CN110903449B - Isatin arene copolymer, preparation method and application - Google Patents
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Abstract
The invention belongs to the field of high molecular materials and polymer ion exchange membranes thereof, and relates to an isatin arene copolymer, a preparation method and application thereof. The invention synthesizes isatin-arene copolymer with ammonium cation by using substituted isatin, methyl piperidone and arene through super acid catalyzed hydroxyalkylation polycondensation, and electrolyte solution and tough polymer anion exchange membrane are conveniently prepared. The intrinsic viscosity of the ammonium isatin aromatic hydrocarbon copolymer prepared according to the invention is 1.5-4.0 dL/g (DMAc,25 ℃), and the polymer can be crosslinked or functionalized by introducing an isatin structural unit, so that the chemical stability and the mechanical property are further improved. The copolymer electrolyte solution and the ion exchange membrane have high ion conductivity, excellent alkali resistance/oxidation resistance and mechanical properties, and wide application in fuel cells, energy storage cells, electrolysis and other electrochemical devices or membrane separation related fields.
Description
Technical Field
The invention belongs to the field of high molecular materials and polymer ion exchange membranes thereof, and relates to an isatin arene copolymer, a preparation method and application thereof.
Background
The polymer ion exchange membrane fuel cell is used as a clean hydrogen energy technology, has the advantages of room temperature starting, high energy efficiency, zero pollution and the like, and is widely applied to the fields of transportation, aerospace, ships and military science and technology. At present, a Proton Exchange Membrane Fuel Cell (PEMFC) needs a noble metal platinum catalyst during operation, and an expensive perfluoropolymer ionic membrane such as Nafion ionic membrane of dupont in the united states is used, so that the PEMFC has a high cost, and the popularization and application of the PEMFC are limited. An alkaline Anion Exchange Membrane Fuel Cell (AEMFC) can use non-noble metal catalysts such as nickel, cobalt, silver and the like when operating under an alkaline condition, avoids using noble metal platinum catalysts with limited resources, and has high-efficiency oxygen reduction kinetics, so the AEMFC has the advantages of low technical cost and high cell performance, and has great attention in recent years.
At present, one of the bottleneck problems existing in the AEMFC is poor mechanical performance and chemical stability of the polymer ion membrane in an alkaline environment, and poor performance of the fuel cell caused by poor performance of the electrolyte solution in the membrane electrode, so that the development of the alkaline ion membrane material and the polymer electrolyte solution which can meet the practical application is urgently needed. Olsson et al, stable for 15 days at 60 deg.C in 2M NaOH and have a hydroxide conductivity of 89mS cm at 80 deg.C -1 [Olsson J S et al,Advanced Functional Materials,2018,28(2):1702758]. Peng et al synthesized poly-N-methyl piperidine aromatic hydrocarbon copolymer, the peak power density in hydrogen-oxygen fuel cell is as high as 1.5W cm -2 The stable operation of the battery reaches 100H [ Peng H, et al. journal of Power Sources,2018,390:165-]。
Disclosure of Invention
Aiming at the key problem that the polymer ion membrane in the existing alkaline fuel cell has poor mechanical property and chemical stability, the invention provides an isatin arene copolymer with good mechanical property and high alkali resistance stability, an electrolyte solution thereof, an ion exchange membrane thereof, a preparation method and application thereof. The isatin structural unit is introduced into the copolymer, so that the polymer can be conveniently crosslinked and functionalized, the mechanical properties and the chemical stability of a polymer ionic membrane and an electrolyte solution (Ionomer) are further improved, and the polymer ionic membrane and the electrolyte solution are widely applied to the fields of fuel cells, energy storage cells, hydrogen production by electrolyzing water, membrane separation, other electrochemical devices and the like.
The invention is realized by adopting the following technical scheme:
an isatin arene copolymer, which has a structure shown in a general formula I:
wherein n is more than 0 and less than 1;
r is H or C 1 ～C 12 Alkyl, dibromoalkane, alkene, benzylstyrene, epoxy, acrylate or- (CH) 2 ) n’ -G, wherein G is an alkylated ammonium ion of trimethylamine, N-methylpiperidine, N-methylpyrrole or N-methylmorpholine; n' is 1 to 10.
Ar is aromatic hydrocarbon and has the following structure:
wherein R is 1 Is methyl or C 1 ～C 12 Alkyl group of (1).
A preparation method of isatin arene copolymer comprises the following specific steps:
step one, synthesis of substituted isatin
Dissolving isatin in solvent A to obtain 1-20 wt% solution, adding excessive anhydrous K 2 CO 3 Stirring to dissolve, adding the compound B, and controlling the molar ratio of the isatin to the compound B to be 1: 1-1: 3, reacting for 10-50h at 20-60 ℃; and after the reaction is finished, pouring the reaction solution into ice water, extracting by using an extracting agent, carrying out rotary evaporation, and recrystallizing the crude product by using ethanol to obtain the substituted isatin.
The solvent A is one or a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, chloroform, dimethyl sulfoxide and N-methylpyrrolidone.
The compound B is alkyl bromide, olefin bromide, vinyl benzyl chloride, glycidyl acrylate (GMA), alkyl ammonium bromide Br- (CH) 2 ) n’ -G or 1, 6-dibromoalkane.
The extractant is one or more of methanol, toluene, acetone, petroleum ether, diethyl ether and chloroform.
