specific embodiment that the disclosure proposes can be readily used for
Improve or design the basis of other embodiments with the disclosure with identical purpose.Those skilled in the art will also be appreciated that this
A little equivalent embodiments are without departing from the spirit and scope illustrated such as appended claims of the disclosure.
Description of the drawings
Below by referring in particular to appended illustration, the present invention will be described in detail：
Fig. 1 is the cross-sectional view of one embodiment of the present of invention, and wherein hydrophilic graphite ink material gathers coated with PEG or PEO
Object is closed, this polymer architecture may cause to form orderly water layer in CNT surface, and water layer is abutted with CNT surface.
Fig. 2 is the cross-sectional view of the embodiment comprising graphite material of the present invention, wherein water layer and graphite material table
The spacing in face is in nanometer range.
Specific embodiment
Various embodiments are described below with reference to illustration, identical unit is usually indicated by the like numerals in illustration.
By following detailed description, it is well understood that the relationship of each unit of embodiment and effect.However, embodiment is not limited to insert
Those contents illustrated in figure.It is to be understood that these illustrations were not necessarily drawn to scale, and in certain situations
Under, the unnecessary details for understanding embodiments disclosed herein, such as conventional making and assembling may be omitted.
Although having the research work of a large amount of antifouling property for improving filter membrane at present, so far, there are no one
Kind countermeasure fundamentally solves the root of dirt.Use various countermeasures that hydrophilic radical is introduced into hydrophobic film surface, but
In most cases, the quantity of hydrophilic radical and density is not enough.As a result, there are no necessary for most of commodity filter membranes
Hydrophily generates three principal elements of dirt to overcome：The mutual affinity interaction of hydrophobe-hydrophobe, the charges of different polarity with
Film surface charge attract each other and the release of low entropy surface water.
Hydrophilic graphite ink material disclosed by the invention can solve the limitation of above-mentioned traditional filtering film.With literalness stone
Ink material is compared, and hydrophilic graphite ink material disclosed in this invention presents excellent wetability and resistance to soiling.
In some embodiments, graphite material can be amorphous graphite or kish.In other embodiments, graphite
Material can be graphene film or graphene powder.Graphite material may include fullerene.
In some embodiments, graphite material can include various carbon nanotubes.Carbon nanotube is strong with excellent mechanics
Degree and chemical stability are the ideal candidates materials of membrane material.Graphite material can include with film, cloth, film, paper, fiber or
Carbon nanotube existing for powder type.Carbon nanotube can be single-walled carbon nanotube, multi-walled carbon nanotube or double-walled carbon nano-tube.
Graphite material can be carbon nanotube thin film.Carbon nanotube thin film can be synthesized using fixed method, such as, but not limited to floating catalytic
Learn vapour deposition process.Carbon nanotube can be randomly oriented in the film, can be part or it is sufficiently directional, can also
It is being a horizontally oriented or vertical orientation.
Without being bound by theory, graphene and carbon nanotube have the positive charge and negative electricity of strong dipole or alternation
Lotus (or Partial charge), thus have strong interaction with dipole molecule such as hydrone.To the current research of CNT and graphene
Progress shows there is separation of charge phenomenon in CNT and grapheme material.P tracks on carbon atom can reconfigure and form molecule
Track.This atomic orbital reconfigures the non-homogeneous cloud density distribution caused in CNT surface between each carbon atom.
In other words, the non-homogeneous cloud density distribution in CNT surface can be construed to separation of charge.
Newest CNT progress shows that a thin layer of hydrone (layer thickness is in nanometer range) is wrapped in naturally
On single wall CNT.This layer of water has close interaction with CNT, thus is very different with the water in common solution.For example,
Even if this layer of water also is difficult to remove under high temperature high vacuum.However, only this layer of constitution water is likely to that CNT films is insufficient to allow to have
There is the hydrophily for reaching filtering requirement.Without being bound by theory, hydrophilic graphite ink material disclosed in this invention exists
The ordered structure between hydrone is further extended on the basis of single water layer, so as to play one layer in graphite material surface construction
Thick entropy is built.
