CN106492654A - A kind of multifunctional graphite vinyl/polymer composite water permeable membrane and its production and use - Google Patents
A kind of multifunctional graphite vinyl/polymer composite water permeable membrane and its production and use Download PDFInfo
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Abstract
The present invention relates to a kind of multifunctional graphite vinyl/polymer composite water permeable membrane and its preparation method and application.Macromolecule is organically led wet polymer and forms the effectively chemical bond linkage such as hydrogen bond, ionic bond, covalent bond with graphene-based composite by polar group functional group by the technology, so as to form the water-permeable passage with reinforcing hydrophilic-hydrophobic group on the basis of wet polymer is led, mechanical strength of the water permeable membrane during permeable, rub resistance intensity and the anti-pollution ability of acid-proof alkaline, antibacterial, heat conduction and the characteristic such as heat-resisting are significantly improved simultaneously, without the need for changing, having the multifunctional composite water permeable membrane of automatical cleaning ability during being a kind of long-life, work.This composite film material can be applicable to total-heat exchanger, humidistat, sewage disposal and other be suitable to the occasion of permeable or filter water.
Description
Technical field
The invention belongs to the preparation field of polymer composite, specifically, is related to one kind
Multifunctional graphite vinyl/polymer composite water permeable membrane and its production and use.
Background technology
In recent years, with the continuous expansion deepened continuously with application market of membrane separation technique research
Greatly, membrane separation technique has become an important force of water treatment field.In membrane material,
Macromolecular material has its unrivaled superiority.Constitute the high score of polymer membrane for water treatment
There is polytype in son.For example, poly- alum (PS) class, Kynoar (PVDF) class, poly- second
The various macromolecule materials such as alkene (PE) class, cellulose acetate (CA) class, polyacrylonitrile (PAN) class
Material, is used as polymer membrane for water treatment as seperation film.For the existence form of membrane material,
Flat Membrane, hollow-fibre membrane etc. can be divided into, can be selected according to concrete application.
According to the difference that film can retain particle size, membrane for water treatment can be divided into microfiltration membranes,
Milipore filter, NF membrane and reverse osmosis membrane (RO).Microfiltration membranes can remove micron and submicron order
Other colloidal solid, as general standard, microfiltration membranes can filter as little as 0.1pm
Grain.The aperture of milipore filter typically between 5nm to 100nm, can be with 100% removing water in
Bacterium and virus etc..NF membrane and reverse osmosis membrane are then used for less particle size range, can be with
The impurity such as the metal ion in removing water.
For NF membrane, its aperture in more than 1nm, typically in 1-2nm, for counter-infiltration
Film, then in 0.1nm or so.Due to imperceptible aperture, although water purification validity compared with
Height, but hole can be caused extremely easily to be blocked by fine particle or bacterial virus or adhered to so that
There is obstacle in Water warfare, brings using upper inconvenience.And as bacterial virus is in blocking
Position or the breeding of attachment area, cause a certain degree of pollution of purified water, so as to need frequency
Numerous replacing, increased financial cost.
Reverse osmosis membrane, be make under stress solute in solution reverse osmosis membrane concentration high one
Side concentration is raised, and is declined in the low side concentration of reverse osmosis membrane concentration, so as to separate with solvent
During apply, it is therefore desirable to possess stronger mechanical strength.Existing reverse osmosis membrane by
In the performance issue of the aspects such as mechanical strength, resistance to acids and bases and heat resistance, should Long-Time Service,
But it is accomplished by changing immediately once there is breakage in use, except bringing using upper inconvenience
Outside, also reduce operating efficiency.
As can be seen here, usually as the performance required by polymer membrane for water treatment, except target
Stalling characteristic beyond, can also enumerate:Have excellent water penetration, physical strength excellent,
Stability (i.e. resistance to chemical reagents) relative to various chemical substances is high, it is dirty to be difficult attachment when filtering
Dirty (i.e. stain resistance is excellent) etc..Conventional macromolecule member material, mostly porous material, this
Although meet the problem of water penetration, exist in terms of anti-pollution ability very big not
Performance in terms of foot, mechanical strength also has much room for improvement, so a new water process of exploitation
Membrane material is imperative.
Graphene is a kind of SP2Hydridization has cellular material with carbon element, the thickness of single-layer graphene
Degree only has 0.334nm, is to be currently known most thin material.Graphene has the ratio table of super large
Area is up to about 2600m2/ g, in view of the characteristic of the specific surface area of its superelevation, grapheme material
Obtain in terms of environment absorption and purification of air widely studied；And because Graphene material
Material itself is highly stable, generally chooses the load which is composite in material science research
Body, for preparing graphene-based composite.Graphene is also because having very high conductive performance
With carrier's rate performance, can be applicable in electronic information technology；And have because of which super
Big thermal conductivity (- 5000W/m*K), Graphene also result in the researcher in terms of heat transfer
Great interest, apply it in heat-conducting medium, prepare high heat conductance heat transfer medium.
