CN108905652A - A kind of preparation method of sandwich structure high-performance CMC cation-exchange membrane - Google Patents
A kind of preparation method of sandwich structure high-performance CMC cation-exchange membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
The invention discloses a kind of preparation methods of sandwich structure high-performance CMC cation-exchange membrane, and steps are as follows：（1）Dissolution preparation CMC cation casting solution in solvent is added in sodium carboxymethylcellulose；（2）Appropriate carboxylic carbon nano-tube modification CMC is added in above-mentioned cationic casting solution；（3）Thermoplastic polyurethane is prepared by melt-spraying spinning technology（TPU）Non-woven cloth；（4）TPU conduction non-woven cloth is prepared using the method for swelling, ultrasound modification；（5）Using dipping, coating method by the above-mentioned CMC casting solution through carbon nano-tube modification and the compound CMC cation-exchange membrane for preparing high performance sandwich structure of TPU conduction non-woven cloth.Carboxylic carbon nano-tube in TPU conduction non-woven cloth can form intermolecular hydrogen bonding with CMC casting solution, be conducive to the enhancing of intermolecular force between TPU non-woven cloth and CMC film, to improve the thermal stability and electric conductivity of CMC cation-exchange membrane.
Description
Technical field
The present invention is applied to the technical field of membrane of electro synthesis, wastewater treatment, a kind of sandwich structure high-performance CMC cation
The preparation method of exchange membrane.
Background technique
In recent years, while economic rapid development brings convenient, also waste resource constantly, resource reclaim is again
Utilizing question is urgently to be resolved.Amberplex is a kind of new membrane, is widely used in sewage treatment, heavy metal recovery field.So
And there are many problems in the application in it, such as：Fouling membrane is serious, it is expensive, be difficult to recycling and reusing etc. so that ionic membrane
Application receive great obstruction.It is especially heavy to develop high comprehensive performance, the ionic membrane of cheap, recyclable recycling
It wants.
Cation-exchange membrane is that have the film of selection index system to cation, usually sulfonic acid type, with fixed group and can
The ion of dissociation, if sodium form sulfonic acid type fixed group is sulfonate radical, dissociating ions are sodium ions.Cation-exchange membrane is considered as
It is a kind of polyelectrolyte, since anode membrane is negatively charged, although the cation dissociated originally is dissociated to water by hydrone effect
In, but under electric field action, the cation with positive charge be may be selected by through anode membrane, and anion because the same sex repels and
It cannot pass through, so having selective penetrated property.
The common cation-exchange membrane prepared by cationic casting solution has the disadvantage that：It is easy to become in use process
Shape；Thermal stability is bad；Resistance is higher；Energy consumption is high in use process.In recent years, have and answer cationic casting solution and metal nickel screen
Conjunction prepares the report of cation-exchange membrane.This novel cation-exchange membrane resistance is low, and mechanical stability is obviously improved.But
This cation-exchange membrane is needed using metal nickel screen, and cost is very high, and the physical property of metal nickel screen itself also determines system
The poor in flexibility of the standby cation-exchange membrane come out, restricted application.
Summary of the invention
Technical problem to be solved by the present invention lies in defect in the prior art is overcome, a kind of high-performance carboxymethyl is provided
Sodium cellulosate（CMC）The preparation method of cation-exchange membrane is led cationic casting solution and TPU using the method for dipping, coating
Electric non-woven cloth is compound, prepares that cost is relatively low, the CMC sun that mechanical property, electrical property and thermal stability are significantly increased from
Proton exchange.
