A kind of side chain random polyaryl ether sulfone and its preparation method and homogeneous anion exchange membrane

An anion exchange membrane and polyaryl ether sulfone technology, which is applied in the field of homogeneous anion exchange membranes, can solve the problems of reduced anion selectivity and flux, unstable modified layer, low selectivity coefficient, etc., so as to maintain long-term stability performance. , good chemical stability and mechanical properties, low cost effect

Active Publication Date: 2022-07-22
ZHEJIANG UNIV OF TECH
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Problems solved by technology

However, there are usually problems in the preparation of monovalent anion-selective ion membranes using the above surface modification strategies: (i) the modified layer is unstable; (ii) the selectivity coefficient is low. (iii) High membrane surface resistance (ACS Sustainable Chem.Eng.7(2019)44429–4442; J.Membr.Sci.599(2020)No.117818)
For example, an anion exchange membrane prepared by using a polyelectrolyte whose hydrophilic conductive groups are directly connected to the hydrophobic main chain, the adjacent hydrophilic groups inhibit the self-aggregation between the hydrophobic main chains to a certain extent, resulting in higher water absorption. (swelling rate) and impermeable ion channels, which significantly reduce anion selectivity and flux (J.Membr.Sci.553(2018)43–53; ACS Sustainable Chem.Eng.7(2019)44429–4442)

Method used

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  • A kind of side chain random polyaryl ether sulfone and its preparation method and homogeneous anion exchange membrane
  • A kind of side chain random polyaryl ether sulfone and its preparation method and homogeneous anion exchange membrane
  • A kind of side chain random polyaryl ether sulfone and its preparation method and homogeneous anion exchange membrane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] Preparation of 3,3'-dibromo-4,4'-difluorodiphenylsulfone (db-DFPS): Weigh 25.4 g of 4,4'-difluorodiphenylsulfone (0.10 mol) into a 250 mL round bottom flask , and then 150 mL of concentrated sulfuric acid was added, and the mixture was stirred and dissolved at 25 °C in a nitrogen atmosphere. Then, 14.2 g (0.22 mol) of N-bromosuccinimide (NBS) was added in 3 batches at 15 min intervals, and the mixture was rapidly stirred for 6 h. The resulting mixture was poured into ice water (500 mL). The precipitate was obtained by filtration, then washed with 600 mL of deionized water and 100 mL of n-hexane, respectively. Finally, it was purified by crystallization from toluene. Vacuum drying at 60° C. for 12 h yielded 18.3 g of db-DFPS.

[0067] Preparation of modified 4,4'-difluorodiphenylsulfone (m-DFPS): Weigh 8.0 g (19.4 mmol) of 3,3'dibromo-4,4'difluorodiphenylsulfone, 3.5 g (41.2 mmol) 1-hexene, 0.262 g (1.07 mmol) of palladium acetate, 0.2120 g (0.582 mmol) of sodium dip...

Embodiment 1-2

[0074] Preparation of side-chain random polyaryl ether sulfone anion exchange membrane: 2.8 g of the side-chain random polyaryl ether sulfone prepared in Example 1 was dissolved in 60 mL of NMP solvent, and magnetically stirred at 80°C until completely dissolved to obtain Film casting solution: Degas the casting solution, then pour the defoamed casting solution into a clean glass mold, and dry it at 80°C to form a membrane to obtain a homogeneous side chain random polyarylethersulfone anion exchange film with a film thickness of 106 μm.

[0075] Using the national standard method, the experimental results show that the IEC of the prepared side-chain random polyarylethersulfone anion membrane is 1.82 mmol g –1 , the migration number is 0.97, the tensile strength is 32.9MPa, the Cl – The maximum permeation flux of 7.5 × 10 –8 mol cm –2 s –1 , Cl – selectivity (Cl – / SO 4 2– ) is 7.1 (for specific test methods, see literature reports: Journal of Membrane Science 574 (2019...

Embodiment 2

[0077] Preparation of 3,3'-dibromo-4,4'-difluorodiphenylsulfone (db-DFPS): The same preparation process as in Example 1 was adopted to obtain db-DFPS.

[0078] Preparation of serially modified 4,4'-difluorodiphenylsulfone (m-DFPS): The same preparation process as in Example 1 was adopted to obtain bis(4-fluoro-3-(4-(1-hexene)) phenyl) sulfone.

[0079] Synthesis of 1,n-bis(4-hydroxyphenyl)alkane (1,n-DBA): using the same preparation process as in Example 1, a pure 1,3-bis(4-hydroxyphenyl) chain was obtained alkyl.

[0080] 1-Bromo-6-imidazolium salt hexane chain (Br-(CH 2 ) 6 Synthesis of -IM): The same preparation process as in Example 1 was adopted to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.

[0081] Preparation of side-chain random polyaryl ether sulfone: the same preparation process as in Example 1 was adopted, except that 1,3-bis(4-hydroxyphenyl)alkane (8mmol) and 2,2'-bis( 3-Amino-4-hydroxyphenyl)hexafluoropropane (12 mmol) to give a side chain ran...

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Abstract

The invention discloses a side chain random polyaryl ether sulfone, a preparation method and a homogeneous anion exchange membrane. The side-chain random polyarylether sulfone is composed of the following four repeating structural units, and the four repeating structural units are randomly arranged; the number-average molecular weight of the side-chain random polyarylethersulfone Mn= 40000~100000; repeating structural unit A: repeating structural unit B: repeating structural unit C: repeating structural unit D: wherein, n=3-12, and there are four repeats in the structure of the side-chain random polyarylethersulfone The numbers of structural units A, B, C, and D are represented by a, b, c, and d, respectively, and satisfy the following conditions: (a+b): (c+d)=90-0%: 10-100%, (a +c): (b+d)=10-90%: 90-10%. The present invention provides a homogeneous anion exchange membrane prepared from the side-chain random polyarylethersulfone, which has excellent ionic conductivity, good chemical stability, high monovalent anion selectivity, high monovalent anion flux, etc.

Description

technical field [0001] The invention relates to the field of composite materials, in particular to a side chain random polyaryl ether sulfone, a preparation method thereof, and a homogeneous anion exchange membrane prepared from the side chain random polyaryl ether sulfone. Background technique [0002] At present, the separation of ions with the same charge but different valence states in mixed salt systems 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, the vast majority of commercial ion membrane products in China are heterogeneous membranes, which are mainly used in separation fields such as primary water treatment that require relatively low ion purity. The development of new commercialized high-selectivity ion membranes can not only reduce the dependence on foreign products, but also meet the actual needs of the domestic ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G75/23B01J41/13
CPCC08G75/23B01J41/13
Inventor 廖俊斌俞欣妍沈江南
Owner ZHEJIANG UNIV OF TECH
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