Extend the ordered structure between hydrone can be by introducing a kind of polymer at the surface of adjacent graphite material
To realize.Known PEG or PEO molecules can be with the formation of induced order water-bound.In PEG or PEO molecules repetitive unit (-
CH2CH2- O-) it can be regarded as dipole：C-terminal is electron-deficient, thus band part positive charge, and O ends are electron riches, thus
Band part negative electrical charge.These dipoles link together in polymer architecture.Due to the Cloud Distribution of carbon nano tube surface
This structure of uneven (separation of charge), PEG or PEO with CNT particularly suitable for occurring strong interaction.Not by any
In the case of theory constraint, the orderly layer of water is will further result in the ordered structure of the PEG or PEO of carbon nano tube surface adjoining
The formation of shape structure.Therefore, the carbon nanotube that PEG or PEO non-covalent bonds deposit significantly becomes more hydrophilic and resistance to dirt.
Graphite material can be covered completely or substantially by PEG or PEO polymer.Graphite material can be carbon nanotube thin film.
In carbon nanotube thin film, what carbon nanotube can be randomly oriented, can be part or it is sufficiently directional, can also be horizontal fixed
To or vertical orientation.In some embodiments, carbon nanotube thin film used contains the carbon nanotube of random orientation.
Fig. 1 shows one embodiment, PEG or PEO polymer 11 therein is with being distributed on the surface of graphite material 10
Electron cloud interacts, and then water forms orderly water layer on PEG or PEO polymer.
In the case where being not bound by any theory, the positive charge and negative electrical charge of the alternation in CNT polymerize with PEG or PEO
Strong interaction occurs for O atom (band part negative electrical charge) and C/H atoms (band part positive charge) in object chain.In this structure
There are a variety of advantageous interactions.First, even if in the case of only noncovalent interaction, electronics knot orderly CNT
Structure can enhance the stability of the orderly PEG or PEO structures around CNT.Secondly, orderly PEG or PEO polymer makes water
Molecule ensures there is thicker orderly water layer around CNT close to CNT.Orderly water layer can protect PEG around CNT or
PEO polymer, prevents polymer degradation.Third, orderly water layer may be with orderly CNT structures and highdensity dipole weights
Multiple unit (- CH2CH2- O-) there is stronger interaction.The interaction of these collaborations, makes CNT-PEG/PEO polymer-H2O
This total and orderly water layer are all highly stable, so as to which CNT membrane materials be made to become because there is a thicker orderly water layer
It is abnormal hydrophilic.
In the case where being not bound by any theory, PEG/PEO polymer introduces around graphite material a thickness and is had
The water of sequence.Orderly water layer can be adsorbed steadily around CNT so that and carried out with traditional CNT surface chemical method
Prepared by functionalization, CNT was compared, and CNT films of the invention are more hydrophilic.This method in the present invention does not need to pass through oxidation
Property strong acid treatment come covalently introduce hydroxyl or carboxyl.It is well known that the surface that this strong acid treatment will damage CNT, and can not
Have an impact CNT mass with avoiding the defects of.
Presence of the PEG/PEO polymer in CNT surface, for CNT brings a floor height stability, highdensity height has
The water of sequence.In the case where being not bound by any theory, to ion present in aqueous solution, particle or microbial contamination, water
Orderly layer can play the role of barrier action, or play entropy base.It is well known that the hydrone closest to film surface has difference
Property.For example, the dielectric constant of first to the second layer water near a plane is 6, and Jie of the water in regular solution
Electric constant is 80.Clearly as the influence on surface, interact by the hydrone and external charge (ion) of near surface, it is and general
The situation of hydrone in logical solution has very big difference.Due to the orientation (aligning) of the water near surface, these are in table
The interaction of hydrone in itself near face also should be different from the interaction between the hydrone in regular solution.Such one
Layer structural water molecule has apparent difference with the water in regular solution, is also therefore stabilized to and is enough to inhibit by being present in feedwater
Surface scale caused by pollutant.