In order to solve the above technical problems, the present invention uses following technical scheme：
The preparation method of sandwich structure high-performance CMC cation-exchange membrane of the present invention, steps are as follows：
（1）CMC cation casting solution is obtained by the CMC of certain mass is soluble in water；
（2）The functionalized multi-wall carbonnanotubes of certain mass are added to step（1）Casting solution in, prepare carbon nano tube modified
Modified CMC casting solution；
（3）With thermoplastic polyurethane（TPU）For raw material, TPU non-woven cloth is prepared using the method for melt-spraying spinning；
（4）The conductive modification of TPU non-woven cloth：By functionalized multi-wall carbonnanotubes（c-MWCNTs）It is added in dimethylbenzene, puts
Enter in ultrasonic washing instrument, ultrasonic vibration 60-90 minutes in 50-75 DEG C of water-bath, obtains carbon nano tube dispersion liquid；By TPU
Non-woven cloth is placed in dispersion liquid, ultrasonic vibration 1-3 minutes, take out and dried in 50-70 DEG C of baking oven 5-10 minutes to get
TPU conduction non-woven cloth；
（5）By step（4）Obtained TPU conduction non-woven cloth is placed in step（2）Modification CMC cation casting solution in, dipping
After take out, drying at room temperature obtains high-performance CMC cation-exchange membrane.
The step（1）The mass fraction of middle CMC cation casting solution is 2.5%-3.5%.
The step（2）The quality of middle c-MWCNTs is the 0.1%-0.3% of CMC mass in casting solution.
The step（3）The technological parameter that middle melt-spraying spinning prepares TPU non-woven cloth is：The set temperature of screw extruder
For 155-165 DEG C of 1st area, 2 200-210 DEG C of areas, 3 210-220 DEG C of areas, 4 220-230 DEG C of areas；The temperature of meltblown beam is 220-225
℃；The wind-warm syndrome and wind pressure of drawing-off hot wind are respectively 210-220 DEG C and 0.25-0.35 Pa；The reception distance of lace curtaining is 20-30
Cm, the movement speed of lace curtaining are 0.3-0.5 m/ minutes.
The step（3）It is middle melt-blown TPU non-woven cloth with a thickness of 20-60 μm.
The step（4）The concentration of middle carbon nano tube dispersion liquid is 0.01-0.20 mg/mL.
The step（4）The resistivity of obtained TPU conduction non-woven cloth is less than 50 Ω m.
The step（5）Dip time of the middle TPU conduction non-woven cloth in cationic casting solution is 40-60 minutes, leaching
Stain temperature is 22-30 DEG C.
Beneficial effects of the present invention：The present invention is prepared for TPU melt-blow nonwoven by melt-spraying spinning technology, and fiber is thinner
（<10 µm）, large specific surface area, melt-blown TPU non-woven cloth is with excellent flexibility.Based on TPU non-woven cloth large specific surface area
Functionalized multi-wall carbonnanotubes are uniformly modified using the method for ultrasonic disperse and TPU conduction are made in fiber surface by this feature
Non-woven cloth not only contributes to the raising of the evenly dispersed and non-woven cloth electric conductivity of conducting particles, is significantly reduced conduction
The dosage of particle, save the cost.Functionalized multi-wall carbonnanotubes are used in the present invention, functionalized multi-wall carbonnanotubes are due to having
More polar functional group enhances with the intermolecular active force of TPU, is conducive to the structure of conductive network in TPU conduction non-woven cloth
The stabilization with electric conductivity is built, the resistance of CMC cation-exchange membrane is significantly reduced.After resistance reduces, cation-exchange membrane
Operating voltage and operating power consumption are reduced, and are had the advantages that apparent energy-saving.TPU conduction non-woven cloth has excellent
Different elasticity, tear resistance and flexility, it is compound with CMC cation casting solution dipping, it can not only play backing material
Effect ,-the NH in TPU2It can occur with-the COOH in CMC appropriately crosslinked, be conducive to CMC cation-exchange membrane mechanicalness
The improvement of energy and the raising of structural stability.Carboxylic carbon nano-tube in TPU conduction non-woven cloth can be formed with CMC casting solution
Intermolecular hydrogen bonding, is conducive to the enhancing of intermolecular force between TPU non-woven cloth and CMC film, to improve the exchange of CMC cation
The thermal stability and electric conductivity of film.
Detailed description of the invention
Fig. 1 is the electric performance test curve for the CMC cation-exchange membrane that embodiment 1 is prepared；
Fig. 2 is the Mechanics Performance Testing curve for the CMC cation-exchange membrane that embodiment 1 is prepared；
Fig. 3 is the thermal gravimetric analysis curve for the CMC cation-exchange membrane that embodiment 1 is prepared；
Fig. 4 is the scanning electron microscope diagram for the CMC cation-exchange membrane that embodiment 1 is prepared.