Find that Graphene has certain anti-microbial property in conventional research, subsequently occur one
Graphene with the preferable anti-microbial property/silver nanoparticle composite antibacterial material of series, research are sent out
Existing such material is respectively provided with certain complexity in the technique for preparing or using effect has
Certain limitation.Some researchs are chosen titanium dioxide and carry out cooperateing with and promote Graphene/silver
Anti-microbial property, this are higher photocatalytic activity, the nothings using photocatalysis material of titanium dioxide
The technical characterstic such as toxicity, stable chemical nature, anti-light corrosive nature be strong, in studying in the past
There is substantial amounts of report to prove that titanium dioxide can be used in field of environment protection (such as：Purification of air,
Sterilization of water etc.).Which can be directly affected in the agglomeration for considering nano titanium oxide
Catalytic performance, from the big Graphene of specific surface area as carrier, can enable it to effectively
It is dispersed in graphene sheet layer and represents more preferable catalytic antimicrobial performance.
Content of the invention
In order to overcome the membrane material for meeting water penetration requirement in existing water technology anti-
Need to improve in terms of pollution antibacterial ability, the deficiency that the performance of mechanical strength also has much room for improvement,
The present invention targetedly develops a kind of new permeable membrane material.This kind of permeable membrane material
Mechanical strength, anti fouling performance, resistance to acids and bases, heat resistance, the multiple function phase such as thermal conductivity
Existing water permeable membrane is significantly increased, therefore this kind of water permeable membrane is referred to as multi-functional permeable
Film.
Specifically, first aspect present invention is multiple there is provided a kind of multifunctional graphite vinyl/macromolecule
Condensation material water permeable membrane, it is characterised in that the water permeable membrane includes：
A) wet polymer polymer is led selected from following at least one：Lead wet homopolymers, lead wet
Copolymer and its any combination；
B) Graphene or graphene composite material；With
C) microporous substrate,
Wherein, described in the microporous substrate wet polymer compound is led with the Graphene or stone
Black alkene composite forms hydrogen bond, ionic bond and/or covalent bond by polar group functional group
Effective chemical bond linkage, so as to form the water-permeable passage with reinforcing hydrophilic-hydrophobic group,
Achieve water permeable membrane selectively permeable, finally give high purity water.Add the Graphene or
Graphene composite material can be led the 0.01% of wet polymer polymer quality and arrived based on described
5%.
A kind of technical scheme for adopting of the present invention be described lead wet polymer polymer for selected from
Following at least one：Commercialization polyethylene glycol oxide (PEO), polystyrene sulphuric acid, polyester,
Merlon (PC), poly- (methyl methacrylate) (PMMA), polyamide (PA), polyurethane
(PU), the SBR styrene butadiene rubberses (SBR) of sulfonation, styrene-acrylate, polyethers ether
Ketone (PEEK) etc. and their polymer or mixture.Described lead the flat of wet polymer polymer
Average molecular weight can be selected in 10000 to 1000000 scope.This leads wet polymer polymer can
Containing selected from following at least one polar group functional group：-OH、-SH、-COOH、-OR、
-COOR、-PO3H2、-SO3H、-NH2Deng.May be used also in water permeable membrane provided by the present invention
Containing d) selected from following at least one additive：Antioxidant, UV stabilizer or oxidation,
Heat and ultraviolet degradation inhibitor, crosslinking agent and their mixture.
Graphene used in the present invention or graphene composite material can be partial oxidation or complete
Graphene oxide sheet, graphene oxide/ag material, graphene oxide/titanic oxide material,
Or graphene oxide/silver/titanium dioxide composite.The Graphene or Graphene composite wood
Material is containing selected from following at least one polar group functional group：-OH、-SH、-COOH、
-OR、-COOR、-PO3H2、-SO3H、-NH2Deng.Described partial oxidation or total oxygen
There is graphite alkene piece laminate structure and lamella is 1-10 carbon atomic layer thickness, lamella
Big I is 1-100 μm.
The machinery of multifunctional graphite vinyl provided by the present invention/polymer composite water permeable membrane
Intensity, rub resistance intensity are significantly improved, and can bear pressure not less than 0.1 MPa (MPa),
Preferably not less than 0.15MPa, more preferably no less than 0.2MPa.
In the different operating condition with permeable film process water, if the resistance to acids and bases of film is not
By force, heat resistance is not strong, and long-term use in the environment compared with severe corrosive or hyperpyrexia can reduce film
Mechanical strength, so as to have influence on the durability of film, and the water permeable membrane of the present invention is especially at this
Aspect has the incomparable advantage of other films.
