CN110760079A - Preparation method of alkyl side chain type polyarylether sulphone anion exchange membrane with homogeneous cross-linked structure - Google Patents
Preparation method of alkyl side chain type polyarylether sulphone anion exchange membrane with homogeneous cross-linked structure Download PDFInfo
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Abstract
A preparation method of an alkyl side chain type polyarylether sulphone anion exchange membrane with a homogeneous cross-linked structure comprises the following steps: step 1: reacting 3-bromopropylamine-methylimidazolium bromate (I) with x-chlorine-1-alkanol (II) to generate x-dihydroxy-alkyl chain side chain imidazolium salt (III); step 2: the compound (III) reacts to prepare the side chain imidazole of the x-dichloro-alkyl chainAzolium salt (IV); and step 3: dissolving polyarylethersulfone (V) containing amino groups, x-dichloro-alkyl chain side chain imidazolium salt (IV) and 1-bromo-3-methyl imidazolium salt-alkyl chain (VI) in an organic solvent, and standing and defoaming to obtain a casting solution; and 4, step 4: and (3) coating the casting solution obtained in the step (3) on a clean glass plate, and carrying out in-situ reaction and vacuum drying to obtain the alkyl side chain type polyarylether sulfone anion exchange membrane with the homogeneous cross-linked structure. The anion exchange membrane prepared by the invention has the characteristics of low swelling rate, good structural stability and high single-multivalence permeability selectivity.
Description
(I) technical field
The invention relates to the field of polymer high molecular materials, in particular to a preparation method of an alkyl side chain type polyarylether sulphone anion exchange membrane with a homogeneous cross-linked structure.
(II) background of the invention
The process for preparing the salt by concentrating the seawater by utilizing the common electrodialysis technology has the problems that: monovalent anion Cl–(or monovalent cation Na+) While migrating to the concentrating compartment, polyvalent anions, e.g. SO4 2–、CO3 2–Etc. (or polyvalent metal cations, e.g. Ca)2+、Mg2+Etc.) also to the concentrating compartment. When concentrating CaSO in the chamber4、CaCO3When the concentration of the sodium chloride is higher than the solubility product of the sodium chloride, precipitates are formed and deposited on the surface of a membrane, the membrane surface resistance is increased, the current efficiency of the electrodialyzer is reduced, the energy consumption is remarkably increased, even the membrane burning phenomenon is caused, and the salt manufacturing cost is remarkably increased. If the ionic membrane in the common electrodialysis membrane stack is partially replaced or additionally added with a monovalent selective ionic membrane to construct selective electrodialysis, the monovalent selective ionic membrane is utilizedBlocking polyvalent anion SO4 2–、CO3 2–Etc. to allow monovalent ion Cl–By the characteristics, the reverse osmosis concentrated seawater is effectively concentrated to prepare high-purity salt, and the problem of scale formation of insoluble salt on the surface of a membrane is solved. The choice of monovalent selective ionic membranes is crucial for the particular mixed salt system to be separated. However, at present, most of domestic commercial ionic membrane products are heterogeneous membranes, and are mainly used in separation fields such as primary water treatment and the like with relatively low requirements on ion purity. For monovalent selective anionic membranes, researchers at home and abroad adopt various strategies to carry out relevant research according to the separation mechanism of pore size screening effect, electrostatic repulsion effect or ionic hydration energy difference. The main strategies are to utilize electrostatic deposition modification and chemical bond grafting modification to perform crosslinking on the surface of a commercial ionic membrane to form a compact layer, introduce a charge layer and the like. For example: in Cl–/SO4 2–In the separation process, polyethyleneimine is deposited on the surface of the quaternary ammonium polyphenyl ether anionic membrane through electrodeposition, and Cl is caused by the increase of the compactness of the membrane surface layer–/SO4 2–The relative selectivity of (A) was increased from 0.79 to 4.27(J.Membr.Sci.2017,539, 263-272). A dense charge-carrying layer, such as a "sandwich" structure or the like, is introduced on the membrane surface to function as a pore size sieving or electrostatic exclusion (j.membr. sci.2018,556, 98-106). The electro-deposition method is used for preparing the selective anion membrane with the simulated cell membrane structure, and the surface resistance of the membrane is only 1.92 omega cm2But Cl–/SO4 2–The relative selectivity of (d) is 2.20(sci. rep.2016,6, 1-13); the PSS and the HACC electrolyte layer are connected through covalent bonds by utilizing a small-molecule photocrosslinking agent to ensure the stability of a modified layer and optimize Cl of a selective anionic membrane–The selectivity was 4.36 (4.46. omega. cm)2) (J.Membr.Sci.2017,543, 310-318). The main problems that exist are: the falling off of the modified layer leads to the shortening of the service life; thin modified layers exhibit lower permselectivity; the increase of the surface density and the introduction of the opposite charge layer increase the surface resistance of the film.