Specific embodiment
Below with reference to the embodiment of the present invention, technical solution of the present invention is clearly and completely described.Obviously, it is retouched
The embodiment stated is only a part of the embodiment of the present invention, instead of all the embodiments.Based on implementation disclosed in this invention
Example, those of ordinary skill in the art can carry out partial modification or equivalent replacement to technical solution of the present invention, not pay
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
The preparation method of the present embodiment sandwich structure high-performance CMC cation-exchange membrane, steps are as follows：
（1）By cationic film forming matter sodium carboxymethylcellulose（CMC）It is dissolved in preparing in aqueous solvent and obtains the CMC of mass fraction 3%
Cationic casting solution；
（2）By the functionalized multi-wall carbonnanotubes of certain mass（c-MWCNTs）It is added to step（1）Casting solution in, c-
MWCNTs mass is the 0.1% of CMC mass, prepares the CMC casting solution of carbon nano tube modified modification, corresponding amberplex mark
It is denoted as mCMC；
（3）With thermoplastic polyurethane（TPU）For raw material, TPU non-woven cloth is prepared using the method for melt-spraying spinning.Wherein, screw rod
The set temperature of extruder is 165 DEG C of 1st area, 2 210 DEG C of areas, 3 220 DEG C of areas, 4 230 DEG C of areas；The temperature of meltblown beam is 225 DEG C；
The wind-warm syndrome and wind pressure of drawing-off hot wind are respectively 220 DEG C and 0.35 Pa；The reception distance of lace curtaining is 30 cm, the mobile speed of lace curtaining
Degree is 0.5 m/ minutes.Prepared TPU melt-blow nonwoven with a thickness of 25 μm, fibre diameter is 7 μm or so.
（4）The conductive modification of TPU non-woven cloth：By functionalized multi-wall carbonnanotubes（c-MWCNTs）It is added to dimethylbenzene
In, the mixed solution of 0.05 mg/mL, 0.1 mg/mL, 0.15 mg/mL and 0.2 mg/mL is respectively configured, it is clear to be put into ultrasonic wave
It washes in instrument, ultrasonic vibration 60 minutes, obtains carbon nano tube dispersion liquid in 60 DEG C of water-baths；TPU non-woven cloth is placed in above-mentioned
In dispersion liquid, 100 s of ultrasonic vibration takes out and dries 10 minutes in 50 DEG C of baking ovens to get TPU conduction non-woven cloth；
（5）By step（4）Obtained TPU conduction non-woven cloth is placed in step（2）Modification CMC cation casting solution in, dipping
60 minutes, dipping temperature was 27 DEG C, takes out drying at room temperature and obtains high-performance CMC cation-exchange membrane.For simplicity, 0.05 mg/
The TPU/CMC cation prepared under mL, 0.1 mg/mL, 0.15 mg/mL and 0.2 mg/mL carboxylic carbon nano-tube concentration conditions
Exchange membrane is respectively labeled as 0.05-mCMC, 0.10-mCMC, 0.15-mCMC and 0.20-mCMC, as illustrated in the accompanying drawings from 1 to 3.
The electric performance test of TPU/CMC cation-exchange membrane is prepared as shown in Figure 1, can be seen by Fig. 1 in the present embodiment
Out, the resistivity of modified CMC cation-exchange membrane reduces.Compared with CMC film, the CMC film after 0.1% carbon nano-tube modification
（mCMC）Resistivity be reduced to 14.82 Ω m by 32.34 Ω m, resistivity reduces 54.17%, this is because carbon
Nanotube itself has good electric conductivity, evenly dispersed in CMC casting solution, is conducive to mentioning for CMC cationic membrane electric conductivity
It is high.
