CN113321807A - Preparation method of crown ether-containing copolymerized polyimide and phosphoric acid-doped proton exchange membrane thereof - Google Patents
Preparation method of crown ether-containing copolymerized polyimide and phosphoric acid-doped proton exchange membrane thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof. The copolymer polyimide containing crown ether has a structure shown in a formula I, can be used as a phosphoric acid-doped proton exchange membrane material, is obtained by synthesizing a diamine monomer A containing imide chain links and a diamine monomer B containing crown ether rings by adopting dianhydride and diamine and polymerizing under the action of an initiator. The molecular chain of the copolymerization type polyimide provided by the invention has a troger base structure, and the main chain of the copolymerization type polyimide contains a crown ether structure. The copolymerized polyimide prepared from the copolymer has excellent film forming property and mechanical property and higher thermal stability. The phosphoric acid doped proton exchange membrane has good mechanical property, strong hydrolytic resistance and oxidation resistance and good dimensional stability, has good conductivity in the environment from low temperature to high temperature and low humidity, and has wide application prospect when being used as a wide-temperature-range proton exchange membrane of a fuel cell.
Description
The invention belongs to the technical field of new polyimide materials, and particularly relates to a preparation method of crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof.
Background
In order to find an alternative energy source to fossil fuel, fuel cells have been widely studied to directly convert chemical energy of fuel such as hydrogen and methanol into electric energy. Among the various types of fuel cells, Proton Exchange Membrane Fuel Cells (PEMFCs) are particularly important because they can be used as portable, vehicular, and stationary energy sources. The traditional perfluorinated sulfonic acid proton exchange membrane represented by Nafion, Flemion, Aciplex and Dow has excellent conductivity and chemical corrosion resistance, and is widely applied to proton exchange membranes and industry. Currently, the most studied high temperature proton exchange membranes are phosphoric acid doped Polybenzimidazole (PBI) membranes, but even today, the synthesis of high molecular weight and membrane-formable PBI remains a challenge. Polyimides are known for their high heat resistance, solvent resistance and good overall properties. However, the application of the membrane is limited to Sulfonated Polyimide (SPI), which can be used as a proton exchange membrane in a low-temperature hydration state. In the high temperature proton exchange membrane, although the synthesis of polyimides containing benzimidazole moieties in the polymer backbone or as substituents has been reported, polyimide proton exchange membranes have been largely excluded from the use of polyimides without benzimidazole substitution in fuel cells at low humidity, high temperatures.
Sulfonated Polyimides (SPI), especially sulfonated hexacyclic naphthalene polyimides, are considered promising candidates for proton exchange membranes due to their excellent chemical and thermal stability, high mechanical strength, good membrane forming ability, and low fuel cell gas (or liquid) crossover. SPI based on 1,4,5, 8-naphthalene tetracarboxylic dianhydride (NTCDA) inBoth at high relative humidity and high temperature show proton conductivity comparable to or higher than Nafion, almost 10 times lower methanol permeability than Nafion. SPIs prepared based on 4, 4-binaphthyl-1, 1',8,8' -tetracarboxylic dianhydride (BNTDA) have better oxidation resistance and hydrolytic stability. Based on BNTDA, has a proton conductivity of 0.11S cm at 20 ℃ with a basic triphenylamine group (SPI-t)-1The methanol permeability is 2.7X 10-7cm2s-1Hydrolytic stability at 90 ℃ for 1000 hours. The novel high-temperature polyimide proton exchange membrane containing benzimidazole substituent groups is also researched and synthesized, and the proton conductivity is 0.017-0.043Scm under the anhydrous condition of 160 DEG C-1The phosphoric acid absorption rate is 89% -116%. (references: chem.rev.,112(2012), pp.2780-2832; Fuel Cells II 2008,216,185; J.Membr.Sci.2008,314, 24; J.Membr.Sci.2015,483, 144;).