Step two, synthesis of isatin arene copolymer
Adding the substituted isatin, the N-methyl-4-piperidone and the aromatic hydrocarbon obtained in the step one into dichloromethane, and stirring and dissolving in ice bath to enable the monomer concentration of the substituted isatin to be 15-40 wt% to obtain a mixed solution; adding trifluoromethanesulfonic acid and trifluoroacetic acid into the mixed solution as catalysts, and stirring and reacting at 0-5 ℃ for 14-48 h; after the reaction is finished, the product is poured into ice water and filtered, and NaHCO is used as the product 3 Removing excessive acid, washing with water, filtering, and vacuum drying to obtain white fibrous isatin arene copolymer; dissolving the copolymer in a solvent A, then pouring the solution into a precipitator, filtering and drying the solution to obtain the refined fibrous isatin arene copolymer.
The ratio of the total mole number of the substituted isatin and the N-methyl-4-piperidone to the mole number of the aromatic hydrocarbon is (1-1.1): 1; the molar ratio of the substituted isatin to the N-methyl-4-piperidone is 1: 9-4: 6; the molar ratio of the trifluoromethanesulfonic acid to the aromatic hydrocarbon is (6-14): 1; the volume ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid is (8-14): 1.
the aromatic hydrocarbon is biphenyl, p-terphenyl, m-terphenyl, 9-dialkyl fluorene or bisphenol fluorene.
The precipitant is one or more of methanol, ethanol, water, petroleum ether, ethyl acetate, acetone, and diethyl ether.
A method for preparing an anion exchange membrane by using an isatin arene copolymer comprises the following steps:
step (1), synthesis of isatin arene copolymer with ammonium cation
Dissolving isatin arene copolymer in solvent A to obtain 5-20 wt% solution, adding methyl iodide or bromoalkane R 1 -Br, wherein methyl iodide or R 1 The molar ratio of-Br to isatin arene copolymer is (5-15): 1, reacting for 20-100 h at 30-100 ℃; after the reaction is finished, pouring the reaction liquid into a precipitator, filtering, and washing the product with water to obtain the isatin arene copolymer with ammonium cations, wherein the structure of the isatin arene copolymer is shown as a general formula II:
wherein n is more than 0 and less than 1; x - Is a counterion of Br - Or OH - Ions; r is 1 Is methyl or C 1 ～C 12 The alkyl group of (1).
The solvent A is one or a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, chloroform, dimethyl sulfoxide and N-methylpyrrolidone.
The precipitant is one or more of methanol, ethanol, water, petroleum ether, ethyl acetate, acetone, and diethyl ether.
Step (2), preparation of electrolyte solution (Ionomer) of isatin arene copolymer with ammonium cations
And (2) adding the isatin arene copolymer with the ammonium cations prepared in the step (1) into a solvent A, stirring for dissolving, and defoaming to obtain a transparent and uniform electrolyte solution (Ionomer), wherein the concentration of the solution is determined according to actual needs.
Step (3), preparation of isatin arene copolymer anion exchange membrane
Spreading a membrane on the electrolyte solution with the concentration of 3-15 wt% obtained in the step (2), immersing the membrane into a 1M NaOH or KOH solution at the temperature of room temperature to 80 ℃ for ion exchange for 2-24 h, soaking the membrane in room temperature deionized water for 24-48 h, washing the membrane to be neutral, and drying the membrane to obtain an isatin arene copolymer anion exchange membrane; when R in the structural general formula of the isatin arene copolymer is olefin, styrene benzyl, epoxy group or acrylate, adding a thermal initiator or a photoinitiator during film preparation to obtain a cross-linked isatin arene copolymer anionic film; and when R is dibromoalkane, adding diamine or triamine to carry out chemical crosslinking during membrane preparation to obtain the cross-linked isatin arene copolymer anionic membrane.
The bromoalkane R 1 -Br, wherein, R 1 Is methyl or C 1 ～C 12 Alkyl group of (1).
The isatin arene copolymer electrolyte solution (Ionomer) is used as a resin binder in a fuel cell and is used for preparing a membrane electrode.
The isatin arene copolymer anion exchange membrane is applied to the fields of fuel cells, flow batteries, electrolysis, electrodialysis or separation membranes.
The synthetic routes of the isatin arene copolymer, the electrolyte solution and the ion exchange membrane are as follows:
a method for preparing a composite membrane by using isatin arene copolymer comprises the following specific steps:
step (1), synthesis of isatin arene copolymer with ammonium cation
Dissolving isatin arene copolymer in solvent A to obtain 5-20 wt% solution, adding methyl iodide or bromoalkane R 1 -Br, wherein methyl iodide or R 1 The molar ratio of-Br to the isatin arene copolymer is (5-15): 1, reacting for 20-100 h at 30-100 ℃; after the reaction is finished, pouring the reaction liquid into a precipitator, filtering, and washing the product with water to obtain the isatin arene copolymer with ammonium cations, wherein the structure of the isatin arene copolymer is shown as a general formula (II):
wherein n is more than 0 and less than 1; x - Is a counterion of Br - Or OH - Ions; r 1 Is methyl or C 1 ～C 12 The alkyl group of (1).
The solvent A is one or a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, chloroform, dimethyl sulfoxide and N-methylpyrrolidone.
The precipitant is one or more of methanol, ethanol, water, petroleum ether, ethyl acetate, acetone, and diethyl ether.
Step (2), preparation of isatin arene copolymer solution with ammonium cation
And (2) adding the isatin arene copolymer with the ammonium cations prepared in the step (1) into a solvent A, stirring and dissolving to prepare a 1-10 wt% solution, and defoaming to obtain a transparent and uniform isatin arene copolymer solution with the ammonium cations.