The CMC film modified through TPU conduction non-woven cloth, with the increase of carbon nanotube concentration in conductive non-woven cloth, electricity
Resistance rate is gradually reduced, and electric conductivity is become better and better.The resistance of 0.05-mCMC, 0.10-mCMC, 0.15-mCMC and 0.20-mCMC film
Rate be respectively 14.34 Ω m, 13.35 Ω m, 7.35 Ω m and 2.46 Ω m.TPU conduction non-woven cloth is impregnated
Modified CMC cation-exchange membrane is prepared in CMC casting solution, is equivalent to the TPU conduction that high conduction performance is introduced in CMC film
Web is conducive to the raising of CMC cation-exchange membrane electric conductivity.Compared with before modified, the resistivity of 0.05-TPU/CMC
56 % are reduced, the resistivity of 0.2-TPU/CMC reduces 92%.
The Mechanics Performance Testing curve for the CMC cation-exchange membrane that the present embodiment is prepared is as shown in Figure 2.It can by Fig. 2
Know, compared with CMC, the CMC film of carbon nano-tube modification（mCMC）Tensile strength increase 17.33 MPa by 8.95 MPa,
Improve 94%.Elongation at break increases to 42.31% by 15.6%, improves 171%.Main cause is that carbon nanotube itself has
Good mechanical property, and it is evenly dispersed in CMC solution.Through the modified CMC film of TPU conduction non-woven cloth, modified CMC film
Tensile strength and elongation at break increase.Compared with CMC, 0.05-mCMC, 0.10-mCMC, 0.15-mCMC, 0.20-
The tensile strength of mCMC film has increased separately 224%, 241%, 169% and 162%, and elongation at break has increased separately 23.18%,
34.11%, 25.04%, 22.52%.There is excellent flexibility and elasticity mainly due to TPU non-woven cloth, between CMC film liquid
Interface binding power it is stronger, be conducive to effective transmitting of the stress between CMC film and non-woven cloth, improve tensile strength and tough
Property.
The thermal gravimetric analysis curve for the CMC cation-exchange membrane that the present embodiment is prepared is as shown in Figure 3.It can from figure
Out, on the whole, the thermogravimetric curve of the modified caudacoria of CMC is mobile to high temperature direction, and thermal stability improves.Compared with CMC, carbon nanometer
Pipe Modified Membrane（mCMC）200oC~250 oC-stage thermogravimetric curve slope dramatically increases, and illustrates that the introducing of carbon nanotube improves
The tolerable temperature of CMC film, so that thermal stability improves 5oC.TPU conduction non-woven cloth Modified Membrane compared with CMC obviously to
High temperature direction is mobile, especially 24oC ~290 oC range, film weight-loss ratio are gradually reduced with temperature increase.It can by comparison
Know, 24oC~290 oIn C temperature range, the sequence of thermal stability is：CMC after TPU conduction non-woven cloth modification
Amberplex is better than carbon nano tube modified CMC film, and the thermal stability of CMC is minimum.This is because in CMC cation-exchange membrane
CMWCNTs is introduced, cMWCNTs has excellent thermal stability, and draw ratio is big, and a small amount of cMWCNTs can significantly change
The thermal stability of kind film.In addition, with CMC appropriately crosslinked, intermolecular hydrogen between cMWCNTs and TPU non-woven cloth can occur for cMWCNTs
Key is conducive to the heat-staple improvement of CMC cation-exchange membrane.
The SEM figure for the CMC cation-exchange membrane that the present embodiment is prepared is as shown in Figure 4.As seen from the figure, through TPU
Conductive non-woven cloth is modified, and the structure of CMC film is " sandwich " structure, and casting solution is infiltrated well in TPU non-woven cloth,
Increase the interface binding power of non-woven cloth Yu CMC ionic membrane.Stronger interface binding power is advantageous between non-woven cloth and CMC film
In the raising of film thermal stability, structural stability and mechanical property.