In some embodiments, the weight average molecular weight of PEG/PEO polymer or viscosity average molecular weigh be about 35000,
100000th, 200000,300000,400000,600000,900000,1000000,2000000,4000000,5000000 or
8000000Da or polymer are weight average molecular weight or viscosity average molecular weigh about 35000 to the PEG/ between about 8000000Da
The mixture of PEO.
The preparation method of hydrophilic graphite ink material：
In some embodiments, a kind of method for preparing hydrophilic material is disclosed.This method may include in graphite material
Surface forms polymer coating.Polymer coating may include weight average molecular weight or viscosity average molecular weigh be about 35000,100000,
200000th, 300000,400000,600000,900000,1000000,2000000,4000000,5000000 or 8000000Da
PEG and PEO or including weight average molecular weight or viscosity average molecular weigh about 35000 to the PEG/PEO between about 8000000Da
Mixture.
PEG or PEO polymer can be introduced on graphite material by following processes.First, dry graphite material, so
Afterwards, the graphite material dried at a temperature of 25 DEG C to 150 DEG C with solid PEG or PEO polymer treatments.Can using or
In the case of without using other solvents, PEG or PEO is added under vacuum conditions or under atmospheric pressure, last from a few houres to
24 hours or 72 hours.In some embodiments, PEG the or PEO polymer of solid form to be sprayed directly on to fine powder the same
Graphite material on.When the reactions are completed, graphite material can be rinsed with deionized water, is polymerize with removing extra PEG or PEO
Then resulting materials are dried or impregnated in water by object in air.
In other embodiments, the painting of PEG or PEO polymer can be formed on graphite material by PEG or PEO polymer solutions
Layer.PEG or PEO polymer solution graphite spraying materials can be used or by graphite material in PEG or PEO polymer solutions
It impregnates for a long time.After removing solvent, graphite material and polymer can be further heated at a temperature of 80 DEG C to 100 DEG C.Reaction
After the completion, it can be rinsed to remove extra polymer with deionized water.These processes can be applied to different graphite materials, such as
Carbon nanotube thin film, powder, fiber or graphene film or powder.
The product that method limits：
In some embodiments, a kind of preparation process of hydrophilic material is included at a temperature of between 80 DEG C and 100 DEG C
With PEG or PEO polymer treatment graphite materials, graphite material can be carbon nanotube thin film.In the film, carbon nanotube can be with
It is machine orientation, partially or completely orienting, horizontal orientation or vertical orientation.PEG or PEO polymer used is divided equally again
Son amount or viscosity average molecular weigh are about 35000,100000,200000,300000,400000,600000,900000,
1000000th, 2000000,4000000,5000000 or 8000000Da or polymer used are weight average molecular weight or glue equal
Weight molecule amount is the mixture of 35000 to 8000000Da PEG/PEO.
In some embodiments, preparing the process of hydrophilic material can be included within the temperature range of 60 DEG C to 120 DEG C
Heat PEG and PEO polymer and graphite material.Heating temperature can be 70 DEG C to 120 DEG C, 80 DEG C to 120 DEG C, 90 DEG C to 110
DEG C or 90 DEG C to 100 DEG C.In some embodiments, heating temperature is 90 DEG C.
In some embodiments, heating stepses described above can continue from 10 hours to 48 hour or by 96 hours not
Deng.Heating time can from 10 hours to 30 hour, differ within 20 hours to 48 hours, 48 hours to 96 hours.Heating time
It can be about 24 hours.
In certain embodiments, preparing the process of hydrophilic material can include using the stone of PEG or PEO solution treatments first
Ink material, processing time from 10 minutes to 1 hour, to the times of 72 hours or longer, solvent is then removed, then in decompression item
PEG or PEO polymer and graphite material under part within the temperature range of 60 DEG C to 110 DEG C obtained by heating.It also can be in vacuum item
PEG the or PEO polymer and graphite material of heating gained under part.In some embodiments, it can be released before graphite material is cooled down
Put vacuum.In further embodiments, vacuum can be first discharged, then, continues heating 5 minutes to 60 minutes, 10 minutes to 50 points
Clock, 5 minutes to 30 minutes, 20 minutes to 40 minutes or 30 minutes to 60 minutes.