Step (3), preparation of composite film
Soaking the base membrane in ethanol at room temperature for 3-24 h, taking out and spreading the base membrane, uniformly dropwise adding a small amount of solvent A on the surface to soak the base membrane, casting the isatin aromatic hydrocarbon copolymer solution with ammonium cations prepared in the step (2) on the base membrane for self-leveling, and drying the base membrane in a drying oven to constant weight; then, immersing the obtained base membrane into 1M NaOH at the room temperature of 80 ℃ for 2-24 h of ion exchange, placing the base membrane into deionized water at the room temperature for 24-48 h, taking out the base membrane, and drying the base membrane in vacuum to constant weight to obtain the isatin arene copolymer composite membrane.
The basement membrane is a polytetrafluoroethylene or polyethylene microporous membrane, and the porosity is more than 90%.
The prepared isatin arene copolymer composite membrane is applied to fuel cells, flow batteries, electrolysis, electrodialysis or separation membranes.
Compared with the prior art, the invention has the beneficial effects that:
the intrinsic viscosity of the isatin arene copolymer with the ammonium cation prepared by the invention is 1.5-4.0 dL/g in N, N-dimethylacetamide at 25 ℃. The electrolyte solution of isatin arene copolymer prepared according to the present invention and its anion exchange membrane have high ionic conductivity, e.g. OH at 80 ℃ - The ionic conductivity can reach 100mS/cm, both a wet membrane and a dry membrane have very strong toughness and excellent mechanical properties, the ionic conductivity is reduced less when the membrane is soaked in a 1M NaOH solution for 30-40 days at 80 ℃, the alkaline-resisting stability is excellent, and the membrane can be widely applied to the related fields of fuel cells, flow batteries, electrolysis and electrodialysis plasma membranes.
Drawings
FIG. 1 is a schematic representation of the allylisatin of example 1 1 H-NMR spectrum.
FIG. 2 is a drawing showing the spiro ammonium isatin-piperidone-biphenyl copolymer of example 1 1 H-NMR spectrum.
FIG. 3 is a drawing showing the preparation of the copolymer of hexylmethyl-piperidinium salt isatin-methylpiperidinone-biphenyl in example 8 1 H-NMR spectrum.
FIG. 4 is a drawing of the allylisatin-methylpiperidinone-terphenyl copolymer of example 6 1 H-NMR spectrum.
Detailed Description
The isatin aromatic hydrocarbon copolymer, the preparation method and the application thereof of the present invention are further illustrated in detail by the following examples, but are not intended to limit the scope of the present invention.
Examples relate to test methods:
the IEC test method comprises the following steps: about 0.2g of isatin arene copolymer is taken and soaked in 100mL of 1mol/L NaCl solution for 24 hours respectively. And soaking the mixture for 24 hours by using deionized water, drying the mixture by using a vacuum oven, and weighing and recording the mixture. Then soaked in 25mL of 0.5M NaNO 3 Adding potassium chromate solution indicator into the solution for 24h, and adding 0.1M AgNO 3 Titrating the solution, recording consumed AgNO when brick red precipitate appears and does not change color within 30 seconds to represent that the titration is finished 3 Volume of solution. Mixing AgNO 3 And dividing the product of the concentration and the volume of the solution by the mass of the dried membrane to obtain IEC.
Alkali resistance stability: soaking the membrane in 1M NaOH solution at 80 deg.C, taking out the membrane at certain time interval, washing with deionized water to neutrality, and testing room temperature conductivity.
Example 1
10mol of isatin is dissolved in dimethyl sulfoxide, and 15mol of anhydrous K is added 2 CO 3 Dissolved at room temperature with stirring. 12mol of bromopropylene is added to react for 24 hours at 60 ℃. Pouring the reaction solution into ice water, extracting with diethyl ether, removing the diethyl ether by rotary evaporation, and recrystallizing the product with ethanol to obtain the allyl isatin.
Adding allyl isatin and 4-piperidone hydrochloride into a reactor, adding biphenyl, adding dichloromethane, stirring at 0 ℃, and dissolving to ensure that the monomer concentration is 20 wt%. Then trifluoromethanesulfonic acid and trifluoroacetic acid were added, the reaction was stirred at 0 ℃ for 20h, and when the system became viscous the polymerization product was poured into a large amount of ice water, with 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the allyl isatin-piperidone-biphenyl copolymer. Wherein the molar ratio of the allyl isatin to the piperidone monomer is 1: 4, the ratio of the total number of moles of allylisatin and 4-piperidone hydrochloride to the number of moles of biphenyl is 1: 1, the molar ratio of trifluoromethanesulfonic acid to biphenyl is 8: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 8.
wherein, the piperidine structure N-H of the allyl isatin-piperidone-biphenyl copolymer and slightly excessive 1, 5-dibromopentane generate a ring reaction under the action of a catalyst to generate a spiro-aminated copolymer. The specific reaction is as follows:
1.3mol of the copolymer is dissolved in N, N-dimethylformamide to prepare a 5 wt% solution, 1.5mol of 1, 5-dibromopentane DMAc solution is added dropwise, 1.5mol of N, N-diisopropylethylamine is added as a catalyst, and the reaction is carried out at 60 ℃ for 36 h. After the reaction is finished, pouring acetone into the mixture for precipitation, filtering, washing by using acetone, washing by using water, and drying in vacuum to obtain the spiro-aminated allyl isatin-piperidone-biphenyl copolymer.
