CN108786482A - A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique - Google Patents
A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique Download PDFInfo
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- CN108786482A CN108786482A CN201810570687.0A CN201810570687A CN108786482A CN 108786482 A CN108786482 A CN 108786482A CN 201810570687 A CN201810570687 A CN 201810570687A CN 108786482 A CN108786482 A CN 108786482A
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- photocuring
- exchange membrane
- printing technique
- anion
- quaternary anion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The present invention relates to a kind of quaternary anion-exchange membranes based on photocuring 3D printing technique.The present invention is by by a certain proportion of 4- vinyl benzyl chlorides, bisphenol-a epoxy acrylate, isooctyl methacrylate and phenyl bis- (2; 4; 6- trimethylbenzoyls) phosphine oxide is mixed with photosensitive resin; then it is printed as smooth film through photocuring 3D printer, then reacts the quaternary anion-exchange membrane (QPAEK) for preparing different ions exchange capacity with trimethylamine.The preparation method has the characteristics that shaping speed is fast, precision is high and easy to operate；The anion-exchange membrane of gained has the characteristics that ionic conductivity is high, water absorption rate is low, good mechanical property, thermal stability is good, solvent resistance is good.
Description
Technical field
The present invention relates to a kind of quaternary anion-exchange membranes based on photocuring 3D printing technique, belong to anion
Exchange membrane field.
Background technology
Membrane separation technique based on amberplex has the significant advantages such as low energy consumption, low stain, high efficiency, exists
The numerous areas such as environmental protection, functional protein separation, the development and utilization of new energy obtain more and more extensive research and utilization.
However, anion-exchange membrane is mainly prepared by solution casting method at present, that there are toxicity is big, the production cycle is long, easy crosslinking etc. one
Number of disadvantages hinders the commercialization process of anion-exchange membrane.
Photocuring 3D printing technique is under the ultraviolet light in specific wavelength and path, and photoinitiator is because occurring photodissociation
Reaction generates living radical, and oligomer/monomer to cause liquid crosslinks polymerization by program and obtains 3 D stereo
The forming technique of product.It has many advantages, such as that energy-efficient, formed precision is high and speed is fast.It is prepared with photocuring 3D printing technique
Amberplex the shortcomings that being expected to overcome solution casting method, promotes the large-scale production of amberplex.
Ionic conductivity and ion selectivity are two core capabilities of amberplex, the chemical group with amberplex
At there is close contact between structure.The rational composition for preparing photosensitive resin makes gained amberplex have lower
Water absorption rate（<50 wt%）, the performances such as higher ionic conductivity and selectivity, higher mechanical strength, be to utilize photocuring 3D
Printing technique prepares the important prerequisite of anion-exchange membrane.
Invention content
The present invention in order to overcome the deficiencies of the prior art, it is cloudy to provide a kind of quaternary based on photocuring 3D printing technique
Amberplex, preparation method is simple, and shaping speed is fast, and products therefrom water absorption rate is low, ionic conductivity is high, mechanical performance and
Thermal stability is good, solvent resistance is good, has broad application prospects in anion-exchange membrane field.
To achieve the above object, the present invention is realised by adopting the following technical scheme：
Quaternary anion-exchange membrane based on photocuring 3D printing technique, by a certain proportion of 4- vinyl benzyl chlorides, bisphenol-A
Type epoxy acrylate and isooctyl methacrylate are raw material, in the presence of photoinitiator, through photocuring 3D printer
Then printing-filming steeps and reacts 2 days and obtain in trimethylamine aqueous solution.
Wherein, the throwing of 4- vinyl benzyl chlorides, bisphenol-a epoxy acrylate, isooctyl methacrylate, photoinitiator
Expect that mass ratio is 10 ~ 30：50~30：35：5；Photoinitiator is bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl；Light
The lamp source wavelength for curing 3D printer is 402nm, and base's hardening time is 15 ~ 30s, and it is 6 ~ 20 layers that base, which prints the number of plies,；Front three
The mass fraction of trimethylamine is 10 ~ 40% in amine aqueous solution, in trimethylamine and impregnated film the molar ratio of 4- vinyl benzyl chlorides for 5 ~
100：1.
Quaternary anion-exchange membrane of the gained based on photocuring 3D printing technique of the invention compared with prior art, this
Invention has the advantages that：
（1）It is with short production cycle, it is at low cost.Conventional solution casting method prepare anion-exchange membrane time be generally it is tens small
When, and photocuring 3D printing technique is utilized, a few minutes can produce required film product.
（2）It is high to produce precision.It is difficult to accurately control film forming thickness that conventional solution casting method, which prepares anion-exchange membrane, and light
The precision of solidification 3D printer can reach 0.01mm, can effectively control the thickness requirement of film.