In some embodiments, graphite material is handled with PEG or PEO, PEG or PEO polymer is to the weight of graphite material
Than 0.1:1 to 100:In the range of 1.In certain embodiments, PEG or PEO polymer exists to the weight ratio of graphite material
0.5:1 to 10:1、1:1 to 25:1、1:1 to 50:1、1:1 to 20:1 or 1:1 to 5:In the range of 1.PEG/PEO polymer pair
The weight ratio of graphite material can be 0.5:1 to 1:1.
The application method of hydrophilic graphite ink material：
The described hydrophilic graphite ink material of present patent application can be used for any filter membrane.Filter membrane can be used for water
It is detached with dissolving any in water or suspension substance.
In some embodiments, hydrophilic graphite ink material may be homogenously dispersed in polymer composites.
In other embodiments, hydrophilic graphite ink material can be the film adjacent with other membrane materials.The film can
To be placed between the waterproof sheet material in spiral wound membrane element and porous sheet material.Hydrophilic graphite ink material can be used for reverse osmosis
Permeable membrane, ultrafiltration membrane or NF membrane.These films can be used for the ion gone in removing water, the substance dissolved or microorganism.
In some embodiments, a kind of method that water is removed from aqueous solution is provided.This method may include aqueous solution
It is introduced into the device with film.The film can include hydrophilic graphite ink material as described above.This method may also include
Aqueous solution is contacted, and pass water through film and generated drainage with the film.
In some embodiments, hydrophilic graphite ink material can be used in solar cell, stored energy application or battery.Due to this
The disclosed graphite material of invention has splendid hydrophily, which can be used for the sensing device based on CNT, special
It is not electrochemical sensor.Hydrophilic graphite ink material is antifouling, available for requiring the application of minimum biological interaction
In.For example, hydrophilic graphite ink material may be used as the coating of implantable medical device or be held for modifying with important biomolecule
Learn the vessel surface of the solution of meaning.
Embodiment 1：Water penetration is tested
Under middle pressure, unmodified carbon nanotube thin film is usually waterproof.By carbon nanotube thin film sample (about 2mg, diameter
It 25mm) is placed in the sleeve for the stainless steel syringe formula filter that a trade mark is Millipore, which one
Polypropylene syringe.Syringe plunger is with the hands pressed, does not observe the infiltration of water.
Identical carbon nanotube thin film sample is placed on air drying, is then placed in a vial and in vacuum drying oven
In heated 24 hours at 100 DEG C.Then, carbon nanotube thin film is assembled in Millipore stainless steel syringe formula filter
In sleeve, flow is tested.As a result the infiltration of water is not observed yet.
After impregnating 2 days in deionized water, film is put into filter sleeve, the flux rate of gained is 0.6g/min.
It impregnates 8 days for a long time in deionized water, the flux rate of gained is 0.98g/min.After impregnating 17 days again, flux rate reaches 2g/
min.It can be seen that it is a slowly process that simple immersion, which makes unmodified carbon nanotube thin film become hydrophilic,.
Under vacuum, only with the unmodified carbon nano-tube film of water process, to improving the permeability of water nor having very much
Effect.For example, a carbon nanotube thin film sample (about 2mg, diameter 25mm) is placed in a vacuum chamber, and heated 2 hours at 100 DEG C,
Then deionized water covering sample is added in.After 24 hours, vacuum is discharged, the carbon nanotube thin film water penetration of gained is used and is existed as described above
Millipore stainless steel syringes filter carries out water penetration experiment.The flux rate of gained is 1.20g/min.Continue in water
Carbon nanotube thin film is impregnated, water flux can not be increased.Dry CNT films after 3 days in air, water flux then drop to 0.5g/min with
Under.