And dissolving the spiro-aminated copolymer in N-methyl pyrrolidone to prepare a membrane casting solution. Pouring on a clean glass plate, and drying. And soaking the membrane in 1M NaOH at 80 ℃ for ion exchange for 2h, soaking in deionized water for 24h, and washing with water to obtain the copolymer anion exchange membrane.
Dissolving the spiro-ammonium copolymer in N-methylpyrrolidone to prepare 10 wt% of membrane casting solution. A small amount of 2,2- (1, 2-ethanediylbis-oxo) bisethanethiol is added as a crosslinker and a photoinitiator is added. And pouring the casting solution on a clean glass plate, and irradiating by using a 365nm ultraviolet lamp for crosslinking. And drying in an oven to obtain the cross-linked spiro-ammonium copolymer anionic membrane.
The structural formula of the spiro-aminated copolymer is as follows:
FIG. 1 is of allylisatin 1 H-NMR spectrum. Chemical shifts are at 7.53 and 7.6, 7.09 and 7.01ppm of the protons on the benzene ring of isatin, at 5.8, 5.32 and 5.15ppm of the protons on the double bond of alkene isatin and at 4.27ppm of the protons on the methylene group attached to the N atom of isatin. The above analysis indicated successful synthesis of allylisatin.
FIG. 2 is a drawing of an allylisatin-piperidone-biphenyl copolymer and a spirocyclic aminated polyallylnisatin-piperidone-biphenyl anionic membrane 1 H-NMR spectrum. As can be seen from FIG. 2, the peaks at chemical shifts of 7.09 to 7.6ppm are the proton peaks on the benzene ring, the characteristic peaks at 8.9ppm are the peaks of N-H on piperidine, the characteristic peaks at 5.9, 5.16 and 1.9ppm are the peaks of double bond hydrogen bonded to the isatin atom, and the peaks at 3.06, 2.69 and 2.18ppm are the peaks of piperidineProton peak of methylene on the ring. After the N atom on the piperidone forms a ring, the N-H peak disappears, and chemical shift peaks at 1.76 and 1.56ppm appear, which are characteristic peaks of protons on the N spiro ring. This indicates that the above-described copolymer and spiro-aminated copolymer anionic membranes have been successfully synthesized. The prepared anion membrane is transparent and light yellow and has better flexibility.
Through experimental tests: the ion exchange capacity IEC was 1.03mmol/g, the hydroxide ion conductivity at 80 ℃ was 53mS/cm, the water absorption at 80 ℃ was 45%, and the degree of swelling was 5.5%. The ionic conductivity retention was 90% by soaking at 80 ℃ for 570h in 1M NaOH solution.
Example 2
Synthesis of allyl isatin: the procedure is as in example 1, 10mol of isatin are dissolved in dimethyl sulphoxide and 15mol of anhydrous K are added 2 CO 3 The mixture was dissolved by stirring at room temperature. 10mol of bromopropylene is added and reacted for 50h at 20 ℃. And pouring the reaction solution into ice water, extracting with diethyl ether, removing the diethyl ether by rotary evaporation, and recrystallizing the product with ethanol to obtain the allyl isatin.
Adding allyl isatin and N-methyl-4-piperidone into a reactor, and adding biphenyl. Methylene chloride was added and dissolved at 0 ℃ with stirring to give a monomer concentration of 20% by weight. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 0 deg.C for 14h, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the allyl isatin-methyl piperidone-biphenyl copolymer. Wherein the mol ratio of the allyl isatin to the N-methyl-4-piperidone is 2: 3, the ratio of the total moles of allylisatin and N-methyl-4-piperidone to the moles of biphenyl is 1: 1, the molar ratio of trifluoromethanesulfonic acid to biphenyl is 6: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 14.
2mol of the copolymer is dissolved in N, N-dimethylacetamide to prepare 15 wt% solution, and 30mol of methyl iodide is added to react at 40 ℃ for 24 h. And pouring the polymer solution into acetone to separate out, filtering, washing with water, and drying in an oven to obtain the aminated copolymer. The aminated copolymer was added to dimethylacetamide and dissolved by stirring to obtain a clear electrolyte solution (Ionomer). Pouring the mixture on a clean glass plate, and drying the mixture in an oven at 60 ℃ to obtain the anion exchange membrane of the aminated copolymer. The film thickness is adjusted by the solution concentration, and the concentration of the casting solution is generally 5 to 15 wt%.
Or dissolving the aminated copolymer in dimethylacetamide to prepare 8 wt% of casting solution. Pouring the mixture on a clean glass plate, adding a photoinitiator, and placing the mixture under a 365nm ultraviolet lamp for irradiating for 30min to obtain the anion exchange membrane of the crosslinking type ammonium copolymer.
The formula of the aminated copolymer is as follows:
the hydroxyl ion conductivity is 100mS/cm at 80 ℃, the alkali resistance is 1800 hours in 1M NaOH at 80 ℃, and the conductivity is reduced by 15 percent.
Example 3
Synthesis of hexyl isatin: the procedure is as in example 1, with bromohexane instead of bromopropene, 10mol of isatin being dissolved in dimethyl sulfoxide, 20mol of anhydrous K being added 2 CO 3 The mixture was dissolved by stirring at room temperature. 30mol of bromohexane was added and reacted at 50 ℃ for 10 hours. Pouring the reaction solution into ice water, extracting with diethyl ether, removing the diethyl ether by rotary evaporation, and recrystallizing the product with ethanol to obtain hexyl isatin.