The acid-proof alkaline of water permeable membrane provided by the present invention is significantly improved, such as in running water
Under the conditions of the conventional water treatment for the treatment of plant, service life increases significantly, more than 10 years.Institute
The anti-pollution ability of antibacterial for stating water permeable membrane is also significantly improved, and mould proof grade is 0 grade, i.e., not long
Bacterium, during operation without the need for changing, there is automatical cleaning ability.The heat conduction system of the water permeable membrane
Number and temperature capacity are also significantly improved, and thermal conductivity factor is not less than 0.3W/mK, preferably not less than
0.5W/mK；Heat resisting temperature preferably reaches 200 DEG C up to 150 DEG C.
The thickness of multifunctional graphite vinyl provided by the present invention/polymer composite water permeable membrane
In 1-300 μm of scope, 5-250 μm can be selected in, 20-100 μm of scope.At this
When bright provided multifunctional graphite vinyl/polymer composite water permeable membrane is the film of crosslinking,
Its above-mentioned multi-functional performance is more projected.
Graphene-containing or the multifunctional macromolecule film of graphene composite material that the present invention is provided
Material has good mechanical strength, heat resistance, heat conduction while with excellent water penetration
Property, acid-proof alkaline and anti-microbial property, are because which belongs to and receive Porous materials, i.e., wherein constitute
Molecule forms to have by group coupled action receives the material of microchannel structure, specifically,
The characteristics of which projects is the membrane material by leading wet polymer compound with Graphene or graphite
Alkene composite forms having for hydrogen bond, ionic bond and/or covalent bond by polar group functional group
Effect chemical bond linkage, so as to form the water-permeable passage with reinforcing hydrophilic-hydrophobic group, because
This significantly enhances its mechanical strength and acid-proof alkaline in water treatment procedure.Because right
The selection of hydrone is extremely strong by property, so the multifunctional graphite vinyl/macromolecule with the present invention
The aqueous solution of the permeable film process gained of composite is high purity water.
To achieve these goals, another aspect of the present invention provides a kind of multifunctional graphite vinyl
The preparation method of/polymer composite water permeable membrane, it is characterised in that including following system
Standby step：
A) under the constant temperature of 10-100 DEG C of scope, make to lead wet polymer polymer with
The time of pre-determining and order are dissolved in multiple organic solvents formation solution, be sufficiently stirred for
It is well mixed；
B) add in the solution that Graphene or graphene composite material to previous step are obtained, fill
Divide stirring to be well mixed；And
C) film forming procedure：In temperature under conditions of 10-200 DEG C of scope, by step B)
In the solution that obtains be applied on a surface or two sides of microporous substrate.Form thickness to exist
Uniform membrane material in 10-250 μ ms, had both ensured the mechanical strength of membrane material, again might be used
To meet its water penetration.
The preparation method is in step A) and B) between can also include step：A ') add to
A kind of few additive is to step A) in be thoroughly mixed in the solution that obtains uniform.This system
Preparation Method is preferably included in C) it is crosslinked after film forming procedure, formed with the microporous substrate
The coating of continuous crosslinking permeable polymer.
The multi-functional embodiment of the composite water permeable membrane that the present invention is provided with this kind of preparation method
The significantly improving of the performances such as mechanical strength, rub resistance intensity and acid and alkali-resistance in membrane material, longevity
Life increases significantly, the anti-pollution ability of antibacterial is significantly improved, thermal conductivity factor and the ability such as heat-resisting show
Write and improve.The permeable membrane material can bear pressure reduction not less than 0.1MPa, such as originally
Under the conditions of the conventional water treatment of water treatment plant, service life is not less than 10 years, and market class
It it is only half a year like the normality service life of the water permeable membrane of function；The permeable membrane material is in work
Period is without the need for changing, there is automatical cleaning ability；The thermal conductivity factor of the permeable membrane material is not little
In 0.3W/mK, 200 DEG C of high temperature can be born, and the water permeable membrane of market similar functions is only capable of
The temperature of 125 DEG C or so of tolerance；The permeable membrane material is Porous materials, the anti-pollution ability received
Splendid, according to standard GB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and
Antibacterial effect》, it is determined as strong antibacterial (0 grade).
And, a kind of multifunctional graphite vinyl/polymer composite that the present invention is provided is permeable
The superiority of the preparation method of film also resides in reagent and material is cheap and simple and easy to get, operation side
Method is also relatively easy, and in operating process, variable is easily controlled.
Another aspect of the present invention additionally provides the multifunctional graphite vinyl/polymer composite
The purposes of water permeable membrane, due to the performances such as its mechanical strength, rub resistance intensity and acid and alkali-resistance notable
Improve, the life-span increases significantly, the anti-pollution ability of antibacterial is significantly improved, thermal conductivity factor and heat-resisting
Significantly improve etc. ability, it can be applicable to total-heat exchanger, humidistat (for humidifying
And/or dehumidifying), sewage disposal, fuel cell, yarn fabric, wound dressing and other be suitable to
The purposes of permeable or filter water.
Description of the drawings
Polar group functional group key links of the Fig. 1 for multifunctional graphite vinyl/polymer composite
And water-permeable passage schematic diagram.