（3）The water absorption rate of products therefrom is low, ionic conductivity is high, good mechanical property, thermal stability are good, solvent resistance is good.
（4）The ion exchange capacity of products therefrom can be the ability to easily control by the inventory of 4- vinyl benzyl chlorides.
Description of the drawings
Fig. 1 is the scanning electricity of the quaternary anion-exchange membrane based on photocuring 3D printing technique in the embodiment of the present invention
Mirror figure.
Fig. 2 is the infrared light of the quaternary anion-exchange membrane based on photocuring 3D printing technique in the embodiment of the present invention
Spectrogram.
Fig. 3 is that the thermogravimetric of the quaternary anion-exchange membrane based on photocuring 3D printing technique in the embodiment of the present invention is bent
Line chart.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further.
Embodiment 1：The allotment of photosensitive resin
4- vinyl benzyl chlorides, bisphenol-a epoxy acrylate, isooctyl methacrylate and phenyl are weighed in ratio shown in table 1
Bis- (2,4,6- trimethylbenzoyl) phosphine oxides, are stirred 15 minutes in beaker, be ultrasonically treated 1 minute, PAEK- is made
10, tri- kinds of photosensitive resins of PAEK-20 and PAEK-30.
The allotment of 1 photosensitive resin of table
Embodiment 2：The photocuring 3D printing of film
A series of prepared photosensitive resins are printed respectively with MOONRAY high-precision photocuring 3D printers.Photocuring
The lamp source wavelength of 3D printer is 402nm, and adjusting base's hardening time is 30s, and it is 8 layers that base, which prints the number of plies, and grouping is printed
The film of the mm × 0.2 of 50 mm × 10 mm.
Embodiment 3：The preparation of quaternary anion-exchange membrane based on photocuring 3D printing technique
Film in embodiment 2 ethyl alcohol and deionized water are respectively washed 3 times, the trimethylamine for being then immersed in 20wt% is water-soluble
It is reacted two days in liquid, then takes out film, the vacuum drying 24 hours under the conditions of 80 DEG C.PAEK-10, PAEK-20 and PAEK-30
QPAEK-10, QPAEK-20 and QPAEK-30 are reacted into respectively.Through characterization, QPAEK-10, QPAEK-20 and QPAEK-30 are insoluble
In any solvent, correlated performance data is as shown in table 2.
The performance data of quaternary anion-exchange membrane of the table 2 based on photocuring 3D printing technique
Claims (5)
1. a kind of quaternary anion-exchange membrane based on photocuring 3D printing technique, which is characterized in that by a certain proportion of
4- vinyl benzyl chlorides, bisphenol-a epoxy acrylate and isooctyl methacrylate are raw material, in the presence of photoinitiator
Under, through photocuring 3D printer printing-filming, then steeps and react 2 days and obtain in trimethylamine aqueous solution.
2. the quaternary anion-exchange membrane according to claim 1 based on photocuring 3D printing technique, feature exist
It is in the mass ratio that feeds intake of, 4- vinyl benzyl chlorides, bisphenol-a epoxy acrylate, isooctyl methacrylate, photoinitiator
10~30：50~30：35：5.
3. the quaternary anion-exchange membrane according to claim 1 based on photocuring 3D printing technique, feature exist
In photoinitiator is bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl.
4. the quaternary anion-exchange membrane according to claim 1 based on photocuring 3D printing technique, feature exist
In the lamp source wavelength of photocuring 3D printer is 402nm, and base's hardening time is 15 ~ 30s, and it is 6 ~ 20 layers that base, which prints the number of plies,.
5. the quaternary anion-exchange membrane according to claim 1 based on photocuring 3D printing technique, feature exist
In the mass fraction of trimethylamine is 10 ~ 40% in trimethylamine aqueous solution, and trimethylamine rubs with 4- vinyl benzyl chlorides in impregnated film
You are than being 5 ~ 100：1.
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| CN201810570687.0A CN108786482A (en) | 2018-06-05 | 2018-06-05 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
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| CN201810570687.0A CN108786482A (en) | 2018-06-05 | 2018-06-05 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113021877A (en) * | 2021-03-16 | 2021-06-25 | 杭州电子科技大学 | Preparation method of 3D printing patterned ion exchange membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113021877A (en) * | 2021-03-16 | 2021-06-25 | 杭州电子科技大学 | Preparation method of 3D printing patterned ion exchange membrane |
| CN113021877B (en) * | 2021-03-16 | 2022-09-02 | 杭州电子科技大学 | Preparation method of 3D printing patterned ion exchange membrane |
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Application publication date: 20181113 |
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