Adding hexyl isatin and N-methyl-4-piperidone into a reactor, and adding p-terphenyl. Methylene chloride was added thereto and dissolved with stirring at 0 ℃ to give a monomer concentration of 30% by weight. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 5 deg.C for 48h, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the hexyl isatin-methyl piperidone-terphenyl copolymer. Wherein the molar ratio of the hexyl isatin to the N-methyl-4-piperidone is 1: 4, the ratio of the total number of moles of hexyl isatin and N-methyl-4-piperidone to the number of moles of p-terphenyl is 1: 1, the molar ratio of trifluoromethanesulfonic acid to p-terphenyl is 12: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 8.
10mol of the copolymer is dissolved in N, N-dimethylformamide to prepare a 10 wt% solution, and 50mol of methyl iodide is added to react for 100 hours at 30 ℃. And pouring the polymer solution into ethanol for precipitation, filtering, washing with water, and drying in an oven to obtain the aminated copolymer.
The method of example 2 was used to prepare the electrolyte solution of the aminated copolymer and anion exchange membrane by soaking the membrane in 1M NaOH for 24h at room temperature, soaking in deionized water for 48h and washing with water.
The formula of the aminated copolymer is as follows:
the conductivity of hydroxide ions is 85mS/cm at 80 ℃, the alkali resistance is 1700h in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
Example 4
Adding isatin and N-methyl-4-piperidone into a reactor, and adding biphenyl. Methylene chloride was added thereto and dissolved with stirring at 0 ℃ to give a monomer concentration of 35% by weight. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 0 deg.C for 20h, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the isatin-methyl piperidone-biphenyl copolymer. Wherein the mol ratio of isatin to N-methyl-4-piperidone is 15: 85, the ratio of the total moles of isatin and N-methyl-4-piperidone to the moles of biphenyl is 1.1: 1, the molar ratio of trifluoromethanesulfonic acid to biphenyl is 10: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 12.
10mol of the copolymer is dissolved in dimethylacetamide to prepare a 10 wt% solution, and 60mol of methyl iodide is added to react at 60 ℃ for 48 h. And pouring the polymer solution into acetone for precipitation, filtering, washing with water, and drying in an oven to obtain the aminated isatin-methyl piperidone-biphenyl copolymer.
The method of example 2 was used to prepare an electrolyte solution of the ammonified copolymer and an anion exchange membrane, wherein the membrane was immersed in 1M NaOH at 80 ℃ for ion exchange for 2h, then immersed in deionized water for 24h, and washed with water.
FIG. 3 is a diagram of an aminated isatin-methylpiperidinone-biphenyl copolymer 1 H-NMR spectrum. The chemical shift is 10.84ppm of N-H peak of amido bond in isatin, the characteristic peak is the chemical shift of proton on benzene ring at 7.05-7.58ppm, the characteristic peak is the characteristic peak of methyl proton on piperidine N atom at 3.15ppm, and the characteristic peak is the proton of methylene on piperidine ring at 2.84 ppm. Indicating the successful synthesis of the methylammonium isatin-methylpiperidinone-biphenyl copolymer.
The formula of the ammonified copolymer is as follows:
the conductivity of hydroxide ions is 85mS/cm at 80 ℃, the alkali resistance is 1700h in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
Example 5
Vinylbenzylisatin was synthesized as in example 2.
Adding vinylbenzyl isatin and N-methyl-4-piperidone into a reactor, and adding m-terphenyl. Methylene chloride was added thereto and dissolved with stirring at 0 ℃ to give a monomer concentration of 28% by weight. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 0 deg.C, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the vinylbenzyl isatin-methyl piperidone-biphenyl copolymer. Wherein the mol ratio of the vinylbenzyl isatin to the N-methyl-4-piperidone is 3: 7, the ratio of the total moles of vinylbenzylisatin and N-methyl-4-piperidone to the moles of m-terphenyl is 1.05: 1, the molar ratio of the trifluoromethanesulfonic acid to the m-terphenyl is 6: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 10.
10mol of the copolymer was dissolved in N, N-dimethylacetamide to prepare a 3 wt% solution, and 60mol of bromohexane was added thereto to react at 50 ℃ for 36 hours. And pouring the polymer solution into methanol for precipitation, filtering, washing with water, and drying in an oven to obtain the aminated copolymer.
An electrolyte solution and an anion exchange membrane of the ammonium copolymer were prepared by the method of example 2.
The crosslinked ammonium ion membrane was prepared as in example 2.
The formula of the ammonified copolymer is as follows:
the hydroxyl ion conductivity is 80mS/cm at 80 ℃, the alkali resistance is 2000h in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
Example 6
Allylisatin was synthesized as in example 1.
Adding allyl isatin and N-methyl-4-piperidone into a reactor, and adding p-terphenyl. Methylene chloride was added thereto and dissolved with stirring at 0 ℃ to give a monomer concentration of 30% by weight. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 0 deg.C for 22h, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the allyl isatin-methyl piperidone-terphenyl copolymer. Wherein the mol ratio of the allyl isatin to the N-methyl-4-piperidone is 1: 9, the ratio of the total number of moles of allylisatin and N-methyl-4-piperidone to the number of moles of p-terphenyl is 1.1: 1, the molar ratio of the trifluoromethanesulfonic acid to the p-terphenyl is 9: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 10.
10mol of the copolymer is dissolved in N, N-dimethylacetamide to prepare 8 wt% solution, and 100mol of methyl iodide is added to react at 70 ℃ for 48 h. And pouring the polymer solution into ether to separate out, filtering, washing with water, and drying in an oven to obtain the ammonium copolymer.