Embodiment 2
The preparation method of the present embodiment sandwich structure high-performance CMC cation-exchange membrane, steps are as follows：
（1）By cationic film forming matter sodium carboxymethylcellulose（CMC）It is dissolved in preparing in aqueous solvent and obtains mass fraction 3.5%
CMC cation casting solution；
（2）By the functionalized multi-wall carbonnanotubes of certain mass（c-MWCNTs）It is added to step（1）Casting solution in, c-
MWCNTs mass is the 0.2% of CMC mass, prepares the CMC casting solution of carbon nano tube modified modification, corresponding amberplex mark
It is denoted as mCMC；
（3）With thermoplastic polyurethane（TPU）For raw material, TPU non-woven cloth is prepared using the method for melt-spraying spinning.Wherein, screw rod
The set temperature of extruder is 160 DEG C of 1st area, 2 205 DEG C of areas, 3 220 DEG C of areas, 4 225 DEG C of areas；The temperature of meltblown beam is 220 DEG C；
The wind-warm syndrome and wind pressure of drawing-off hot wind are respectively 215 DEG C and 0.35 Pa；The reception distance of lace curtaining is 30 cm, the mobile speed of lace curtaining
Degree is 0.5 m/ minutes.About 60 μm of the thickness of prepared TPU non-woven cloth, about 8 μm of fibre diameter；
（4）The conductive modification of TPU non-woven cloth：By functionalized multi-wall carbonnanotubes（c-MWCNTs）It is added in dimethylbenzene, point
The mixed solution for not configuring 0.03 mg/mL, 0.08 mg/mL, 0.13mg/mL and 0.18mg/mL, is put into ultrasonic washing instrument
In, ultrasonic vibration 60 minutes, obtains carbon nano tube dispersion liquid in 65 DEG C of water-baths；TPU non-woven cloth is placed in above-mentioned dispersion liquid
In, ultrasonic vibration 2min takes out and dries 5 minutes in 60 DEG C of baking ovens to get TPU conduction non-woven cloth；
（5）By step（4）Obtained TPU conduction non-woven cloth is placed in step（2）Modification CMC cation casting solution in, dipping
60 minutes, dipping temperature was 28 DEG C, takes out drying at room temperature and obtains high-performance CMC cation-exchange membrane.
Embodiment 3
The preparation method of the present embodiment sandwich structure high-performance CMC cation-exchange membrane, steps are as follows：
（1）By cationic film forming matter sodium carboxymethylcellulose（CMC）It is dissolved in preparing in aqueous solvent and obtains mass fraction 3.5%
CMC cation casting solution；
（2）By the functionalized multi-wall carbonnanotubes of certain mass（c-MWCNTs）It is added to step（1）Casting solution in, c-
MWCNTs mass is the 0.15% of CMC mass, prepares the CMC casting solution of carbon nano tube modified modification, corresponding amberplex mark
It is denoted as mCMC；
（3）With thermoplastic polyurethane（TPU）For raw material, TPU non-woven cloth is prepared using the method for melt-spraying spinning.Wherein, screw rod
The set temperature of extruder is 155 DEG C of 1st area, 2 200 DEG C of areas, 3 210 DEG C of areas, 4 230 DEG C of areas；The temperature of meltblown beam is 225 DEG C；
The wind-warm syndrome and wind pressure of drawing-off hot wind are respectively 210 DEG C and 0.25Pa；The reception distance of lace curtaining is 25cm, the movement speed of lace curtaining
It is 0.4m/ minutes.About 60 μm of the thickness of prepared TPU non-woven cloth, about 10 μm of fibre diameter；
（4）The conductive modification of TPU non-woven cloth：By functionalized multi-wall carbonnanotubes（c-MWCNTs）It is added in dimethylbenzene, point
Not Pei Zhi 0.01mg/mL, 0.05 mg/mL, 0.1mg/mL and 0.15mg/mL mixed solution, be put into ultrasonic washing instrument,
Ultrasonic vibration 70 minutes, obtains carbon nano tube dispersion liquid in 55 DEG C of water-baths；TPU non-woven cloth is placed in above-mentioned dispersion liquid,
Ultrasonic vibration 1min takes out and dries 10 minutes in 60 DEG C of baking ovens to get TPU conduction non-woven cloth；
（5）By step（4）Obtained TPU conduction non-woven cloth is placed in step（2）Modification CMC cation casting solution in, dipping
60 minutes, dipping temperature was 30 DEG C, takes out drying at room temperature and obtains high-performance CMC cation-exchange membrane.