The unmodified carbon nanotube thin film of the organic solvents such as spent glycol and methanol processing can temporarily increase water penetration.For example,
One carbon nanotube thin film sample (about 2mg, diameter 25mm) in ethylene glycol is impregnated 24 hours, is rinsed with water, tests water penetration immediately,
The water flux of gained about 9g/min.Continuous dipping 3 days in deionized water, do not increase water flux.It is thin that CNT is dried in air
After film 3 days, water flux quickly falls to below 2g/min.It repeats to impregnate identical carbon nanotube thin film in ethylene glycol, then can make water again
Flux is significantly increased.After impregnating 10 days in deionized water, water flux reaches 11.86g/min when carrying out above-mentioned test.In air
After middle drying 3 days, water flux then drops to 1.2g/min.
Carbon nanotube thin film is only impregnated in methyl alcohol 24 hours and tested immediately, also observe similar result.Continuous leaching in water
For bubble after 3 days, maximum water flux reaches about 8.6g/min.Carbon nanotube thin film is dried 3 days in air, water flux drops to 2.99g/
min.The carbon nanotube thin film is impregnated 24 hours in methyl alcohol again, then impregnates the time up to 8 days in deionized water, gained is most
Big water flux is 14.6g/min.After further impregnating 2 days in water, gained water flux is about 10g/min.Although under water flux
The speed of drop is slower than what spent glycol was handled, and water flux also drops to about 7-8g/min after drying 3 days in air.In air
After re-dry 7 days, water flux is further lowered into about 2.5g/min.Continuous drying 12 weeks in air, water flux further under
Drop to 2.06g/min.Therefore, it is easy to evaporate since the water layer that organic solvent impregnates and is formed is unstable around carbon nanotube.One
Denier loses such water layer, and CNT films just become hydrophobic so as to also waterproof.
Carbon nanotube thin film sample (about 2mg, diameter 25mm) is immersed in the methanol solution of PEG (weight average molecular weight Mw2000)
24 hours in (10mg/ml, 1ml), solution is poured out, with water cleaning down film until bubble-free is visible in flushing water.
Film is continued to impregnate in water 5 days, then carries out water flux test.Initial water flux reaches 10.24g/min.It is further continued for soaking
After steeping 3 weeks, water flux is declined slightly to 8.04g/min.It dries 5 weeks in air, tests water flux once in a while therebetween, it is found that water leads to
Amount gradually decreases down 3.66g/min.In air after continuous drying 10 weeks, water flux drops to 0.48g/min.
New carbon nanotube thin film sample (about 2mg, diameter 25mm) is separately immersed in the methanol solution of the PEG of different molecular weight
24 hours in (10mg/ml, 1ml), the weight average molecular weight Mw of PEG is 5000,10000 and 20000 respectively.Then solution is fallen
Go out, with water cleaning down film until bubble-free is visible in flushing water.Initial water flux reaches more than 8g/min.Continuous leaching
After steeping 3 weeks, water flux is maintained at 8g/min or so.It dries in air 5 weeks, carries out water flux test, water flux once in a while therebetween
Or the same gradually decreases to 4-5g/min.In air after continuous drying 10 weeks, water flux drops to about 1g/min.
It is well known that when using nonionic surfactant polyethylene glycol alkyl ether, such as(its chemical composition
For the stearic alcohol ether of polyoxyethylene (100), can be represented with skeleton symbol C18EG100, molecular formula C18H37(OCH2CH2)nOH, n are about
100) after handling, CNT can become more hydrophilic.Therefore, carbon nanotube thin film sample (about 2mg, diameter 25mm) is immersed inMethanol solution (10mg/ml, 1ml) in 24 hours, then the bottle for holding sample is placed on to 75 DEG C of electric heating
Make solvent on plate in evaporation of the solvent.Bottle with aluminium foil is covered, is placed in one 90 DEG C of vacuum drying oven, protects under vacuum conditions
It holds 24 hours.Vacuum is discharged, is taken out after sample is toasted 30 minutes at 90 DEG C, is cooled to room temperature, is then filled with deionized water
Divide rinsing, until there is no bubble visible.Carbon nanotube thin film touch gets up to have slight soapy feeling.It is surveyed immediately after rinsing
Examination, the water flux about 5g/min of gained.After impregnating 3 days in water again, water flux increases to about 6.7g/min.It is however, CNT is thin
Film sample in air dry 1 day after, water flux quickly falls to about 2.5g/min, this show around CNT due toPresence and the hydrated sheath that is formed is highly unstable.