An electrolyte solution and an anion exchange membrane of the aminated copolymer were prepared by the method of example 2.
The crosslinked ammonium ion membrane was prepared as in example 2.
The formula of the ammonified copolymer is as follows:
the hydroxyl ion conductivity is 80mS/cm at 80 ℃, the alkali resistance is 2000h in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
FIG. 4 is a drawing showing the preparation of the allylisatin-methylpiperidinone-terphenyl copolymer of example 6 1 H-NMR chart.
Example 7
Synthesis of hexyl isatin: the reaction was carried out in the same manner as in example 1 except that bromohexane was used instead of bromopropene.
Adding hexyl isatin and N-methyl-4-piperidone into a reactor, and adding biphenyl. Methylene chloride was added and dissolved with stirring at 0 ℃ to give a monomer concentration of 15 wt%. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 0 deg.C for 30h, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the hexyl isatin-methyl piperidone-biphenyl copolymer. Wherein the molar ratio of the hexyl isatin to the N-methyl-4-piperidone is 1: 4, the ratio of the total number of moles of hexylisatin and N-methyl-4-piperidone to the number of moles of biphenyl is 1: 1, the molar ratio of trifluoromethanesulfonic acid to biphenyl was 14: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 10.
1mol of the copolymer is dissolved in N, N-dimethylacetamide to prepare 8% solution, and 10mol of methyl iodide is added to react at 30 ℃ for 24 h. And pouring the polymer solution into methanol for precipitation, filtering, washing with water, and drying in an oven to obtain the aminated copolymer.
An electrolyte solution and an anion exchange membrane of the ammonium copolymer were prepared by the method of example 2.
The formula of the ammonified copolymer is as follows:
the hydroxyl ion conductivity is 85mS/cm at 80 ℃, the alkali resistance is 1600 hours in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
Example 8
Bromohexyl N-methylpiperidine salts are synthesized by reacting N-methylpiperidine with excess dibromohexane via a Moxiau reaction.
Synthesis of N-methylhexylpiperidine salt isatin: the reaction was otherwise the same as in example 1, except that bromohexyl N-methylpiperidine salt was used instead of bromopropene.
Adding N-methylhexylpiperidine isatin and N-methyl-4-piperidone into a reactor, and adding biphenyl. Methylene chloride was added and dissolved with stirring at 0 ℃ to give a monomer concentration of 20% by weight. Triflic acid and trifluoroacetic acid were added, the reaction was stirred at 0 ℃ for 38h, and when the system became viscous the polymer was poured into a large amount of ice water, with 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the copolymer of hexyl methyl piperidine salt isatin-methyl piperidone-biphenyl. Wherein the mol ratio of the N-methylhexylpiperidine salt isatin to the N-methyl-4-piperidone is 2: the ratio of the total moles of the 3, N-methylhexylpiperidinium isatin and N-methyl-4-piperidone to the moles of biphenyl is 1: 1, the molar ratio of the trifluoromethanesulfonic acid to the biphenyl is 7: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 8.
3mol of the copolymer is dissolved in N, N-dimethylacetamide to prepare 8% solution, and 20mol of iodohexane is added to react at 60 ℃ for 24 h. And pouring the polymer solution into methanol for precipitation, filtering, washing with water, and drying in an oven to obtain the aminated copolymer.
An electrolyte solution and an anion exchange membrane of the ammonium copolymer were prepared by the method of example 2.
The formula of the ammonified copolymer is as follows:
the conductivity of hydroxide ions is 110mS/cm at 80 ℃, the alkali resistance is 1800h in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
Example 9
The synthesis of vinylbenzylisatin is the same as in example 2.
Adding vinylbenzyl isatin and N-methyl-4-piperidone into a reactor, and adding bisphenol fluorene. Adding dichloromethane at 0 deg.C, stirring to dissolve and make the monomer concentratedThe degree was 35 wt%. Adding trifluoromethanesulfonic acid and trifluoroacetic acid, stirring at 0 deg.C for 20h, pouring the polymerization product into a large amount of ice water when the system becomes viscous, and adding 1M NaHCO 3 Removing excessive acid, washing the product with water, filtering, and drying in vacuum to obtain the vinylbenzylisatin-methylpiperidinone-bisphenol fluorene copolymer. Wherein the mol ratio of the vinyl benzyl isatin to the N-methyl-4-piperidone is 1: 4, the ratio of the total moles of vinylbenzylisatin and N-methyl-4-piperidone to the moles of bisphenol fluorene is 1: 1, the molar ratio of trifluoromethanesulfonic acid to p-bisphenol fluorene is 8: 1, the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1: 10.
10mol of the copolymer is dissolved in dimethyl sulfoxide to prepare a 10 wt% solution, and 60mol of methyl iodide is added to react for 48h at 50 ℃. And pouring the polymer solution into ether for precipitation, filtering, washing with water, and drying in an oven to obtain the ammonium copolymer.
An electrolyte solution and an anion exchange membrane of the aminated copolymer were prepared by the method of example 2.
The crosslinked ammonium ion membrane was prepared as in example 2.
The formula of the ammonified copolymer is as follows:
the conductivity of hydroxide ions at 80 ℃ is 75mS/cm, the alkali resistance is 2000h in 1M NaOH at 80 ℃, and the conductivity is reduced by 15%.