Aqueous water 1 is passed through being combined by macromolecule in microporous matrix from the high-pressure side 7 of water permeable membrane
Material 4 and multifunctional graphite vinyl 3 form bonded and reinforcing parent by polar group functional group 2
The water-permeable passage of water-hydrophobic grouping, with steam state hydrone 5 under the collective effect of pressure reduction
Form reaches low-pressure side 6.
Fig. 2 is multifunctional graphite vinyl/polymer composite water permeable membrane electron microscope.Understand film
Material is to receive Porous materials, and surface major part is smooth, has partial function Graphene added material
Micro-structural manifests.
Collection of illustrative plates of the Fig. 3 and 4 for the EDX constituent analyses of membrane material.Wherein, Fig. 3 is EDX
The collection of illustrative plates (spectrum) 1 of constituent analysis, which show the front of membrane material, and Fig. 4 is EDX
The collection of illustrative plates 2 of constituent analysis, which show the back side of membrane material.From element (Element), weight
Knowable to amount percentage (Weight%) and atomic percent (atomic%) data binding analysis, just
Face mainly contains C, and O, H (H cannot be measured) element is hydrophobic side, the back side mainly contain C,
The presence of O, Si, S, H, wherein S demonstrates the presence of sulfonic acid group, is water-wet side,
Hydrone can be permeated from water-wet side toward hydrophobic side.
Specific embodiment
It is saturating that an aspect of of the present present invention provides a kind of multifunctional graphite vinyl/polymer composite
Moisture film, the water permeable membrane include：
A) wet polymer polymer is led selected from following at least one：Lead wet homopolymers, lead wet
Copolymer and its any combination；
B) Graphene or graphene composite material；With
C) microporous substrate,
Wherein, described in the microporous substrate wet polymer polymer is led with the Graphene or stone
Black alkene composite forms hydrogen bond, ionic bond and/or covalent bond by polar group functional group
Effective chemical bond linkage, so that form the water-permeable passage with reinforcing hydrophilic-hydrophobic group.
According to a concrete technical scheme of the present invention, in the multifunctional graphite vinyl/high score
Described in sub- composite water permeable membrane lead wet polymer polymer be selected from following at least
A kind of：Commercialization polyethylene glycol oxide, polystyrene sulphuric acid, polyester, Merlon, poly- (first
Base methyl acrylate), polyamide, polyurethane, the SBR styrene butadiene rubberses of sulfonation, benzene
Ethylene-acrylate, polyether-ether-ketone, their polymer and their mixture.
According to a concrete technical scheme of the present invention, in the multifunctional graphite vinyl/high score
Described in sub- composite water permeable membrane lead wet polymer polymer contain selected from following extremely
A kind of few polar group functional group：-OH、-SH、-COOH、-OR、-COOR、-PO3H2、
-SO3H and-NH2.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
Composite water permeable membrane also includes：D) following at least one additive is selected from：Antioxidant,
UV stabilizer or oxidation, heat and ultraviolet degradation inhibitor, crosslinking agent and their mixing
Thing.
According to a concrete technical scheme of the present invention, in the multifunctional graphite vinyl/high score
The Graphene or graphene composite material in sub- composite water permeable membrane is partial oxidation
Or oxidized graphene film, graphene oxide/ag material, graphene oxide/titanium dioxide titanium
Material or graphene oxide/silver/titanium dioxide composite.
According to a concrete technical scheme of the present invention, in the multifunctional graphite vinyl/high score
The Graphene or graphene composite material in sub- composite water permeable membrane contains selected from such as
Under at least one polar group functional group：-OH、-SH、-COOH、-OR、-COOR、
-PO3H2、-SO3H and-NH2.
According to a concrete technical scheme of the present invention, in the multifunctional graphite vinyl/high score
Above-mentioned partial oxidation or oxidized graphene film in sub- composite water permeable membrane has thin layer
Structure and lamella are 1-10 carbon atomic layer thickness, and the size of lamella is in 1-100 μm of model
In enclosing.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
The mechanical strength of composite water permeable membrane, rub resistance intensity are significantly improved, the pressure reduction that can be born
It is not less than 0.1MPa, acid-proof alkaline is significantly improved.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
The anti-pollution ability of the antibacterial of composite water permeable membrane is significantly improved, and mould proof grade is not long bacterium
0 grade, during operation without the need for changing, there is automatical cleaning ability.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
The thermal conductivity factor and temperature capacity of composite water permeable membrane is significantly improved, and thermal conductivity factor is not less than
0.3W/mK, heat resisting temperature reach 200 DEG C.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
The thickness of composite water permeable membrane is in the range of 1-300 μm.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
Composite water permeable membrane is the film of crosslinking.