Disclosure of the invention
The invention aims to provide a preparation method of a homogeneous cross-linked alkyl side chain type polyarylether sulphone anion exchange membrane with low swelling ratio, good structural stability and high single-multivalence permeability selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an alkyl side chain type polyarylether sulphone anion exchange membrane with a homogeneous cross-linked structure comprises the following steps:
step 1: reacting 3-bromopropylamine-methylimidazolium bromate shown in formula (I) with x-chlorine-1-alkanol shown in formula (II) in an organic solvent to generate x-dihydroxy-alkyl chain side chain imidazolium salt shown in formula (III), wherein x is the carbon chain length of the x-chlorine-1-alkanol, and x is 2,3,4 or 5;
step 2: using anhydrous AlCl as x-dihydroxy-alkyl chain side chain imidazole salt shown in formula (III) in an organic solvent3As a catalyst, and introducing anhydrous HCl gas for reaction to prepare an x-dichloro-alkyl chain side chain imidazole salt shown in a formula (IV);
and step 3: dissolving polyarylethersulfone containing amino groups shown in a formula (V), x-dichloro-alkyl chain side chain imidazolium salt shown in a formula (IV) and 1-bromo-3-methyl imidazolium salt-alkyl chain shown in a formula (VI) in an organic solvent according to a molar ratio of 4:0.5-1.5:1-3, standing and defoaming to obtain a casting solution, wherein the mass volume concentration of the polyarylethersulfone containing amino groups in the casting solution is 3-8% (preferably 5%); the organic solvent is one or more of DMF, DMAc and NMP; the polyarylether sulfone containing amino groups is a random copolymer, the molecular weight is 30000-60000, y and 100-y in the formula (V) respectively represent the mol percent of corresponding chain links as y percent and (100-y)%, and y is 25-95;
and 4, step 4: and (3) coating the casting solution obtained in the step (3) on a clean glass plate, reacting in situ for 6-12 hours at 40-90 ℃, and then drying in vacuum at 40-150 ℃ to obtain the alkyl side chain type polyarylether sulphone anion exchange membrane with the homogeneous cross-linked structure.
The components of the homogeneous cross-linked alkyl side chain type polyarylether sulphone anion exchange membrane prepared by the invention are cross-linked alkyl side chain type polyarylether sulphone, and because the cross-linking sites are uncertain, a plurality of possible cross-linking structures exist, wherein one possible cross-linking structure is as follows:
the invention forms high-efficiency ion transfer rate and excellent selective ion transmission channel by regulating and controlling the length of the hydrophobic chain segment, the hydrophilic chain segment and the alkyl in the cross-linked side chain; meanwhile, a proper amount of flexible side alkyl chain terminal imidazole, a cross-linked homogeneous membrane structure formed by chemical bonds between a conductive side chain and a rigid main chain ensure low surface resistance and structural stability of the membrane.