Example 10
The aminated allyl isatin-methylpiperidinone-biphenyl copolymer prepared in example 2 was added to dimethyl sulfoxide, and dissolved by stirring to prepare a 3 wt% solution, and then, defoaming was performed to obtain a transparent and uniform copolymer solution.
At room temperature, the thickness of the glass is 2.0X 3.0cm 2 Soaking the polytetrafluoroethylene PTFE microporous membrane in ethanol for 10 hours. Taking out the PTFE membrane, flatly paving the PTFE membrane, uniformly dripping dimethyl sulfoxide by using a dropper, and sucking the liquid on the surface of the PTFE membrane by using filter paper. The copolymer solution is dripped on the surface of a PTFE membrane for self-leveling, and then the membrane is put into an oven for drying at 60 ℃ to constant weight. Immersing the obtained filmAnd (3) performing ion exchange in 1M NaOH at 80 ℃ for 2h, then placing in deionized water at room temperature for 24h, and drying to constant weight to obtain the composite membrane.
The conductivity of the hydroxide ion is 60mS/cm at 80 ℃, the alkali resistance is 2300h in 1M NaOH at 80 ℃, and the conductivity is reduced by 12%.
Example 11
The aminated allylisatin-methylpiperidinone-terphenyl prepared in example 6 was added to dimethylacetamide (DMAc), stirred and dissolved to prepare a 1 wt% solution, and defoamed to obtain a transparent and uniform copolymer solution.
At room temperature, the thickness of the glass is 2.0X 3.0cm 2 The polyethylene microporous membrane is soaked in ethanol for 3 hours. Taking out the polyethylene microporous membrane, spreading the polyethylene microporous membrane flatly, dripping a plurality of drops of DMAc (dimethyl acetamide) uniformly by using a dropper, and sucking the liquid on the surface of the membrane by using filter paper. And (3) dropwise adding the aminated copolymer solution on the surface of the PTFE membrane for self-leveling, and then putting the membrane into an oven for drying at 60 ℃ to constant weight. And soaking the obtained membrane in 1M NaOH at room temperature for 24h for ion exchange, then placing the membrane in deionized water at room temperature for 48h, taking out the membrane, and drying the membrane until the weight is constant to obtain the composite membrane.
Example 12
The aminated hexylmethylpiperidine salt isatin-methylpiperidinone-biphenyl copolymer prepared in example 8 was added to DMAc, stirred and dissolved to prepare a 10 wt% solution, and defoamed to obtain a transparent and uniform copolymer solution.
At room temperature, the thickness of the glass is 2.0X 3.0cm 2 Soaking the polytetrafluoroethylene PTFE microporous membrane in ethanol for 24 hours. Taking out the PTFE membrane, spreading the PTFE membrane, uniformly dropwise adding DMAc solvent by using a dropper, and sucking the liquid on the surface of the PTFE membrane by using filter paper. The copolymer solution is dripped on the surface of a PTFE membrane for self-leveling, and then the membrane is put into an oven for drying at 60 ℃ to constant weight. And immersing the obtained membrane into 1M NaOH at 80 ℃ for 6h of ion exchange, then placing the membrane into deionized water at room temperature for 30h, and drying the membrane to constant weight to obtain the composite membrane.
Claims (8)
1. An isatin aromatic hydrocarbon copolymer, which is characterized by having a structure shown as a general formula I:
wherein n is more than 0 and less than 1;
r is H or C 1 ～C 12 Alkyl groups of (a);
ar is aromatic hydrocarbon and has the following structure:
wherein R is 1 Is C 1 ～C 12 Alkyl group of (1).
2. The preparation method of the isatin arene copolymer is characterized by comprising the following specific steps:
step one, synthesis of substituted isatin
Dissolving isatin in solvent A to obtain 1-20 wt% solution, adding excessive anhydrous K 2 CO 3 Stirring to dissolve, adding the compound B, and controlling the molar ratio of the isatin to the compound B to be 1: 1-1: 3, reacting for 10-50h at 20-60 ℃; after the reaction is finished, pouring the reaction solution into ice water, extracting by using an extracting agent, carrying out rotary evaporation, and recrystallizing the crude product by using ethanol to obtain substituted isatin;
the solvent A is one or a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, chloroform, dimethyl sulfoxide and N-methylpyrrolidone;
the compound B is brominated alkane, brominated olefin, vinyl benzyl chloride or glycidyl acrylate GMA;
the extractant is one or more than two of methanol, toluene, acetone, petroleum ether, diethyl ether and chloroform;
step two, synthesis of isatin arene copolymer
Adding the substituted isatin, the N-methyl-4-piperidone and the aromatic hydrocarbon obtained in the step one into dichloromethane, and stirring and dissolving in ice bath to enable the monomer concentration of the substituted isatin to be 15-40 wt% to obtain a mixed solution; adding trifluoromethanesulfonic acid and trifluoroacetic acid into the mixed solution as catalysts, and stirring at 0-5 ℃ to react for 14-48h; after the reaction is finished, the product is poured into ice water and filtered, and NaHCO is used as the product 3 Removing excessive acid, washing with water, filtering, and vacuum drying to obtain white fibrous isatin arene copolymer; dissolving the copolymer in a solvent A, then pouring the solution into a precipitator, filtering and drying the solution to obtain a refined fibrous isatin arene copolymer;
the ratio of the total mole number of the substituted isatin and the N-methyl-4-piperidone to the mole number of the aromatic hydrocarbon is (1-1.1): 1; the molar ratio of the substituted isatin to the N-methyl-4-piperidone is 1: 9-4: 6; the molar ratio of the trifluoromethanesulfonic acid to the aromatic hydrocarbon is (6-14): 1; the volume ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid is (8-14): 1;
the aromatic hydrocarbon is biphenyl, p-terphenyl, m-terphenyl, 9-dialkyl fluorene or bisphenol fluorene;
the precipitant is one or more of methanol, ethanol, water, petroleum ether, ethyl acetate, acetone, and diethyl ether.