According to a further aspect in the invention, the invention provides above-mentioned multifunctional graphite vinyl/height
The preparation method of molecular composite material water permeable membrane, which comprises the steps：
A) under the constant temperature of 10-100 DEG C of scope, make to lead wet polymer polymer with
The time of pre-determining and order are dissolved in multiple organic solvents formation solution, be sufficiently stirred for
It is well mixed；
B) add in the solution that Graphene or graphene composite material to previous step are obtained, fill
Divide stirring to be well mixed；And
C) film forming procedure：In temperature under conditions of 10-200 DEG C of scope, by step B)
In the solution that obtains be applied on one or two surface of microporous substrate.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
The preparation method of composite water permeable membrane is in step A) and B) between also include step：A ') add
Plus at least one additive is to step A) in be thoroughly mixed in the solution that obtains uniform.
According to a concrete technical scheme of the present invention, the multifunctional graphite vinyl/macromolecule
The preparation method of composite water permeable membrane is additionally included in C) it is crosslinked after film forming procedure, with
The microporous substrate forms the coating of continuous crosslinking permeable polymer.
According to a further aspect in the invention, the invention provides above-mentioned multifunctional graphite vinyl/height
Molecular composite material water permeable membrane is used for total-heat exchanger, humidistat, sewage disposal, combustion
Material battery, yarn fabric, wound dressing and other be suitable to the purposes of permeable or filter water.
The graphene-containing provided from above-mentioned Fig. 2 electron microscopes, the present invention or Graphene are compound
The surface major part of the permeable membrane material of the multifunctional macromolecule of material is smooth, has partial function stone
The micro-structural of black alkene added material manifests, and belongs to and receives Porous materials.And film used in prior art
Aperture minimum also have 0.1nm or so, so the present invention provide permeable membrane material substantially excellent
Film used in existing water technology.
Passed through by macromolecule from the high-pressure side 7 of water permeable membrane from Fig. 1, aqueous water 1 is illustrated
Composite 4 and multifunctional graphite vinyl 3 are formed bonded and strong by polar group functional group 2
Change the water-permeable passage of hydrophilic-hydrophobic group, with steam state hydrone 5 under the collective effect of pressure reduction
Form reach low-pressure side 6.Which passes through the Graphene of high-specific surface area or graphene-based compound
Material and the group coupled action of macromolecule water permeable membrane storeroom, especially by selected from following
At least one leads wet polymer polymer：Lead wet homopolymers, lead wet copolymer and its any
Combination, in microporous substrate, passes through polar group sense with Graphene or graphene composite material
Group forms the effectively chemical bond linkage such as hydrogen bond, ionic bond, covalent bond, has by force so as to be formed
Change the water-permeable passage of hydrophilic-hydrophobic group.
"/" in " graphene/polymer composite material " described herein is in order to by composite
In component Graphene or graphene composite material and high molecular polymer separate display, " oxygen
Graphite alkene/ag material ", " graphene oxide/titanic oxide material ", " graphene oxide/silver
"/" in/composite titania material " is to separate the different component in display material.
" homopolymers " described herein refers to the polymer being polymerized by a kind of monomer.Described herein
" copolymer " refers to the polymer containing two or more monomeric unit, copolymer type
Citing includes random copolymer, alternate copolymer, block copolymer and graft copolymer etc..
" leading wet " described herein instigates (polymer) moisture or water vapor permeation.
The technical solution used in the present invention is to lead wet height from one or more better performances
Molecularly Imprinted Polymer, such as commercialization polyethylene glycol oxide (PEO), polystyrene sulphuric acid, polyester,
Merlon (PC), poly- (methyl methacrylate) (PMMA), polyamide (PA), polyurethane
(PU), the SBR styrene butadiene rubberses (SBR) of sulfonation, styrene-acrylate, polyethers ether
Ketone (PEEK) etc. and their polymer or mixture.This leads wet polymer polymer and can contain
-OH、-SH、-COOH、-OR、-COOR、-PO3H2、-SO3H、-NH2Isopolarity
Base functional group.
EDX constituent analyses referring specifically to Fig. 3 and 4 membrane materials.Fig. 3 is EDX compositions
The collection of illustrative plates 1 of analysis, which show the front of membrane material, and Fig. 4 is EDX constituent analyses
Collection of illustrative plates 2, which show the back side of membrane material.From element, percentage by weight and atomic percent
Understand than data binding analysis, front mainly contains C, O, H (H cannot be measured) element is
Hydrophobic side, the back side mainly contain C, O, Si, S, H, and the wherein presence of S demonstrates sulphur
The presence of acid groups, is water-wet side, and hydrone can be from water-wet side toward hydrophobic side infiltration.
" EDX " described herein represents energy dispersion X-ray spectroscopic methodology (Energy Dispersive
X-Ray Spectroscopy), its elemental characteristic X ray ripple sent by means of analysis sample
Long and intensity, the element according to contained by wavelength determines sample, according to the phase of strength detection element
To content.