Preferably, the thickness of the alkyl side chain type polyarylether sulphone anion exchange membrane with the homogeneous cross-linked structure is controlled to be 50-200 mu m.
Preferably, in step 1, the organic solvent is acetonitrile, and 3-bromopropylamine-methylimidazolium bromate is reacted with x-chloro-1-alkanol in acetonitrile at 30-60 ℃ for 5-24 hours to form x-dihydroxy-alkyl chain side imidazole salt.
Preferably, in step 1, the feeding molar ratio of the 3-bromopropylamine-methylimidazolium bromate to the x-chloro-1-alkanol is 1 (1-10).
Preferably, in step 2, the organic solvent is CH2Cl2The reaction temperature is 20-60 ℃, and the reaction time is 5-10 hours.
Preferably, in step 2, the x-dihydroxy-alkyl chain side chain imidazolium salt is reacted with anhydrous AlCl3The mass ratio of (1): 0.01-0.1.
preferably, in step 4, the reaction is carried out in situ at 80 ℃ for 12 hours.
In the present invention, the amino group-containing polyarylethersulfones of the formula (V) may be prepared by methods disclosed in the literature, such as Journal Membrane Science 574(2019) 181-195; journal Membrane Science 577(2019) 153- "164).
The invention specifically recommends that the amino group-containing polyarylethersulfone is prepared by the following method: adding monomers of 4,4 '-difluorodiphenyl sulfone, 2, 2' -bis (4-hydroxyphenyl) hexafluoropropane and 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane into a high boiling point aprotic solvent, wherein the mole percentage of the 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane is 25 to 95 percent based on 100 percent of the total mole number of the 2,2 '-bis (4-hydroxyphenyl) hexafluoropropane and the 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane fed; copolycondensating for 3-10 hours at the temperature of 100-180 ℃ in nitrogen atmosphere, and carrying out post-treatment on the reaction mixture to obtain the amino group-containing polyarylether sulfone.
Preferably, the ratio of the amount of the substance of 4,4 ' -difluorodiphenyl sulfone to the total amount of the substance of 2,2 ' -bis (4-hydroxyphenyl) hexafluoropropane and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane is 1: 1.
Preferably, potassium carbonate is added to the polymerization system as a catalyst and toluene is added as a water-carrying agent. It is further preferred that potassium carbonate be used in an amount of 2 to 5 times, most preferably 2 times the molar amount of the monomeric 4, 4' -difluorodiphenyl sulfone. It is further preferable that the volume ratio of toluene to the high-boiling aprotic solvent is from 0.2 to 0.7: 1.
Preferably, the high boiling point aprotic solvent used is one or more of Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP).
The copolycondensation reaction in the steps is carried out for 3-10 h at the temperature of 100-180 ℃, and nitrogen is introduced for protection in the whole process to avoid oxidation. Preferably, the copolycondensation reaction conditions are as follows: in N2The reaction was carried out at 155 ℃ for 4 hours under an atmosphere and at 165 ℃ for 3 hours. The reaction is carried out at low temperature of 150 ℃ firstly to avoid gelation, and the temperature is raised laterIt should be advantageous to increase the molecular weight of the polymer.
Preferably, the post-treatment method comprises the following steps: and (3) cooling the polymer solution to room temperature, pouring the polymer solution into an isopropanol or methanol aqueous solution, stirring at a high speed, flocculating to obtain a precipitate, performing suction filtration and separation to obtain a brown solid, repeatedly washing the brown solid with the isopropanol or methanol aqueous solution for multiple times, and performing vacuum drying at 40-80 ℃ for 12-24 hours.
In the present invention, 1-bromo-3-methylimidazolium salt-alkane chain and 3-bromopropylamine-methylimidazolium bromate are known compounds and can be prepared according to the methods disclosed in the prior literatures.
Compared with the prior art, the invention has the advantages that:
(1) the ion exchange membrane prepared by the invention contains crosslinking groups, and a crosslinking network structure can be formed in the membrane material through crosslinking, so that the chemical stability, the swelling ratio and the permeability selectivity of the ion exchange membrane are further improved.