Embodiment 4
The preparation method of the present embodiment sandwich structure high-performance CMC cation-exchange membrane, steps are as follows：
（1）By cationic film forming matter sodium carboxymethylcellulose（CMC）It is dissolved in preparing in aqueous solvent and obtains mass fraction 2.5%
CMC cation casting solution；
（2）By the functionalized multi-wall carbonnanotubes of certain mass（c-MWCNTs）It is added to step（1）Casting solution in, c-
MWCNTs mass is the 0.3% of CMC mass, prepares the CMC casting solution of carbon nano tube modified modification, corresponding amberplex mark
It is denoted as mCMC；
（3）With thermoplastic polyurethane（TPU）For raw material, TPU non-woven cloth is prepared using the method for melt-spraying spinning.Wherein, screw rod
The set temperature of extruder is 165 DEG C of 1st area, 2 205 DEG C of areas, 3 215 DEG C of areas, 4 215 DEG C of areas；The temperature of meltblown beam is 220 DEG C；
The wind-warm syndrome and wind pressure of drawing-off hot wind are respectively 215 DEG C and 0.3 Pa；The reception distance of lace curtaining is 20cm, and the movement speed of lace curtaining is
0.3m/ minutes.About 50 μm of the thickness of prepared TPU non-woven cloth, about 10 μm of fibre diameter；
（4）The conductive modification of TPU non-woven cloth：By functionalized multi-wall carbonnanotubes（c-MWCNTs）It is added in dimethylbenzene, point
Not Pei Zhi 0.1mg/mL, 0.15 mg/mL, 0.17mg/mL and 0.20mg/mL mixed solution, be put into ultrasonic washing instrument,
Ultrasonic vibration 60 minutes, obtains carbon nano tube dispersion liquid in 50 DEG C of water-baths；TPU non-woven cloth is placed in above-mentioned dispersion liquid,
Ultrasonic vibration 2min takes out and dries 10 minutes in 60 DEG C of baking ovens to get TPU conduction non-woven cloth；
（5）By step（4）Obtained TPU conduction non-woven cloth is placed in step（2）Modification CMC cation casting solution in, dipping
50 minutes, dipping temperature was 30 DEG C, takes out drying at room temperature and obtains high-performance CMC cation-exchange membrane.
Embodiment 5
The present embodiment and embodiment 2 the difference is that：Step（4）Middle bath temperature is 75 DEG C, and the ultrasonic vibration time is 30
Minute, the concentration of mixed solution is respectively 0.04 mg/mL, 0.08 mg/mL, 0.12 mg/mL and 0.16 mg/mL.
Embodiment 6
The present embodiment difference from example 1 is that：Step（5）Middle TPU conduction non-woven cloth is in CMC cation casting solution
In dip time be 40 minutes, dipping temperature be 30 DEG C.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (8)
1. a kind of preparation method of sandwich structure high-performance CMC cation-exchange membrane, it is characterised in that steps are as follows：
（1）CMC cation casting solution is obtained by the CMC of certain mass is soluble in water；
（2）The functionalized multi-wall carbonnanotubes of certain mass are added to step（1）Casting solution in, prepare carbon nano tube modified
Modified CMC casting solution；
（3）Using thermoplastic polyurethane as raw material, TPU non-woven cloth is prepared using the method for melt-spraying spinning；
（4）The conductive modification of TPU non-woven cloth：Functionalized multi-wall carbonnanotubes are added in xylene solvent, ultrasound is put into
Wave cleaning device obtains carbon nano tube dispersion liquid ultrasonic vibration 60-90 minutes in 50-75 DEG C of water-bath；By TPU non-woven cloth
It is placed in dispersion liquid, ultrasonic vibration 1-3 minutes, takes out and dries 5-10 minutes in 50-70 DEG C of baking oven to get TPU conduction
Non-woven cloth；
（5）By step（4）Obtained TPU conduction non-woven cloth is placed in step（2）In modified CMC cation casting solution obtained,
It is taken out after dipping, drying at room temperature obtains high-performance CMC cation-exchange membrane.
2. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（1）The mass fraction of middle CMC cation casting solution is 2.5%-3.5%.
3. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（2）The quality of middle functionalized multi-wall carbonnanotubes is the 0.1%-0.3% of CMC mass in casting solution.
4. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（3）The technological parameter that middle melt-spraying spinning prepares TPU non-woven cloth is：The set temperature of screw extruder is 1st area
155-165 DEG C, 2 200-210 DEG C of areas, 3 210-220 DEG C of areas, 4 220-230 DEG C of areas；The temperature of meltblown beam is 220-225 DEG C；It leads
The wind-warm syndrome and wind pressure for stretching hot wind are respectively 210-220 DEG C and 0.25-0.35 Pa；The reception distance of lace curtaining is 20-30 cm, net
The movement speed of curtain is 0.3-0.5 m/ minutes.
5. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（3）It is middle melt-blown TPU non-woven cloth with a thickness of 20-60 microns.
6. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（4）The concentration of middle carbon nano tube dispersion liquid is 0.05-0.20 mg/mL.
7. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（4）The resistivity of obtained TPU conduction non-woven cloth is less than 50 Ω m.
8. the preparation method of sandwich structure high-performance CMC cation-exchange membrane according to claim 1, feature exist
In：The step（5）Dip time of the middle TPU conduction non-woven cloth in cationic casting solution is 40-60 minutes, dipping temperature
Degree is 22-30 DEG C.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110008487A (en) * | 2009-07-20 | 2011-01-27 | 한남대학교 산학협력단 | Anion exchange membrane and process for preparing the same |
| CN102580549A (en) * | 2012-01-12 | 2012-07-18 | 福建师范大学 | Method for preparing carbon nano tube modified bipolar membrane with anion groups |
| CN105355949A (en) * | 2015-10-16 | 2016-02-24 | 同济大学 | Preparation method of nanofiber composite proton exchange membrane |
| CN107051217A (en) * | 2017-05-09 | 2017-08-18 | 河南工程学院 | Preparation method of bipolar membrane with high temperature resistance, low resistance and excellent mechanical properties |
| CN107415420A (en) * | 2017-08-02 | 2017-12-01 | 河南工程学院 | It is electromagnetically shielded the preparation method of TPU film |
| CN108097056A (en) * | 2017-12-13 | 2018-06-01 | 河南工程学院 | A kind of preparation method of cation-exchange membrane |
-
2018
- 2018-07-18 CN CN201810791524.5A patent/CN108905652A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110008487A (en) * | 2009-07-20 | 2011-01-27 | 한남대학교 산학협력단 | Anion exchange membrane and process for preparing the same |
| CN102580549A (en) * | 2012-01-12 | 2012-07-18 | 福建师范大学 | Method for preparing carbon nano tube modified bipolar membrane with anion groups |
| CN105355949A (en) * | 2015-10-16 | 2016-02-24 | 同济大学 | Preparation method of nanofiber composite proton exchange membrane |
| CN107051217A (en) * | 2017-05-09 | 2017-08-18 | 河南工程学院 | Preparation method of bipolar membrane with high temperature resistance, low resistance and excellent mechanical properties |
| CN107415420A (en) * | 2017-08-02 | 2017-12-01 | 河南工程学院 | It is electromagnetically shielded the preparation method of TPU film |
| CN108097056A (en) * | 2017-12-13 | 2018-06-01 | 河南工程学院 | A kind of preparation method of cation-exchange membrane |
Non-Patent Citations (3)
| Title |
|---|
| MAHDI TOHIDIAN,SEYED REZA GHAFFARIAN: "《Surface modified multi‐walled carbon nanotubes and Nafion nanocomposite membranes for use in fuel cell applications》", 《POLYMERS ADVANCED TECHNOLOGIES》 * |
| 闫新,宋会芬等: "《热塑性聚氨酯熔喷非织造布的制备及表征》", 《现代纺织技术》 * |
| 陈晓,陈佳辉等: "《功能化多壁碳纳米管负载铁离子改性双极膜的制备与表征》", 《高分子材料科学与工程》 * |
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