In addition, there are patents disclosing studies on polyimide proton exchange membranes. CN 108963308A discloses a polyimide proton exchange membrane, which is a trifunctional polyamine monomer synthesized by using phloroglucinol and 3-nitro-5-trifluoromethylaniline as raw materials; then the polyamine monomer, 4, 4-bis (4-amino-1-naphthyl azo) -2, 2-stilbene disulfonic acid, 2- (4-amino-3-methyl-phenyl) -4-methyl-benzimidazole-5-amine and 3,3,4, 4-biphenyl tetracarboxylic dianhydride are used for synthesizing branched polyimide molecules in m-methylphenol by adopting a one-step method, and the novel polyimide proton exchange membrane is prepared by crosslinking through a crosslinking agent and modification through a coupling agent. CN 103694490B discloses a polyimide proton exchange membrane, which is prepared by introducing nitrogen heterocycle into polyimide, doping phosphoric acid, utilizing the acid-base interaction of nitrogen and phosphoric acid, and using the nitrogen heterocycle to replace water as a proton transmission carrier, and the polyimide proton exchange membrane material which can be used under the high-temperature anhydrous condition of higher than 100 ℃ is prepared, wherein the proton conductivity at 120 ℃ is 10-6-10-3Scm-1. Patent CN 103087297 a discloses a method for preparing a side chain sulfonated polyimide proton exchange membrane containing aliphatic imide structure, which improves proton conductivity and stability by changing the main chain structure of the polymer and further constructing a proton transmission channel in the proton exchange membrane. The substance prepared by the methodThe conductivity of the proton exchange membrane at room temperature is 0.13Scm-1. However, the proton exchange membrane prepared from the sulfonated polyimide has low conductivity, low use temperature and high humidity, and the high-temperature polyimide proton exchange membrane needs to be prepared by introducing substituents such as benzimidazole and the like, so that the phosphoric acid-doped crown ether-containing copolymerized polyimide proton exchange membrane with low humidity and high conductivity from low temperature to high temperature is urgently needed to be prepared.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a copolymer polyimide containing crown ether and a phosphoric acid-doped proton exchange membrane thereof. The copolymerization type polyimide containing crown ether provided by the invention has excellent film forming property and mechanical property and higher thermal stability, and meanwhile, the phosphoric acid doped proton exchange membrane prepared from the copolymerization type polyimide containing crown ether has good mechanical property, oxidation resistance and hydrolytic stability, and has better conductivity and fuel cell performance from low temperature to high temperature under low humidity.
A preparation method of a copolymer polyimide containing crown ether and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the synthesis process, the synthesis conditions and the synthesis structure are as follows:
(1) synthesis of copolymer polyimide containing crown ether:
with dianhydride R1 
And diamine R2H2N-R2-NH2Synthesizing a diamine monomer A containing imide chain links as a raw material
Dissolving the obtained diamine monomer A and crown ether diamine monomer B in an acid solvent, wherein the mass ratio of the diamine monomer A to the crown ether diamine monomer B is 1:9-9:1, preparing a monomer mixed solution, adding an initiator, and reacting under a protective atmosphere to obtain the copolymer polyimide containing crown ether, wherein the specific reaction is as follows:
formula I contains a crown ether copolymer polyimide
In the formula I, R in A1Is dianhydride residue, R in A2Is a diamine residue, R in B3Is a crown ether diamine residue; and n is 9:1-1: 9. The molecular chain of the copolymer polyimide containing crown ether contains troger base and crown ether structure.
