Side chain type random polyether sulphone and preparation method thereof and homogeneous anion exchange membrane

Abstract

The invention discloses side chain type random polyether sulphone and a preparation method thereof and a homogeneous anion exchange membrane. The side chain type random polyether sulphone is composedof the following four repetitive structure units, and the four repetitive structure units are arranged randomly. The number-average molecular weight Mn of the side chain type random polyether sulphoneranges from 40000 to 100000; a repetitive structural unit A:a repetitive structural unit B:a repetitive structural unit C:a repetitive structural unit D is as shown in the description, wherein n is equal to 3-12, the numbers of the four repetitive structure units A, B, C and D in the structure of the side chain type random polyether sulphone are respectively represented by a, b, c and d, and thefollowing conditions are met: (a+b):(c+d)=(90-0%):(10-100%), and (a+c):(b+d)=(10-90%):(90-10%). The invention provides a homogeneous anion exchange membrane prepared from the side chain type random polyether sulphone. The homogeneous anion exchange membrane has the characteristics of excellent ionic conductivity, good chemical stability, high monovalent anion selectivity, high monovalent anion flux and the like.

Description

technical field

[0001] The invention relates to the field of composite materials, in particular to a side chain type random polyarylether sulfone, a preparation method thereof and a homogeneous anion exchange membrane prepared from the side chain type random polyarylether sulfone. Background technique

[0002] At present, the separation of ions with the same charge but different valence 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. The development of new commercially available high-selectivity ionic membranes can not only reduce the dependence on foreign products, but also meet the actual ne...

Examples

Embodiment 1

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

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

Embodiment 1-2

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

[0075] It can be known through experiments using the national standard method that the IEC of the prepared side chain type random polyarylethersulfone anion membrane is 1.82mmol g –1 , the migration number is 0.97, the tensile strength is 32.9MPa, Cl – The maximum permeate flux of 7.5×10 –8 mol cm –2 the s –1 , Cl – selectivity (Cl – / SO 4 2– ) is 7.1 (for specific test methods, please refer to literature reports: Journal of Membrane Science 574 (...

Embodiment 2

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

[0078] Preparation of series modified 4,4'-difluorodiphenyl sulfone (m-DFPS): using the same preparation process as in Example 1 to obtain bis(4-fluoro-3-(4-(1-hexene)) phenyl) sulfone.

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

[0080] 1-bromo-6-imidazolium salt hexane chain (Br-(CH 2 ) 6 -IM) Synthesis: Using the same preparation process as in Example 1, pure 1-bromo-6-methylimidazolium salt-alkane was obtained.

[0081] Preparation of side chain random polyaryl ether sulfone: the same preparation process as in Example 1 was adopted, the only difference being the addition of 1,3-bis(4-hydroxyphenyl)alkane (8mmol) and 2,2'-bis( 3-amino-4-hydroxyphenyl)hexafluoropropane (12mmol), to obtain 2,2'-bis(3-am...

technical field

[0001] The invention relates to the field of composite materials, in particular to a side chain type random polyarylether sulfone, a preparation method thereof and a homogeneous anion exchange membrane prepared from the side chain type random polyarylether sulfone. Background technique

[0002] At present, the separation of ions with the same charge but different valence 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. The development of new commercially available high-selectivity ionic membranes can not only reduce the dependence on foreign products, but also meet the actual ne...

Examples

Embodiment 1

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

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

Embodiment 1-2

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

[0075] It can be known through experiments using the national standard method that the IEC of the prepared side chain type random polyarylethersulfone anion membrane is 1.82mmol g –1 , the migration number is 0.97, the tensile strength is 32.9MPa, Cl – The maximum permeate flux of 7.5×10 –8 mol cm –2 the s –1 , Cl – selectivity (Cl – / SO 4 2– ) is 7.1 (for specific test methods, please refer to literature reports: Journal of Membrane Science 574 (...

Embodiment 2

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

[0078] Preparation of series modified 4,4'-difluorodiphenyl sulfone (m-DFPS): using the same preparation process as in Example 1 to obtain bis(4-fluoro-3-(4-(1-hexene)) phenyl) sulfone.

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

[0080] 1-bromo-6-imidazolium salt hexane chain (Br-(CH 2 ) 6 -IM) Synthesis: Using the same preparation process as in Example 1, pure 1-bromo-6-methylimidazolium salt-alkane was obtained.

[0081] Preparation of side chain random polyaryl ether sulfone: the same preparation process as in Example 1 was adopted, the only difference being the addition of 1,3-bis(4-hydroxyphenyl)alkane (8mmol) and 2,2'-bis( 3-amino-4-hydroxyphenyl)hexafluoropropane (12mmol), to obtain 2,2'-bis(3-am...

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