(2) The micro-phase structure and the density of the polymer are regulated and controlled by regulating the lengths of the hydrophobic chain segment, the hydrophilic chain segment and the alkyl link in the cross-linked side chain, so that a high-efficiency ion transfer rate and an excellent selective ion transmission channel are formed, and monovalent anions (such as Cl) are realized by utilizing the poor hydration energy of ions–Etc.) selectivity.
(3) The proper amount of flexible side alkyl chain terminal imidazole, a cross-linked homogeneous membrane structure formed by chemical bonds between a conductive side chain and a rigid main chain ensure low surface resistance and structural stability of the membrane.
(IV) description of the drawings
FIG. 1 preparation of amino-containing Polyarylethersulfones (PAES) from example 11H NMR spectrum;
FIG. 2 preparation of imidazole salt having terminal dihydroxy-alkyl chain side1H NMR spectrum;
FIG. 3 preparation of imidazole salt having terminal dichloro-alkyl chain side1H NMR spectrum;
FIG. 4 FTIR spectrum of alkyl side chain type polyarylethersulfone with cross-linked structure prepared in example 1;
FIG. 5 thermal weight loss (TGA) spectrum of alkyl side chain type polyarylethersulfone having a cross-linked structure prepared in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Example 1
1) Synthesis of amino-containing polyarylether sulfone: 4,4 ' -Difluorodiphenylsulfone (20mmol, 5.0890g), 2 ' -bis (4-hydroxyphenyl) hexafluoropropane (15mmol, 2.6898g) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (5mmol, 4.3951g) were charged to a 250mL three-necked round bottom flask equipped with a water trap, and NMP (75mL) was used as a solvent while adding 5.5g K2CO3And 40mL of toluene as catalyst and water carrier, respectively. In N2The reaction was carried out at 155 ℃ for 4 hours under an atmosphere and at 165 ℃ for 3 hours. When the polymer solution is cooled to room temperature, the polymer solution is poured into 300mL of isopropanol and flocculated under high-speed stirring to obtain a precipitate. Filtering and separating to obtain brown solid, repeatedly washing with isopropanol and water, and vacuum drying at 80 deg.C for 20 hr. 7.3g of an amino-containing polyarylethersulfone having a 25% molar fraction of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and a number average molecular weight of 42,100 were obtained.
2) And (3) synthesizing an imidazolidinyl side chain:
in a 250mL three-neck round-bottom flask, firstly, 4.3784g (20mmol) of 1, 3-dibromopropane is dissolved in 100mL of acetone, then 1.6412g (20mmol) of 1-methylimidazole is dropwise added to react at 40 ℃, the mixture is stirred for 48 hours, then the acetone is evaporated in a rotary manner to be dried, the obtained solid is alternately washed by ether and ethyl acetate, and the purified 1-bromo-3-methylimidazolium salt-alkyl chain is obtained after drying;
in a 250mL three-neck round-bottom flask, firstly, 4.3784g (20mmol) of 3-bromopropylamine hydrobromide is dissolved in 100mL of acetone, then 1.6412g (20mmol) of 1-methylimidazole is dropwise added to react at 40 ℃, the mixture is stirred for 48 hours, then the acetone is evaporated in a rotary manner to be dried, the obtained solid is alternately washed by diethyl ether and ethyl acetate, and the purified 3-bromopropylamine-methylimidazole bromate is obtained after drying;
3.0102g (10mmol) of 3-bromopropylamine-methylimidazolium bromate was weighed and dissolved in 100mL of acetonitrile, 50mmol of 2-chloro-1-ethanol was added, reaction was carried out at 40 ℃ with stirring for 24 hours, acetonitrile was evaporated to dryness, and the obtained solid was washed with diethyl ether several times to prepare 4.2g of 2-dihydroxy-alkyl chain side-chain imidazolium salt.
