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Ppreparation method for poly(aryl ether sulfone) anion exchange membrane with homogeneous cross-linked structure

A technology of anion exchange membrane and polyarylethersulfone, which is applied in the field of preparation of cross-linked structure polyarylethersulfone anion exchange membrane, can solve the problem of limited screening ability or electrostatic exclusion, performance attenuation, low permeability selectivity, etc. problems, to achieve the effect of improving chemical stability and permeation selectivity, good monovalent anion selectivity, and efficient ion transfer rate

Pending Publication Date: 2020-02-07
ZHEJIANG UNIV OF TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the main problems of the above surface modification strategies are: (i) polyelectrolyte surface modified ordinary anionic membrane, its structure is similar to "bipolar membrane", the modified skin layer and the base membrane are mainly bound by van der Waals force, and when When the applied voltage is higher than the water dissociation voltage of the membrane itself, the shedding of the modified layer leads to a significant attenuation of performance during application and shortens the service life; The sieving ability or electrostatic exclusion effect is limited, showing low permeation selectivity (permeation selectivity <6); (iii) the improvement of surface density, the introduction of opposite charge layer or the increase of membrane thickness, increase the surface resistance

Method used

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  • Ppreparation method for poly(aryl ether sulfone) anion exchange membrane with homogeneous cross-linked structure
  • Ppreparation method for poly(aryl ether sulfone) anion exchange membrane with homogeneous cross-linked structure
  • Ppreparation method for poly(aryl ether sulfone) anion exchange membrane with homogeneous cross-linked structure

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] 1) Synthesis of amino-containing polyarylethersulfone: 4,4'-difluorodiphenylsulfone (20mmol, 5.0890g), 2,2'-di(4-hydroxyphenyl)hexafluoropropane (8mmol, 2.6898g ) and 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (12mmol, 4.3951g) were added into a 250mL three-necked round bottom flask equipped with a water separator, and NMP (75mL) was used as solvent, while adding 5.5gK 2 CO 3 and 40mL toluene as catalyst and water carrier respectively. in N 2 Under the atmosphere, the reaction was carried out at 155°C for 4 hours, and further at 165°C for 3 hours. After the polymer solution dropped to room temperature, it was poured into 300 mL of isopropanol, stirred at high speed, and flocculated to obtain a precipitate. After separation by suction filtration, a brown solid was obtained, which was repeatedly washed with isopropanol and water, and dried under vacuum at 80° C. for 20 hours. The reaction yielded 8.3 g of amino-containing polyarylethersulfone with a molecular...

Embodiment 2

[0051] 1) Synthesis of amino-containing polyarylether sulfone: the same preparation process as in Example 1 was adopted to obtain amino-containing polyarylether sulfone.

[0052] 2) Synthesis of side chains containing imidazole: In a 500mL three-necked round-bottomed flask, 1.0mmol of 1,9-dibromononane was added to 300mL of acetonitrile, heated to 40°C, and then 6.0mmol of 1- Methylimidazole, reacted for 24 hours, the resulting liquid or solid was washed several times with ether, and then vacuum-dried at 40°C for 24 hours to obtain pure 1-bromo-9-methylimidazolium salt-alkane;

[0053] In a 500mL three-neck round-bottomed flask, add 1.0mmol of 1,9-dibromononane to 300mL of acetonitrile, heat to 40°C, then add 6.0mmol of 1-vinylimidazole dropwise, and react for 24 hours to obtain The solid was washed several times with ether or ethyl acetate, and then dried under vacuum at 40°C for 24 hours to obtain pure 1-bromo-9-vinylimidazolium salt-alkane.

[0054] 3) Preparation of side ...

Embodiment 3

[0058] 1) Synthesis of amino-containing polyarylether sulfone: the same preparation process as in Example 1 was adopted to obtain amino-containing polyarylether sulfone.

[0059] 2) Synthesis of side chains containing imidazole: In a 500mL three-necked round-bottomed flask, 1.0mmol of 1,12-dibromododecane was added to 300mL of acetonitrile, heated to 40°C, and then 6.0mmol of 1 -Methylimidazole, reacted for 24 hours, the resulting liquid or solid was washed several times with ether, and then vacuum-dried at 40°C for 24 hours to obtain pure 1-bromo-12-methylimidazolium salt-alkane;

[0060] In a 500mL three-neck round bottom flask, add 1.0mmol of 1,12-dibromododecane to 300mL of acetonitrile, heat to 40°C, then add 6.0mmol of 1-vinylimidazole dropwise, and react for 24 hours. The resulting solid was washed several times with ether or ethyl acetate, and then dried under vacuum at 40°C for 24 hours to obtain pure 1-bromo-12-vinylimidazolium salt-alkane.

[0061] 3) Preparation o...

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Abstract

The invention discloses a preparation method for a poly(aryl ether sulfone) anion exchange membrane with a homogeneous cross-linked structure. The method includes the following steps: step 1, performing a reaction on 1-vinylimidazole and dibromoalkane CH2Br(CH2)nCH2Br to obtain a 1-bromo-(n+2)-vinylimidazole salt-alkane chain represented by a formula (III) shown in the specification; step 2, dissolving amino-contained poly(aryl ether sulfone) represented by a formula (I) shown in the specification into a solvent, adding a 1-bromo-(n+2)-methylimidazole salt-alkane chain represented by a formula(II) shown in the specification, the 1-bromo-(n+2)-vinylimidazole salt-alkane chain represented by the formula (III) and a polymerization inhibitor, and performing a reaction at 20-90 DEG C for 8-24h to obtain imidazole-functionalized poly(aryl ether sulfone); and step 3, dissolving the imidazole-functionalized poly(aryl ether sulfone) into an organic solvent, adding azobisisobutyronitrile to obtain a casting solution, performing defoaming on the casting solution, performing drying at 40-150 DEG C to form the membrane, so as to obtain the poly(aryl ether sulfone) anion exchange membrane withthe homogeneous cross-linked structure. The anion exchange membrane prepared by the method has the characteristics of a low membrane resistance, good structural stability, and high monovalent anion permeability selectivity.

Description

[0001] (1) Technical field [0002] The invention relates to the field of polymer materials, in particular to a method for preparing a cross-linked polyarylethersulfone anion exchange membrane, and belongs to the membrane technology field. [0003] (2) Background technology [0004] At present, anion exchange membranes are widely used in diffusion dialysis, electrodialysis, alkaline fuel cells, recovery of useful metals in sewage, etc. Separation of ions with the same charge but different valence states in the mixed salt system is an important practical application of electrodialysis technology. For the specific mixed salt system to be separated, the choice of monovalent selective ion membrane is very important. However, at present, most of the domestic commercial ionic membrane products are heterogeneous membranes, which are mainly used in primary water treatment and other separation fields that require relatively low ion purity. For monovalent selective anion membranes, dom...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J41/13
CPCB01J41/13
Inventor 廖俊斌沈江南高兴俞欣妍陈权
Owner ZHEJIANG UNIV OF TECH
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