One carbon nanotube thin film sample (2.84mg, diameter 25mm) is placed in a vial, then adds in solid PEG powder
Last (Mw 35000Da, 10.0mg).Solid powder is dispersed on film sample, then by small bottle cap and is prevented with aluminium foil in vacuum
In baking oven, under vacuum conditions, heated 48 hours at a temperature of 90 DEG C.In heating process, white solid powder melts simultaneously
Soak carbon nanotube thin film.After discharging vacuum, film is rinsed with water, until film comes off from glass bottle wall and does not have in flushing liquor
Until visible bubble.Film is put into the sleeve of Millipore syringe type filters.Measured initial water flux is
6.64g/min.Film is impregnated in deionized water 5 days, water flux is maintained at 6.2g/min.It dries 5 days in air, water flux
Remain at 5.7g/min.Continuous drying 10 weeks in air, water flux was also held in 6.0g/min or so.
New carbon nanotube thin film sample (about 2mg, diameter 25mm) is individually positioned in each vial, then in each glass
Be separately added into the solid PEG powder of 10mg in glass bottle, the viscosity average molecular weigh Mv of PEG powder is 600000 respectively, 1000000,
2000000th, 4000000 and 8000000Da.Solid powder is distributed on each film sample.Then with aluminium foil by bottle
It covers and is placed in vacuum drying oven, under vacuum conditions, heated 48 hours at a temperature of 90 DEG C.The powder solid of white exists
Become opaque gel solids on carbon nanotube thin film sample.After discharging vacuum, film is fully rinsed with water, until film is from glass
Until coming off in bottle wall and there is no visible bubble in flushing liquor.Film is put into Millipore syringe type filters
In sleeve.Measured initial water flux is about 3.5-5.4g/min.Film is impregnated in deionized water after 5 days, and water flux is protected
It holds in about 3.6-7.04g/min.It dries 5 days in air, water flux remains at 5.4-6.4g/min.It is continuous dry in air
Dry 10 weeks, water flux was also held in about 4.8-7.2g/min.
Carbon nanotube thin film sample (about 2mg, diameter 25mm) is placed in a vial, it is 35000Da's then to add in Mw
The methanol solution (10mg/ml, 1ml) of PEG.Vial is heated in 70 DEG C of air to remove solvent.Then with aluminium foil by glass
It on glass bottle cap and is put into vacuum drying oven, under vacuum conditions, is heated 24 hours at a temperature of 90 DEG C.After discharging vacuum, use
Water fully rinses film, until film comes off from glass bottle wall and does not have visible bubble in flushing liquor.By film
It is put into the sleeve of Millipore syringe type filters.Measured initial water flux is about 8.89g/min.In deionization
Film is impregnated in water 3 days, water flux is maintained at 8.11g/min.It dries 5 days in air, tests water flux once in a while therebetween, water leads to
Amount remains at about 4.39-7.08g/min.Continuous drying 12 weeks in air, water flux remained at about 7.16g/min.
Carbon nanotube thin film sample (1.75mg, diameter 25mm) is placed in a vial, it is 600000Da then to add in Mv
PEG methanol solution (5mg/ml, 0.5ml).Vial is covered tightly and is heated 6 days at a temperature of 50 DEG C, is subsequently cooled to
Room temperature.Supernatant liquor is sopped up with pipette, then heats to remove remaining solvent in 70 DEG C of air.It then will with aluminium foil
It on glass cap, is placed in vacuum drying oven, under vacuum conditions, is heated 24 hours at a temperature of 90 DEG C.After discharging vacuum, use
Water fully rinses film, until film comes off from glass bottle wall and does not have visible bubble in flushing liquor.By film
It is put into the sleeve of Millipore syringe type filters.Measured initial water flux is 0.84g/min.Film is placed
There is a small amount of water in the bottle that one covers tightly, in bottle so that CNT films to be kept to moisten.After 9 days, water flux increases to 3.12g/
min.Then carbon nanotube thin film is dried 10 weeks in air, carries out water flux test once in a while therebetween, water flux increases to 6.04g/
min.Further in air continuous drying 4 weeks, water flux remained at about 5.86g/min.Carbon nanotube thin film weightening 0.19mg, table
The bright deposition for having PEO/PEG polymer in carbon nanotube thin film.