(2) Preparing a crown ether-containing copolymerized polyimide phosphoric acid-doped proton exchange membrane:
firstly, the copolymer polyimide containing crown ether obtained in the step (1) is dissolved in an aprotic polar solvent (such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and the like) or a nonpolar solvent (such as trichloromethane, dichloromethane and the like) or trifluoroacetic acid and trifluoromethanesulfonic acid to prepare a polymer solution with a solid content of 1-25 wt.%. And then uniformly coating the polymer solution on flat glass, and adjusting the thickness of the coated solution layer to make the dried thickness of the solution layer be 5-150 micrometers. And then the plate glass coated with the polymer solution is put into an inert atmosphere oven or a vacuum oven for drying, or heat treatment is carried out according to a temperature programming mode of 1-10 hours at 60 ℃, 1-10 hours at 90 ℃, 1-10 hours at 120 ℃ and 1-10 hours at 150 ℃. And after cooling to room temperature, peeling the film from the flat glass to obtain the crown ether-containing copolymerized polyimide film, then soaking the obtained film into 25-85% phosphoric acid solution at 10-90 ℃ for 12-120 hours, taking out the film, drying the film in an inert atmosphere oven or a vacuum oven, and carrying out heat treatment according to a heating mode at 60-120 ℃ for 1-120 hours to obtain the phosphoric acid-doped crown ether-containing copolymerized polyimide proton exchange membrane.
In the present invention, the dianhydride residue, diamine residue, or crown ether diamine residue refers to a residue obtained by removing an anhydride group or an amino group from a dianhydride, diamine, or crown ether diamine; m and n represent average polymerization degrees.
The copolymer polyimide containing crown ether provided by the invention has diazacyclo ring
The phosphoric acid is of a twisted structure and has abundant N elements, so that the phosphoric acid doping amount is increased; the copolymer polyimide containing crown ether also has crown ether ring, which is helpful to greatly increase the phosphoric acid adsorption capacity, thereby improving the conductivity.
A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that m: n in the crown ether-containing copolymerized polyimide is selected from 1:9 to 9:1, and can be 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1 and the like. When m is too small, the proportion of the crown ether structure in the molecular chain is too low, the doping amount of the crown ether structure to phosphoric acid is insufficient, and the conductivity is low; when m: n is too large, the proportion of the crown ether structure in the molecular chain is too high, resulting in deterioration of heat resistance and hydrolytic stability of the polymer, and thus it cannot be applied to a high-temperature environment.
A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that x and y are respectively an integer of 1-50, such as 1,2, 3,4, 5, 6,7, 8, 9,10, 12, 15, 18, 20, 25, 30, 35, 40, 45 or 50.
The preparation method of the crown ether copolymer-containing polyimide and the phosphoric acid-doped proton exchange membrane thereof is characterized in that molecular chains of the crown ether copolymer-containing polyimide contain troger base(s) (R) ()
Base, abbreviation TB)
Structure and crown ether structure
A preparation method of copolymer polyimide containing crown ether and phosphoric acid doped proton exchange membrane thereof is characterized in that the weight average molecular weight of the copolymer polyimide containing crown ether is 1 ten thousand to 100 ten thousand; for example, it may be 1 ten thousand, 2 ten thousand, 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, 12 ten thousand, 15 ten thousand, 18 ten thousand, 20 ten thousand, 22 ten thousand, 25 ten thousand, 28 ten thousand, 30 ten thousand, 32 ten thousand, 35 ten thousand, 38 ten thousand, 40 ten thousand, 45 ten thousand, 50 ten thousand, 60 ten thousand, 70 ten thousand, 80 ten thousand, 90 ten thousand, or 100 ten thousand, etc. More preferably 5 to 50 ten thousand.
A preparation method of a copolymer polyimide containing crown ether and a phosphoric acid doped proton exchange membrane thereof is characterized in that in the formula I, R in A is1Any one selected from the following substituted or unsubstituted groups:
wherein the dotted line represents the position of the group attachment, and when the group contains a substituent as described above, the substituent is selected from methyl, methoxy, halogen, hydroxy, oxo, cyano, heteroaryl, heterocyclic, or amino.
A preparation method of a copolymer polyimide containing crown ether and a phosphoric acid doped proton exchange membrane thereof is characterized in that in the formula I, R in A is2Any one selected from the following substituted or unsubstituted groups:
wherein the dotted line represents the position of the group attachment, and when the group contains a substituent as described above, the substituent is selected from any one of methyl, methoxy, halogen, hydroxy, cyano, heteroaryl, heterocycloalkyl, and amino.