3.0g of 2-dihydroxy-alkyl chain side chain imidazolium salt was dissolved in 30mL CH2Cl2In, 0.1g of anhydrous AlCl is used3And continuously introducing sufficient anhydrous HCl gas as a catalyst, reacting at 50 ℃ for 12 hours, alternately washing with diethyl ether and ethyl acetate, and drying in vacuum at 40 ℃ to obtain the purified end-position dichloro-alkyl chain side chain imidazole salt.
3) Preparation of the anion crosslinked membrane with the crosslinked structure: dissolving dichloro-alkyl chain side chain imidazolium salt (0.67mmol), 1-bromo-3-methyl imidazolium salt-alkyl chain (1.35mmol) and amino-containing polyarylether sulfone (3.0 g) (5.38mmol) in 60mL of NMP, and magnetically stirring at 80 ℃ until the materials are completely dissolved to obtain a casting solution; and (2) defoaming the casting solution, then coating the defoamed casting solution on a clean glass plate, reacting at 80 ℃ for 12 hours, drying, and then vacuum-drying at 110 ℃ for 10 hours to obtain the imidazole functionalized polyarylethersulfone anion exchange membrane PAES-25-cIM with a homogeneous cross-linked structure, wherein the membrane thickness is 106 microns.
The experiment proves that the prepared alkyl side chain type imidazole functionalized polyether sulphone anion membrane with the cross-linked structure has the ion exchange capacity of 1.72mmol g–1The swelling ratio was 7.2%, the transference number was 0.97, and the tensile strength was 26.3 MPa. Monovalent anion Cl–(Cl–/SO4 2–) The selectivity is 6.5 (the specific test method refers to J.Membr.Sci.574(2019) 181-195; J.Membr.Sci.577(2019) 153-.
Example 2
1) Synthesis of amino-containing polyarylether sulfone: 4,4 ' -Difluorodiphenylsulfone (20mmol, 5.0890g), 2 ' -bis (4-hydroxyphenyl) hexafluoropropane (13mmol, 4.3710g) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (7mmol, 2.9292g) were charged into a 250mL three-necked round bottom flask equipped with a water separator, and NMP (75mL) was used as a solvent while adding 5.5g K2CO3And 40mL of toluene as catalyst and water carrier, respectively. In N2The reaction was carried out at 155 ℃ for 4 hours under an atmosphere and at 165 ℃ for 3 hours. When the polymer solution is cooled to room temperature, the polymer solution is cooled to room temperatureIt is poured into 300mL of isopropanol and flocculated with high speed stirring to give a precipitate. Filtering and separating to obtain brown solid, repeatedly washing with isopropanol and water, and vacuum drying at 80 deg.C for 20 hr. The amino-containing polyarylether sulphone with the mole ratio fraction of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 35% is obtained, and the number average molecular weight is 40,600.
2) And (3) synthesizing an imidazolidinyl side chain: the same procedures as in example 1 were carried out to obtain 1-bromo-3-methylimidazolium salt-alkyl chain, 3-bromopropylamine-methylimidazolium bromate and terminal dichloro-alkyl chain side-chain imidazolium salt.
3) Preparation of anion membrane with crosslinking structure: dissolving dichloro-alkyl chain side chain imidazolium salt (0.94mmol), 1-bromo-3-methyl imidazolium salt-alkyl chain (1.87mmol) and amino-containing polyarylether sulfone (3.0 g) (5.35mmol) in 60mL of NMP, and magnetically stirring at 80 ℃ until the materials are completely dissolved to obtain a casting solution; and (2) defoaming the casting solution, then coating the defoamed casting solution on a clean glass plate, reacting at 80 ℃ for 12 hours, drying, and then vacuum-drying at 110 ℃ for more than 10 hours to form a membrane, thereby obtaining the imidazole functionalized polyarylethersulfone anion exchange membrane PAES-35-cIM with a homogeneous cross-linked structure, wherein the membrane thickness is 112 microns.