Carbon nanotube thin film sample (1.89mg, diameter 25mm) is placed in a vial.Then adding in Mv is
The methanol solution (5mg/ml, 0.5ml) of the PEG/PEO of 8000000Da.Vial is covered tightly and heats 2 days at 25 DEG C, then
Remove the supernatant liquor in vial.The methanol solution (Mv 8000000,5mg/ml, 0.5ml) of PEG that addition is newly prepared adds
Enter into vial to impregnate carbon nanotube thin film sample 18 days, then remove supernatant liquor.Vial is heated in 70 DEG C of air to remove
Fall remaining solvent, then cover vial with aluminium foil, and put into vacuum drying oven, under vacuum conditions, in 90 DEG C of temperature
The lower heating of degree 24 hours.After discharging vacuum, film is fully rinsed with water, until film comes off and flushing liquor from glass bottle wall
In there is no visible bubble until.Membrane contact gets up to have soapy feeling.Film is put into Millipore syringe type filters
In sleeve.Measured initial water flux is 0.054g/min.Film is placed in a bottle covered tightly, is had in bottle few
The water of amount with keep CNT films moisten.After 8 weeks, water flux increases to 4.12g/min.Then carbon nanotube thin film is dried 4 in air
In week, carry out water flux test once in a while therebetween, water flux increases to 6.36g/min.Carbon nanotube thin film weightening 0.27mg, shows thin in CNT
There is the deposition of PEO/PEG polymer on film.
New carbon nanotube thin film sample (about 2mg, diameter 25mm) is individually positioned in vial, then in each vial
In be separately added into the methanol solution (5mg/ml, 0.5ml) of PEG/PEO, the viscosity average molecular weigh Mv of PEG is 1000000 respectively,
2000000 and 4000000Da.Before solvent is removed, vial is covered tightly and is heated 2 days at 25 DEG C.By vial aluminium foil
It covers, and puts into vacuum drying oven, under vacuum conditions, heated 24 hours at a temperature of 90 DEG C.After discharging vacuum, filled with water
Divide and rinse film, until film comes off from glass bottle wall and does not have visible bubble in flushing liquor.Film is put into
In the sleeve of Millipore syringe type filters.Measured initial water flux is about 0.2-0.4g/min.Film is placed
It protects in moist bottle, and covers at one.After about 3 weeks, water flux increases to about 1.3g/min.Then do in air
Dry, the water flux of film increases to 5-6g/min.
Collected tap water has slight yellow tone, by the carbon nanotube thin film of this tap water dead end filtration mode
Filter filters, and obtained filter liquor is just without the tone of yellow.This shows that carbon nanotube thin film filter can be effectively removed in water
Yellow strain object.These yellow strain objects concentrate on the surface of carbon nanotube thin film filter, can use Chemwipe (trade name) paper handle
These yellow strain objects are wiped from the surface of carbon nanotube thin film filter, this shows that carbon nanotube thin film filter is less scaling.
The carbon nanotube thin film filter of a kind of red plants oil and the mixture dead end filtration mode of water is filtered.Gained
Filter liquor is colourless, and vegetable oil is collected in the filter, and water is removed from oil completely.The oil droplet in carbon nanotube thin film is wiped,
The water flux of the filter will restore completely, and it is highly hydrophilic to further demonstrate that carbon nanotube thin film filter, be not easy hydrophobic
The oily institute's fouling or pollution of property.
By a kind of orange sodium humate aqueous solution (20mg/L) (technical grade, Sigma-Aldrich) dead-end filtration mould
The carbon nanotube thin film filter filtering of formula.Filter liquor is in very slight yellow, and the substance of most of yellow is all collected and filtered in CNT
On device.The substance of yellow is easy to be wiped with Chemwipe paper, and after wiping, water flux is just restored completely.This shows that CNT is thin
Membrane filter can partly remove humic substance without being contaminated.