A preparation method of a copolymer polyimide containing crown ether and a phosphoric acid doped proton exchange membrane thereof is characterized in that in the formula I, R in A is3Any one selected from the following substituted or unsubstituted groups:
wherein the dotted line represents the position of the group attachment, and when the group contains a substituent as described above, the substituent is selected from any one of methyl, methoxy, halogen, hydroxy, cyano, heteroaryl, heterocycloalkyl, and amino.
The preparation method of the copolymer polyimide containing crown ether and the phosphoric acid doped proton exchange membrane thereof is characterized in that the dianhydride R is the preferable technical scheme of the invention1Selected from pyromellitic dianhydride (PMDA), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTCDA), 3,4,9, 10-perylene tetracarboxylic anhydride (PTCDA), triptycene-2, 3,6, 7-tetracarboxylic dianhydride (TTD), 9' -spirobifluorene-2, 2',3,3' -tetracarboxylic dianhydride (BDFDA), 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (SBDA) or 4,4 '-dinaphthalene-1, 1',8, one or a combination of at least two of 8' -tetracarboxylic dianhydride (BNTDA).
The structural formula of the dianhydride is as follows:
a preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that diamine R is prepared2Selected from 2, 6-Diaminotoluene (DAP), 2, 5-dimethyl-1, 4-phenylenediamine (DPD), 4' -diamino-3, 3' -dimethylbiphenyl (o-Tolidine), 1' -binaphthyl-2, 2' -diamine (AMMA), 1, 5-Naphthalenediamine (NPD), 9' -spirobi [ 9H-fluorene)]-2,2' -diamine (SBF), 3' -dimethyl-9, 9' -spirobi [ 9H-fluorene]-2,2' -diamine (CSBF), 6-amino-2- (3-aminophenyl) Benzimidazole (BIA), 9-bis (4-amino-3-methylphenyl) fluorene or 9, 9-bis (4-aminophenyl) fluorene (BAMF), 4' -diaminodiphenylethane (DDE), 4' - (cyclohexane-1, 4-dithiodiphenylamine) (SCHDA), 1, 4-bis [ 2-amino-4- (trifluoromethyl) phenyl ] diphenylamine]Piperazine (AFMT), 5' -isopropylidene bis (2-furfuryl amine) (DAF), 2-bis (4-aminophenyl) norbornane (BANB), 3-bis (4-Aminophenyl) Quinuclidine (AQ), 1-bis (4-aminophenyl) -4-methylcyclohexane (BAME), 1-One or a combination of at least two of bis (4-aminophenyl) cyclohexane (BACH), 1,4:3, 6-dianhydro-2, 5-di-O- (4-aminophenyl) -D-mannitol (DA-IM) or 1, 3-bis (4-aminophenoxymethylene) -1,2, 2-trimethylcyclopentane (BAMT).
The structural formula of the diamine is as follows:
a preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that R3Any one selected from the following substituted or unsubstituted groups: trans-bis (aminobenzo) -12-crown-4, cis-bis (aminobenzo) -12-crown-4, trans-bis (aminobenzo) -15-crown-5, cis-bis (aminobenzo) -15-crown-5, trans-bis (aminobenzo) -18-crown-6, cis-bis (aminobenzo) -18-crown-6, trans-bis (aminobenzo) -21-crown-7, cis-bis (aminobenzo) -21-crown-7, trans-bis (aminobenzo) -24-crown-8, cis-bis (aminobenzo) -24-crown-8.
The structural formula of the crown ether diamine is as follows:
a preparation method of copolymerized polyimide containing crown ether and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the synthesis method in (1) is as follows: dianhydride R1And diamine R2Dissolving in high boiling point solvent, reacting at 0-90 deg.C (such as 0 deg.C, 5 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C or 90 deg.C) for 6-24h (such as 6h, 7h, 8h, 9h, 10h, 12h, 15h, 18h, 20h, 21h or 24 h), adding water-carrying agent, and reflux-reacting at 140-200 deg.C (such as 140 deg.C, 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 175 deg.C, 180 deg.C, 190 deg.C, 195 deg.C or 200 deg.C) for 2-80h (such as 2h, 3h, 4h, 5 h),6h, 7h, 8h, 9h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, 75h or 80h and the like) to obtain the diamine monomer A containing the imide chain segment,
the preparation method of the crown ether-containing copolymerized polyimide and the phosphoric acid-doped proton exchange membrane thereof is characterized in that the high-boiling-point solvent is a solvent with a boiling point of 150-220 ℃, and is preferably one or a combination of at least two of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), m-cresol or dimethyl sulfoxide (DMSO).