The experiment shows that the ion exchange capacity of the prepared alkyl side chain type imidazole functionalized polyether sulphone anion membrane with the cross-linked structure is 1.85mmol g–1The swelling ratio was 8.1%, the transference number was 0.95, and the tensile strength was 28.7 MPa. Monovalent anion Cl–(Cl–/SO4 2–) 8.0 (test method reference J.Membr.Sci.574(2019) 181-); J.Membr.Sci.577(2019) 153-.
Example 3
1) Synthesis of amino-containing polyarylether sulfone: 4,4 ' -Difluorodiphenylsulfone (20mmol, 5.0890g), 2 ' -bis (4-hydroxyphenyl) hexafluoropropane (11mmol, 3.6985g) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (9mmol, 3.7661g) were charged to a 250mL three-necked round bottom flask equipped with a water trap, and NMP (75mL) was used as a solvent while adding 5.5g K2CO3And 40mL of toluene as catalyst and water carrier, respectively. In N2Reacting at 155 ℃ for 4 hours under an atmosphere, and reacting at 165 ℃ againFor 3 hours. When the polymer solution is cooled to room temperature, the polymer solution is poured into 300mL of isopropanol and flocculated under high-speed stirring to obtain a precipitate. Filtering and separating to obtain brown solid, repeatedly washing with isopropanol and water, and vacuum drying at 80 deg.C for 20 hr. To obtain amino-containing polyarylethersulfone with a mole ratio fraction of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 45%, and a number average molecular weight of 39,700.
2) And (3) synthesizing an imidazolidinyl side chain: the same procedures as in example 1 were carried out to obtain 1-bromo-3-methylimidazolium salt-alkyl chain, 3-bromopropylamine-methylimidazolium bromate and terminal dichloro-alkyl chain side-chain imidazolium salt.
3) Preparation of anion membrane with crosslinking structure: dissolving terminal dichloro-alkyl chain side chain imidazolium salt (1.15mmol), 1-bromo-3-methyl imidazolium salt-alkyl chain (2.39mmol) and amino-containing polyarylether sulfone (3.0 g) (5.32mmol) in 60mL of NMP, and magnetically stirring at 80 ℃ until the materials are completely dissolved to obtain a casting solution; and (2) defoaming the casting solution, coating the defoamed casting solution on a clean glass plate, reacting at 80 ℃ for 12 hours, drying, and then vacuum-drying at 110 ℃ for 10 hours to obtain the imidazole functionalized polyarylethersulfone anion exchange membrane PAES-45-cIM with a homogeneous cross-linked structure, wherein the membrane thickness is 115 mu m.
The experiment shows that the ion exchange capacity of the prepared alkyl side chain type imidazole functionalized polyether sulphone anion membrane with the cross-linked structure is 1.91mmol g–1The swelling ratio was 8.4%, the transference number was 0.93, and the tensile strength was 32.1 MPa. Monovalent anion Cl–(Cl–/SO4 2–) 8.5 (test method reference J.Membr.Sci.574(2019) 181-); J.Membr.Sci.577(2019) 153-.
Example 4
1) Synthesis of amino-containing polyarylether sulfone: 4,4 ' -Difluorodiphenylsulfone (20mmol, 5.0890g), 2 ' -bis (4-hydroxyphenyl) hexafluoropropane (9mmol, 3.0261g) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (11mmol, 4.6030g) were charged to a 250mL three-necked round bottom flask equipped with a water trap, and NMP (75mL) was used as a solvent while adding 5.5g K2CO3And 40mL of toluene as catalyst and water carrier, respectively. In N2Under an atmosphere of 1The reaction was carried out at 55 ℃ for 4 hours and at 165 ℃ for 3 hours. When the polymer solution is cooled to room temperature, the polymer solution is poured into 300mL of isopropanol and flocculated under high-speed stirring to obtain a precipitate. Filtering and separating to obtain brown solid, repeatedly washing with isopropanol and water, and vacuum drying at 80 deg.C for 20 hr. -obtaining an amino-containing polyarylethersulfone having a molar fraction of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 55%, and having a number average molecular weight of 39,400.