" microporous substrate " described herein is commonly used in the filming technology of this area, and its aperture can be
Between 5.0nm-1.0mm, for example, there are fluorinated copolymer, Kynoar (PVDF) etc..
D) at least one additive can also be contained in water permeable membrane provided by the present invention, described
Additive is selected from antioxidant, UV stabilizer or oxidation, heat and ultraviolet degradation and suppresses
Agent, crosslinking agent and their mixture.
Because macromolecular material can all occur irreversible structure change in use, i.e.,
Aging, its reason includes the factors such as physics, chemistry, specifically includes heat, light, oxidation, change
Medium etc. is learned, so the conventional antioxidant that adds carrys out delaying aging." antioxygen described herein
Agent " includes amine, phenols, sulfur-bearing, the type such as phosphorous." UV stabilizer " described herein
Refer to and absorb most of for ultraviolet radioactive, and this part energy for being absorbed is converted into harmless
The organic compound that discharges of heat energy.Conventional UV stabilizer has benzophenone, benzo
The derivative of the compound such as triazole and salicylate." oxidation, heat and ultraviolet light described herein
Degradation inhibitor " refers to for delaying due to aoxidizing, heat and ultraviolet light cause polymer aging
Material.
" crosslinking agent " described herein refers to can be in intermolecular bridging action of line style, so that multiple
Linear molecule is mutually bonded and is cross-linked into cancellated material, be also called in plastic industry " Gu
Agent ", " curing agent " etc., commonly used in the prior art for example have cumyl peroxide
(DCP), diethylenetriamines (DTA) etc..
Graphene composite material used in the present invention can be partial oxidation or total oxygen graphite
Alkene piece, graphene oxide/ag material, graphene oxide/titanic oxide material or oxidation stone
Black alkene/silver/titanium dioxide composite and other graphene composite materials commonly used in the art.
" Graphene/silver/titanium dioxide composite " described herein is referred on graphene powder base material
Load silver, titanium dioxide and other particles or ion, form and there is the compound of high-specific surface area
Functional material.The polar group functional group of the Graphene and its composite include-OH,
-SH、-COOH、-OR、-COOR、-PO3H2、-SO3H、-NH2Isopolarity base official
Can group.
There is laminate structure for described partial oxidation or oxidized graphene film and lamella is
1-10 carbon atomic layer thickness, the big I of lamella is 1-100 μm.
The machinery of multifunctional graphite vinyl provided by the present invention/polymer composite water permeable membrane
Intensity, rub resistance intensity are significantly improved, and can be born pressure and are not less than 0.1MPa, preferably not
0.3MPa is less than, more preferably no less than 0.5MPa, acid-proof alkaline are significantly improved, example
Such as under the conditions of the conventional water treatment of water treatment plants, service life increases significantly, 10
More than year.The thermal conductivity factor and temperature capacity of the water permeable membrane is also significantly improved, thermal conductivity factor
It is not less than 0.3W/mK, preferably not less than 0.5W/mK；Heat resisting temperature is up to 150 DEG C, excellent
Choosing reaches 200 DEG C.
The anti-pollution ability of the antibacterial of the water permeable membrane is also significantly improved, and mould proof grade is 0 grade,
I.e. not long bacterium, during operation without the need for changing, there is automatical cleaning ability.According to standard
GB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》, determine
For strong antibacterial (0 grade).The standard is tested using plate culture, and testing conditions are temperature
Degree 28 ± 1 DEG C, relative humidity RH>90%th, time 28 days；Test strain is aspergillus niger
(Aspergillus niger), Aspergillus terreus (Aspergillus terreus), paecilomyces varioti
(Paecilomyces varioti), penicillium funiculosum (Penicillium funiculosum), sprout short
Obstruct mould (Aureobasidium pullulans), Chaetomium globosum (Chaetoomium globsum),
Fungi-growth grade is assessed as：0 grade --- not long, i.e., observe under microscope (amplifying 50 times) and have no
Growth；1 grade --- vestige grows, i.e. naked eyes visible growth, but growth area coverage is less than
10%；2 grades --- growth area coverage is not less than 10%.
The thickness of multifunctional graphite vinyl provided by the present invention/polymer composite water permeable membrane
In 1-300 μm of scope, 5-200 μm of scope, preferably 10-250 μm of model can be selected in
Enclose, optional 20-100 μm of scope.In multifunctional graphite vinyl/high score provided by the present invention
When sub- composite water permeable membrane is the film of crosslinking, its above-mentioned multi-functional performance is more projected.
Provided herein is graphene-containing or graphene composite material multifunctional macromolecule membrane material
Material not only has good mechanical strength, heat resistance, thermal conductivity, acid-proof alkaline and antibacterial
Performance, and there is excellent water penetration, high purity water is obtained after permeable process.This
" high purity water " described in text refer to water temperature be 25 DEG C when, electrical conductivity be less than 0.1 μ S/cm,
PH value is 6.8-7.0 and the water for removing other impurities and bacterium, and this kind of impurities in water amount is less than
0.1mg/L.