3. A method for preparing an anion exchange membrane from the isatin arene copolymer, which is prepared by the method of claim 2, and is characterized by comprising the following steps:
step (1), synthesis of isatin arene copolymer with ammonium cation
Dissolving isatin arene copolymer in solvent A to obtain 5-20 wt% solution, and adding methyl iodide or bromoalkane R 1 -Br, wherein methyl iodide or R 1 The molar ratio of-Br to the isatin arene copolymer is (5-15): 1, reacting for 20-100 h at 30-100 ℃; after the reaction is finished, pouring the reaction liquid into a precipitator, filtering, and washing the product with water to obtain the isatin arene copolymer with ammonium cations, wherein the structure of the isatin arene copolymer is shown as a general formula II:
wherein n is more than 0 and less than 1; x - Is a counter ion of Br - Or OH - Ions; r is 1 Is C 1 ～C 12 Alkyl groups of (a);
the solvent A is one or a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, chloroform, dimethyl sulfoxide and N-methylpyrrolidone;
the precipitant is one or more of methanol, ethanol, water, petroleum ether, ethyl acetate, acetone, and diethyl ether;
step (2) preparation of electrolyte solution of isatin arene copolymer with ammonium cation
Adding the isatin arene copolymer with ammonium cations prepared in the step (1) into a solvent A, stirring for dissolving, and defoaming to obtain a transparent and uniform electrolyte solution, wherein the concentration of the solution is determined according to actual needs;
step (3), preparation of isatin arene copolymer anion exchange membrane
Spreading a membrane on the electrolyte solution with the concentration of 3-15 wt% obtained in the step (2), immersing the membrane into a 1M NaOH or KOH solution at the temperature of room temperature to 80 ℃ for ion exchange for 2-24 h, soaking the membrane in room temperature deionized water for 24-48 h, washing the membrane to be neutral, and drying the membrane to obtain an isatin arene copolymer anion exchange membrane; when the compound B for preparing the isatin arene copolymer is brominated alkane, brominated olefin, vinyl benzyl chloride or glycidyl acrylate GMA, adding a thermal initiator or a photoinitiator during film preparation to obtain the cross-linked isatin arene copolymer anionic film.
4. The method for preparing an anion exchange membrane from the isatin arene copolymer according to claim 3, wherein the electrolyte solution of the isatin arene copolymer with ammonium cations prepared in the step (2) is used as a resin binder in a fuel cell for preparing a membrane electrode.
5. The anion-exchange membrane prepared by the method of claim 3 is applied to fuel cells, flow batteries, electrolysis, electrodialysis or separation membranes.
6. A method for preparing a composite membrane by using the isatin arene copolymer prepared by the method of claim 2, which is characterized by comprising the following specific steps:
step (1), synthesis of isatin arene copolymer with ammonium cation
Dissolving isatin arene copolymer in solvent A to obtain 5-20 wt% solution, adding methyl iodide or bromoalkane R 1 -Br, wherein, methyl iodide or R 1 The molar ratio of-Br to isatin arene copolymer is (5-15): 1, reacting for 20-100 h at 30-100 ℃; after the reaction is finished, pouring the reaction liquid into a precipitator, filtering, washing the product with water to obtain the isatin arene copolymer with ammonium cations, wherein the structure of the isatin arene copolymer is shown as a general formula (II):
wherein n is more than 0 and less than 1; x - Is a counterion of Br - Or OH - Ions; r 1 Is C 1 ～C 12 Alkyl groups of (a);
the solvent A is one or a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, chloroform, dimethyl sulfoxide and N-methylpyrrolidone;
the precipitant is one or more of methanol, ethanol, water, petroleum ether, ethyl acetate, acetone, and diethyl ether;
step (2), preparation of isatin arene copolymer solution with ammonium cation
Adding the isatin arene copolymer with ammonium cations prepared in the step (1) into a solvent A, stirring and dissolving to prepare a 1-10 wt% solution, and defoaming to obtain a transparent and uniform isatin arene copolymer solution with ammonium cations;
step (3), preparation of composite film
Soaking the base membrane in ethanol at room temperature for 3-24 h, taking out and spreading the base membrane, uniformly dropwise adding a solvent A on the surface to soak the base membrane, casting the isatin aromatic hydrocarbon copolymer solution with ammonium cations prepared in the step (2) on the base membrane for self-leveling, and putting the base membrane into a drying oven to be dried to constant weight; and then, immersing the obtained base membrane into 1M NaOH at the room temperature of 80 ℃ for ion exchange for 2-24 h, placing the base membrane into deionized water at the room temperature for 24-48 h, taking out the base membrane, and drying the base membrane in vacuum to constant weight to obtain the isatin arene copolymer composite membrane.
7. The method for preparing the composite membrane by using the isatin arene copolymer according to claim 6, wherein the base membrane is a polytetrafluoroethylene or polyethylene microporous membrane, and the porosity is greater than 90%.
8. The composite membrane prepared by the method of claim 6 is applied to a fuel cell, a flow battery, electrolysis, electrodialysis or a separation membrane.
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