2) And (3) synthesizing an imidazolidinyl side chain: the same procedures as in example 1 were carried out to obtain 1-bromo-3-methylimidazolium salt-alkyl chain, 3-bromopropylamine-methylimidazolium bromate and terminal dichloro-alkyl chain side-chain imidazolium salt.
3) Preparation of anion membrane with crosslinking structure: dissolving dichloro-alkyl chain side chain imidazolium salt (1.45mmol), 1-bromo-3-methyl imidazolium salt-alkyl chain (2.91mmol) and amino-containing polyarylethersulfone (3.0 g) (5.29mmol) in 60mL of NMP, and magnetically stirring at 80 ℃ until the materials are completely dissolved to obtain a casting solution; and (2) defoaming the casting solution, then coating the defoamed casting solution on a clean glass plate, reacting at 80 ℃ for 12 hours, drying, and then vacuum-drying at 110 ℃ for 10 hours to obtain the imidazole functionalized polyarylethersulfone anion exchange membrane PAES-55-cIM with a homogeneous cross-linked structure, wherein the membrane thickness is 112 microns.
The experiment shows that the prepared alkyl side chain type imidazole functionalized polyether sulphone anion membrane with the cross-linked structure has IEC of 1.99mmol g–1The swelling ratio was 7.8%, the transference number was 0.95, and the tensile strength was 34.3 MPa. Monovalent anion Cl–(Cl–/SO4 2–) 9.0 (test method reference J.Membr.Sci.574(2019) 181-); J.Membr.Sci.577(2019) 153-.
Example 5
1) Synthesis of amino-containing polyarylether sulfone: 4,4 ' -Difluorodiphenylsulfone (20mmol, 5.0890g), 2 ' -bis (4-hydroxyphenyl) hexafluoropropane (7mmol, 2.3536g) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (13mmol, 5.4399g) were charged into a 250mL three-necked round bottom flask equipped with a water separator, and NMP (75mL) was used as a solvent while adding 5.5g K2CO3And 40mL of toluene as catalyst and water carrier, respectively. In N2The reaction was carried out at 155 ℃ for 4 hours under an atmosphere and at 165 ℃ for 3 hours. When the polymer solution is cooled to room temperature, the polymer solution is poured into 300mL of isopropanol and flocculated under high-speed stirring to obtain a precipitate. Filtering and separating to obtain brown solid, repeatedly washing with isopropanol and water, and vacuum drying at 80 deg.C for 20 hr. The amino-containing polyarylethersulfone with the mole ratio fraction of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 65 percent is obtained, and the number average molecular weight is 39,100.
2) And (3) synthesizing an imidazolidinyl side chain: the same procedures as in example 1 were carried out to obtain 1-bromo-3-methylimidazolium salt-alkyl chain, 3-bromopropylamine-methylimidazolium bromate and terminal dichloro-alkyl chain side-chain imidazolium salt.
3) Preparation of anion membrane with crosslinking structure: dissolving dichloro-alkyl chain side chain imidazolium salt (1.71mmol), 1-bromo-3-methyl imidazolium salt-alkyl chain (3.42mmol) and amino-containing polyarylethersulfone (3.0 g, 5.26mmol) in 60mL of NMP, and magnetically stirring at 80 ℃ until the materials are completely dissolved to obtain a casting solution; and (2) defoaming the casting solution, then coating the defoamed casting solution on a clean glass plate, reacting at 80 ℃ for 12 hours, drying, and then vacuum-drying at 110 ℃ for 10 hours to obtain the imidazole functionalized polyarylethersulfone anion exchange membrane PAES-65-cIM with a homogeneous cross-linked structure, wherein the membrane thickness is 108 micrometers.