To achieve these goals, another aspect of the present invention preferably provides a kind of multi-functional stone
The preparation method of black alkene/polymer composite water permeable membrane, it is characterised in that including as follows
Preparation process：
A) under the constant temperature of 10-100 DEG C of scope, make to lead wet polymer polymer with
The time of pre-determining and order are dissolved in multiple organic solvents formation solution, be sufficiently stirred for
It is well mixed；
A ') add at least one additive to step A) in be sufficiently stirred for mixing in the solution that obtains
Close uniform；
B) add in the solution that Graphene or graphene composite material to previous step are obtained, fill
Divide stirring to be well mixed；And
C) film forming procedure：Under 10-200 DEG C of temperature conditionss, by step B) in obtain molten
Liquid is applied on a surface or two sides of microporous substrate, and in C) film forming procedure is laggard
Row crosslinking, forms the coating of continuous crosslinking permeable polymer with the microporous substrate.Formed
Uniform membrane material of the thickness in 10-250 μ ms, had both ensured the mechanical strength of membrane material,
Its water penetration can be met again.
Further, the invention provides the multifunctional graphite vinyl/polymer composite
The purposes of water permeable membrane.Because macromolecule is led wet polymer with graphene-based composite wood organically
Material forms the effectively chemical bond linkage such as hydrogen bond, ionic bond, covalent bond by polar group functional group,
There is the permeable logical of reinforcing hydrophilic-hydrophobic group so as to be formed on the basis of wet polymer is led
Road, at the same significantly improve mechanical strength of the water permeable membrane during permeable, rub resistance intensity and
The anti-pollution ability of acid-proof alkaline, antibacterial, heat conduction and the characteristic such as heat-resisting, so described permeable
Film need not be changed during being a kind of long-life, work, there is the multi-functional multiple of automatical cleaning ability
Condensation material water permeable membrane, can be applicable to total-heat exchanger, humidistat (for humidification and/or
Dehumidifying), sewage disposal, fuel cell, yarn fabric, wound dressing and other be suitable to permeable
Or the occasion of filter water.
Embodiment
Will be in the present invention more particularly described below by the following examples.It is not necessarily to be construed as this
Bright it is limited to these embodiments or is limited by these embodiments.Those skilled in the art can be at this
The modification and improvement of various modes are carried out in the technological concept of invention.
<Embodiment 1>
First, under 45-50 DEG C of constant temperature, the pre- wet polymer of leading that chooses is made to be polymerized
Thing (KX-1) is dissolved in corresponding ORGANIC SOLVENT MIXTURES, is sufficiently stirred for until being well mixed.
Then, add the antioxidant (d1) that chooses in advance into obtained solution, fully stir
Mix until being well mixed.
Subsequently, add graphene oxide/silver/titanium dioxide composite (GC-1) supreme
In the solution that step is obtained, it is sufficiently stirred for being well mixed.
Finally, film forming under 60 DEG C of temperature conditionss, the solution that previous step is obtained is applied to
On microporous substrate (c1) surface that chooses in advance, and it is crosslinked after film forming procedure, with institute
State the coating that microporous substrate (c1) forms continuous crosslinking permeable polymer.Forming thickness is
150 μm of uniform membrane material.
After tested, gained membrane material water penetration is good, can bear pressure reduction for 0.12MPa, lead
Hot coefficient is 0.35W/mK, can bear 180 DEG C of high temperature, and GB/T2591-2003 is determined as
Strong antibacterial (0 grade).
<Embodiment 2>
First, under 50 DEG C of constant temperature, make to lead wet polymer polymer (PM-3) each molten
In corresponding ORGANIC SOLVENT MIXTURES, it is stirred well to after being completely dissolved and mixes, continue to stir
Mix until being well mixed.
Then, add the antioxidant (d3) that chooses in advance into obtained solution, fully stir
Mix until being well mixed.
Then, add graphene oxide/silver/titanium dioxide composite (GC-2) to previous step
Suddenly, in the solution for obtaining, it is sufficiently stirred for being well mixed.
Finally, film forming under 70 DEG C of temperature conditionss, the solution that previous step is obtained is applied to
On the two sides of microporous substrate (c2), and it is crosslinked after film forming procedure, with the micropore
Base material (c2) forms the coating of continuous crosslinking permeable polymer.It is 120 μm to form thickness
Uniform membrane material.
After tested, gained membrane material water penetration is good, can bear pressure reduction for 0.11MPa, lead
Hot coefficient is 0.42W/mK, can bear 160 DEG C of high temperature, and GB/T2591-2003 is determined as
Strong antibacterial (0 grade).