A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the water-carrying agent is one or a combination of at least two of toluene, xylene or chlorobenzene.
A preparation method of copolymerized polyimide containing crown ether and phosphoric acid doped proton exchange membrane thereof is characterized in that the synthesis method in (1) further comprises the purification steps of: after the reaction is finished, evaporating the water-carrying agent, adding the reaction solution into the mixed solution of one or the combination of two of methanol and ethanol and water, precipitating a solid product, then dissolving again, pouring into one or the combination of two of methanol and ethanol, precipitating, filtering and drying.
A preparation method of a crown ether-containing copolymer polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that a solvent used for redissolution is one or a combination of at least two of N, N-dimethylformamide, N-dimethylacetamide, trichloromethane, dichloromethane or acetone.
A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that in the step (2), the acidic solvent is one or a combination of at least two of trifluoroacetic acid (TFA), polyphosphoric acid and hydrochloric acid.
The preparation method of the copolymer polyimide containing crown ether and the phosphoric acid doped proton exchange membrane thereof is characterized in that in the monomer mixed solution in the step (2), a diamine monomer A and crown ether diamine R3The total content of (A) is 1-25 wt%; for example, it may be 1 wt%,2 wt%, 3 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, or the like.
A preparation method of a crown ether-containing copolymer polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the initiator in the step (2) is one or a combination of at least two of formaldehyde, paraformaldehyde, Hexamethylenetetramine (HMTA) or Dimethoxymethane (DMM).
The preparation method of the crown ether-containing copolymerized polyimide and the phosphoric acid-doped proton exchange membrane thereof is characterized in that the amount of the initiator is equal to that of the diamine monomer A or crown ether diamine R3The ratio of the total amount of substances is 4-10: 1; for example, it may be 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10: 1.
A preparation method of a crown ether-containing copolymer polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the reaction temperature in (2) is-20-50 ℃, for example, the reaction temperature can be-20 ℃,10 ℃,5 ℃,2 ℃, 0 ℃,2 ℃,5 ℃,8 ℃,10 ℃, 12 ℃, 15 ℃,18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 45 ℃ or 50 ℃ and the like; the time is 2 to 144 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 100 hours, 120 hours, 130 hours, 140 hours, or 144 hours.
A preparation method of copolymerized polyimide containing crown ether and phosphoric acid doped proton exchange membrane thereof is characterized in that (2) the preparation method also comprises the following purification steps: after the reaction is finished, adding alkali liquor into the reaction liquid to separate out a fibrous or powdery solid product, redissolving the obtained fibrous or powdery solid product, pouring the redissolved product into methanol, separating out, washing and drying.
A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the alkali liquor is ammonia water, a sodium carbonate solution or a sodium bicarbonate solution.
A process for preparing the copolymerized polyimide containing crown ether and its phosphoric acid doped proton exchange membrane includes such steps as dissolving the copolymerized polyimide containing crown etherThe solvent for the amine may be selected from N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), trichloromethane (CHCl)3) Or dichloromethane (CH)2Cl2) One or a combination of at least two of trifluoroacetic acid (TFA) or trifluoromethanesulfonic acid (TRA).
A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that acid is phosphoric acid, the concentration of the acid is 25% -85%, the soaking temperature is 10-90 ℃, the soaking time is 12-120 hours, the drying temperature is 60-120 ℃, and the drying time is 1-120 hours.