The carbon nanotube thin film (58mm × 75mm) of rectangle is assembled into flow cell (Sterlitech companies, the U.S.), with cross-flow
Pattern test pure water permeability.Pure water penetration modes are tested.As expected, untreated carbon nanotube thin film is saturating
Water rate is very low, and when transmembrane pressure is 6.8bar, permeability rate is about 10.12kg/ (m2·h·bar).According to scanning electron microscope
(SEM) image, untreated carbon nanotube thin film have the hole more than 200nm.As a comparison, semiaromatic piperazinyl polyamide nanofiltration membrane
The average pore size of NF270 (Dow FilmTec companies, film composite material) is 0.84nm, and permeability rate is about 13.5kg/ (m2·
h·bar).In contrast, PEG/PEO polymer solutions have handled 2 days, then dried carbon nanotube thin film in air, across
Film pressure is measured when being 6.8bar with the pattern of cross-flow, and the initial permeability rate of gained is about 330kg/ (m2·h·bar)。
It is dramatically increased it can be seen that water penetration has, it is shown that PEG/PEO polymer effectively can become CNT surface
Obtaining has hydrophily.
Disclosed herein and requirement of having the right all compositions, material and method can be without undue experimentations
In the case of manufactured and implemented according to the disclosure.The present invention can be carried out with many different forms, but the present invention is excellent
The embodiment of choosing is described in detail herein.Content disclosed in this invention is an example of the principle of the present invention
Card, is not meant to limit the present invention as described specific embodiment.In addition, unless expressly stated to the contrary, using not
Definite article " a (one) " is intended to include " at least one " or " one or more ".A for example, " a device (dress
Put) " it is intended to include " at least one device " or " one or more devices ".
Any range provided with absolute value or approximation is provided to comprising the two, and used any fixed herein
Justice is provided to clarification rather than in order to limit described range.Although illustrate the broad range of numberical range of the present invention and ginseng
Number is all approximation, all is reported as precisely as possible out in the numerical value that specific embodiment is previously mentioned.However, any number
In itself all comprising certain error, standard deviation of these errors necessarily in the presence of respective test measurement causes value
's.It is in addition, disclosed herein so range is understood to include used any range and all subranges (including institute
Some score numerical value and integer numerical value).
In addition, the present invention includes some all possible combinations or whole groups in various embodiments described herein
It closes.It should also be understood that the various changes and modifications of preferred embodiment described herein, for those skilled in the art
For will be apparent.It is this change and modification can under the premise of without departing substantially from the spirit and scope of the present invention, not
It is carried out under the premise of the advantages of its expection can be reduced.Therefore, such change and modification are covered by appended claims.
Claims (8)
1. a kind of hydrophilic material, it is characterised in that：Including graphite material, have a surface and with adjacent poly- in the surface
Object is closed, wherein polymer is made of PEG or PEO polymer.
2. hydrophilic material according to claim 1, it is characterised in that：The Weight-average molecular of the PEG or PEO polymer
Amount or viscosity average molecular weigh about 35000 between about 8000000Da.
3. hydrophilic material according to claim 1 or 2, it is characterised in that：PEG the or PEO polymer and graphite
The water layer of structuring on material surface is adjacent.
4. hydrophilic material according to claim 3, it is characterised in that：The graphite material is carbon nanotube thin film, and is polymerize
Object is PEG or PEO.
5. according to the hydrophilic material described in a claim any in claim 1-4, it is characterised in that：The CNT
Carbon nanotube that film is oriented by random orientation, partly or entirely, being horizontally or vertically oriented forms.
6. according to the hydrophilic material described in a claim any in claim 1-5, it is characterised in that：The graphite
Material is appointing for carbon nanotube (CNT) film, CNT cloth, CNT films, CNT powder, graphene film, graphene powder or these materials
What is combined.
7. according to the hydrophilic material described in a claim any in claim 1-6, it is characterised in that：The PEG
Or the surface of PEO polymer and graphite material is non-covalently bound.
8. the film being made of the hydrophilic material according to a claim any in claim 1-7.
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