Claims (10)
1. a kind of multifunctional graphite vinyl/polymer composite water permeable membrane, it is characterised in that
The water permeable membrane includes：
A) wet polymer polymer is led selected from following at least one：Lead wet homopolymers, lead wet
Copolymer and its any combination；
B) Graphene or graphene composite material；With
C) microporous substrate,
Wherein, described in the microporous substrate wet polymer polymer is led with the Graphene or stone
Black alkene composite forms hydrogen bond, ionic bond and/or covalent bond by polar group functional group
Effective chemical bond linkage, so that form the water-permeable passage with reinforcing hydrophilic-hydrophobic group.
2. multifunctional graphite vinyl as claimed in claim 1/polymer composite water permeable membrane,
Characterized in that,
The wet polymer polymer of leading is selected from following at least one：Commercialization polyoxygenated
Ethene, polystyrene sulphuric acid, polyester, Merlon, poly- (methyl methacrylate), poly-
Acid amides, polyurethane, the SBR styrene butadiene rubberses of sulfonation, styrene-acrylate, poly-
Ether ether ketone, their polymer and their mixture.
3. multifunctional graphite vinyl as claimed in claim 2/polymer composite water permeable membrane,
Characterized in that,
The wet polymer polymer of leading contains selected from following at least one polar group sense
Group：-OH、-SH、-COOH、-OR、-COOR、-PO3H2、-SO3H and-NH2.
4. multifunctional graphite vinyl as claimed in claim 1/polymer composite water permeable membrane,
Characterized in that, the water permeable membrane also includes：
D) following at least one additive is selected from：Antioxidant, UV stabilizer or oxidation,
Heat and ultraviolet degradation inhibitor, crosslinking agent and their mixture.
5. multifunctional graphite vinyl as claimed in claim 1/polymer composite water permeable membrane,
Characterized in that,
The Graphene or graphene composite material be partial oxidation or oxidized graphene film,
Graphene oxide/ag material, graphene oxide/titanic oxide material or graphene oxide/
Silver/titanium dioxide composite.
6. multifunctional graphite vinyl as claimed in claim 5/polymer composite water permeable membrane,
Characterized in that,
The Graphene or graphene composite material contain selected from following at least one polarity
Base functional group：-OH、-SH、-COOH、-OR、-COOR、-PO3H2、-SO3H and
-NH2.
7. multifunctional graphite vinyl/the polymer composite as described in claim 1-6 is arbitrary
The preparation method of water permeable membrane, it is characterised in that comprise the steps：
A) under the constant temperature of 10-100 DEG C of scope, make to lead wet polymer polymer with
The time of pre-determining and order are dissolved in multiple organic solvents formation solution, be sufficiently stirred for
It is well mixed；
B) add in the solution that Graphene or graphene composite material to previous step are obtained, fill
Divide stirring to be well mixed；And
C) film forming procedure：In temperature under conditions of 10-200 DEG C of scope, by step B)
In the solution that obtains be applied on one or two surface of microporous substrate.
8. preparation method as claimed in claim 7, it is characterised in that in step A) and
B also include step between)：
A ') add at least one additive to step A) in be sufficiently stirred for mixing in the solution that obtains
Close uniform.
9. preparation method as claimed in claim 7, it is characterised in that be additionally included in C)
Be crosslinked after film forming procedure, continuous crosslinking permeable polymer is formed with the microporous substrate
Coating.
10. multifunctional graphite vinyl/the polymer composite as described in claim 1-6 is arbitrary
Water permeable membrane is used for total-heat exchanger, humidistat, sewage disposal, fuel cell, weaving
Thing, wound dressing and other be suitable to the purposes of permeable or filter water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012006657A1 (en) * | 2010-07-14 | 2012-01-19 | Monash University | Material and applications therefor |
| CN102614788A (en) * | 2012-02-29 | 2012-08-01 | 青岛大学 | Preparation method for polyether sulfone/graphene oxide composite ultrafiltration membrane |
| CN103623709A (en) * | 2013-11-11 | 2014-03-12 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
| CN103736400A (en) * | 2014-01-06 | 2014-04-23 | 中国海洋大学 | Preparation method of graphene oxide composite nano filter membrane |
| WO2014168629A1 (en) * | 2013-04-12 | 2014-10-16 | General Electric Company | Membranes comprising graphene |
-
2015
- 2015-09-07 CN CN201510567581.1A patent/CN106492654A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012006657A1 (en) * | 2010-07-14 | 2012-01-19 | Monash University | Material and applications therefor |
| CN102614788A (en) * | 2012-02-29 | 2012-08-01 | 青岛大学 | Preparation method for polyether sulfone/graphene oxide composite ultrafiltration membrane |
| WO2014168629A1 (en) * | 2013-04-12 | 2014-10-16 | General Electric Company | Membranes comprising graphene |
| CN103623709A (en) * | 2013-11-11 | 2014-03-12 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
| CN103736400A (en) * | 2014-01-06 | 2014-04-23 | 中国海洋大学 | Preparation method of graphene oxide composite nano filter membrane |
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