The experiment proves that the prepared alkyl side chain type imidazole functionalized polyether sulphone anion membrane with the cross-linked structure has the ion exchange capacity of 2.04mmol g–1The swelling ratio was 8.0%, the transference number was 0.95, and the tensile strength was 28.7 MPa. Monovalent anion Cl–(Cl–/SO4 2–) 8.0 (the test method is referred to Journal Membrane Science 574(2019) 181-); journal Membrane Science 577(2019) 153- "164).
Claims (8)
1. A preparation method of an alkyl side chain type polyarylether sulphone anion exchange membrane with a homogeneous cross-linked structure comprises the following steps:
step 1: reacting 3-bromopropylamine-methylimidazolium bromate shown in formula (I) with x-chlorine-1-alkanol shown in formula (II) in an organic solvent to generate x-dihydroxy-alkyl chain side chain imidazolium salt shown in formula (III), wherein x is the carbon chain length of the x-chlorine-1-alkanol, and x is 2,3,4 or 5;
step 2: using anhydrous AlCl as x-dihydroxy-alkyl chain side chain imidazole salt shown in formula (III) in an organic solvent3The catalyst is added, and anhydrous HCl gas is introduced for reaction, so that x-dichloro-alkyl chain side chain imidazole salt shown in formula (IV) is prepared, wherein x is 2,3,4 or 5;
and step 3: dissolving polyarylethersulfone containing amino groups shown in a formula (V), x-dichloro-alkyl chain side chain imidazole salt shown in a formula (IV) and 1-bromo-3-methyl imidazole salt-alkyl chain shown in a formula (VI) in an organic solvent according to a molar ratio of 4:0.5-1.5:1-3, standing and defoaming to obtain a casting solution, wherein the mass volume concentration of the polyarylethersulfone containing amino groups in the casting solution is 3-8%; the organic solvent is one or more of DMF, DMAc and NMP; the polyarylether sulfone containing amino groups is a random copolymer, the molecular weight is 30000-60000, y and 100-y in the formula (V) respectively represent the mol percent of corresponding chain links as y percent and (100-y)%, and y is 25-95;
and 4, step 4: and (3) coating the casting solution obtained in the step (3) on a clean glass plate, reacting in situ for 6-12 hours at 40-90 ℃, and then drying in vacuum at 40-150 ℃ to obtain the alkyl side chain type polyarylether sulphone anion exchange membrane with the homogeneous cross-linked structure.
2. The method of claim 1, wherein: the thickness of the alkyl side chain type polyarylether sulphone anion exchange membrane with the homogeneous cross-linked structure is controlled to be 50-200 mu m.
3. The method of claim 1, wherein: in the step 1, the organic solvent is acetonitrile, and 3-bromopropylamine-methylimidazolium bromate and x-chlorine-1-alkanol react for 5-24 hours in acetonitrile at the temperature of 30-60 ℃ to generate x-dihydroxy-alkyl chain side chain imidazolium salt.
4. The production method according to claim 1 or 3, characterized in that: in the step 1, the feeding molar ratio of the 3-bromopropylamine-methylimidazolium bromate to the x-chloro-1-alkanol is 1 (1-10).
5. The method of claim 1, wherein: in step 2, the organic solvent is CH2Cl2The reaction temperature is 20-60 ℃, and the reaction time is 5-10 hours.
6. The production method according to claim 1 or 5, characterized in that: in step 2, x-dihydroxy-alkyl chain side chain imidazolium salt and anhydrous AlCl3The mass ratio of (1): 0.01-0.1.
7. the method of claim 1, wherein: in the step 3, the mass volume concentration of the polyarylether sulphone containing amino groups in the membrane casting solution is 5%.
8. The method of claim 1, wherein: in step 4, the reaction is carried out in situ at 80 ℃ for 12 hours.
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