The preparation method of the crown ether-containing copolymerized polyimide and the phosphoric acid-doped proton exchange membrane is characterized in that the thickness of the phosphoric acid-doped proton exchange membrane is 5-150 μm, for example, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the molecular chain structure of the polyimide is designed, so that the obtained copolymer polyimide containing crown ether has good mechanical property and heat-resistant stability, the glass transition temperature of the copolymer polyimide reaches over 380 ℃, the tensile strength reaches 40-150MPa, and the elastic modulus reaches 0.5-2.5 GPa; the phosphoric acid doped proton exchange membrane prepared from the copolymer polyimide containing crown ether has higher conductivity: the conductivity is 10-80mScm at 14% humidity and 80 deg.C-1(ii) a The conductivity is 30-2000mScm at 160 ℃ without humidity-1. Can be used in the field of wide temperature range phosphoric acid doped proton exchange membranes.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a crown ether-containing copolyimide having the following structural formula:
the preparation method comprises the following steps:
(1) preparation of imide-mer-containing diamine monomer A
Adding aliphatic diamine BACH (15.9834g, 60mmol) into a 500mL three-necked flask under the protection of nitrogen, adding NMP 150mL, adding aromatic dianhydride PTCDA (7.8464g, 20mmol) after aliphatic diamine is completely dissolved, stirring at 80 ℃ for reaction for 12 hours, cooling to room temperature after reaction, adding 50mL of water-carrying agent toluene, stirring at 180 ℃ for reflux reaction for 9 hours to obtain a diamine monomer A solution containing imide chain units, stopping heating after toluene is completely evaporated, naturally cooling to room temperature, pouring the reaction solution into a mixture (2L, V) of high-speed stirring methanol and waterMethanol:VWater (W)In 1:1), a precipitate was precipitated, and the obtained precipitate was dissolved in DMF, then precipitated in methanol, filtered, and naturally dried, followed by further vacuum drying at 80 ℃ for 12 hours to obtain an imide-mer-containing diamine monomer a powder.
(2) Preparation of crown ether-containing copolymerized polyimide
1.245g of the diamine monomer A prepared above and 0.181g of the crown ether diamine monomer R2(amount ratio of substances 1.4:0.6) were mixed well, added to a nitrogen-protected three-necked flask, then 1mL of dimethoxymethane (11.2mmol) was added, after stirring well, 75mL of trifluoroacetic acid was added, the reaction system was stirred at 0 ℃ for 96 hours, then carefully basified with 1.5% aqueous ammonia solution, and the resulting solution was stirred to precipitate a white fibrous precipitate. Dissolving the obtained precipitate in chloroform, separating out the filtered solid in methanol, washing with water and methanol for 3 times, filtering, naturally drying, and vacuum drying at 120 deg.C for 24 hr to obtain the final product.
(3) Preparation of phosphoric acid-doped copolymer polyimide proton exchange membrane containing crown ether
Dissolving the prepared branched polyimide in chloroform according to the solid content of 10 wt.%, casting and coating the polymer solution completely dissolved on clean horizontal plate glass, drying at room temperature for 12 hours, then placing the glass plate in a vacuum oven for drying, slowly cooling to room temperature after drying completely according to the conditions of 3 hours at 60 ℃,3 hours at 90 ℃,3 hours at 120 ℃ and 3 hours at 150 ℃, peeling the film from the plate, soaking the film in 75% phosphoric acid solution at room temperature for 96 hours, taking out the film, placing the film in the vacuum oven for drying at 100 ℃ for 12 hours, and slowly cooling to room temperature to obtain the phosphoric acid doped branched polyimide proton exchange membrane. The film thickness was controlled at 45 μm.
Structural characterization:
fourier transform Infrared Spectroscopy (FTIR) showed the polymer to be 1372cm-1，1718cm-1，1781cm-1An absorption peak of an imide ring is displayed nearby;
example 2
This example provides a crown ether-containing copolyimide having the following structural formula:
the preparation method comprises the following steps:
(1) preparation of imide-mer-containing diamine monomer A
Adding aromatic diamine o-Tolidine (12.738g, 60mmol) into a 500mL three-necked flask under the protection of nitrogen, adding NMP 150mL, adding aromatic dianhydride BPDA (5.8844g, 20mmol) after the o-Tolidine is completely dissolved, stirring at 0 ℃ for reaction for 24 hours, adding water-carrying agent toluene 50mL after the reaction is finished, stirring and refluxing at 200 ℃ for reaction for 8 hours to obtain a diamine monomer A solution containing imide chain links, stopping heating after the o-xylene is completely evaporated, naturally cooling to normal temperature, pouring the reaction solution into a mixture (2L, V) of ethanol and water which are stirred at high speedMethanol:VWater (W)1:1), dissolving the obtained precipitate in DMF, precipitating in methanol, filtering, naturally drying, and vacuum drying at 80 deg.C for 1After 2 hours, a powder of the imide-mer-containing diamine monomer A was obtained.
(2) Preparation of crown ether-containing copolymerized polyimide
1.309g of the diamine monomer A prepared above and 0.957g of crown ether diamine R2(amount ratio of substances 1:1) were mixed uniformly, added to a nitrogen-protected three-necked flask, then 2mL of dimethoxymethane (22.4mmol) was added, after stirring uniformly, 150mL of trifluoroacetic acid was added, the reaction system was stirred at-5 ℃ for 120 hours, then carefully basified with 1% aqueous sodium bicarbonate solution, and the resulting solution was stirred to precipitate a white fibrous precipitate. The solid was filtered off and washed 3 times with water and then with methanol. Dissolving the obtained fibrous precipitate with chloroform, precipitating in ethanol, filtering, naturally drying, and vacuum drying at 120 deg.C for 24 hr to obtain copolymerized polyimide.
(3) Preparation of phosphoric acid-doped copolymer polyimide proton exchange membrane containing crown ether
Dissolving the prepared branched polyimide in dichloromethane according to 25 wt.% of solid content, salivating and coating a polymer solution completely dissolved on clean horizontal plate glass, drying at room temperature for 24 hours, then placing the glass plate in a vacuum oven for drying, slowly cooling to room temperature after drying completely according to the conditions of 2 hours at 60 ℃,2 hours at 90 ℃,2 hours at 120 ℃ and 2 hours at 150 ℃, peeling off the film from the plate, soaking the film in a 65% phosphoric acid solution at room temperature for 72 hours, taking out the film, placing the film in the vacuum oven for drying at 80 ℃ for 12 hours, and slowly cooling to room temperature to obtain the phosphoric acid doped branched polyimide proton exchange membrane. The film thickness was controlled at 40 μm.
Structural characterization:
fourier transform Infrared Spectroscopy (FTIR) showed the polymer to be 1373cm-1，1717cm-1，1776cm-1An absorption peak of an imide ring is shown in the vicinity of the vicinity;
example 3
This example provides a copolymer polyimide containing crown ether and its phosphoric acid doped proton exchange membrane, and the difference between the preparation method and the example 1 is that, in the step (2)Diamine monomer A1.6 g, crown Ether diamine monomer R30.060g, the ratio of the amounts of the two substances was 9:1, and the other steps were the same as in example 1.
Structural characterization:
fourier transform Infrared Spectroscopy (FTIR) showed the polymer to be 1371cm-1，1715cm-1，1781cm-1An absorption peak of an imide ring is displayed nearby;
performance testing was performed on the polymers of examples 1-3 and their proton exchange membranes. The polymer molecular weight was measured using Gel Permeation Chromatography (GPC) with chloroform (CHCl) as the solvent3) N, N-Dimethylformamide (DMF); the PEM conductivity was tested using a four electrode system, an electrochemical workstation, a universal tensile machine for mechanical properties, and a dynamic thermomechanical analyzer (DMA) for glass transition temperature.
The test results are shown in the following table.
| Example 1 | Example 2 | Example 3 | |
| Molecular weight (Mn) | >50000 | >100000 | >180000 |
| Molecular weight distribution index (D) | 3.01 | 3.12 | 3.08 |
| Conductivity, mS cm-1(21％RH,30℃) | >8 | >13 | >6 |
| Conductivity, mS cm-1(10％RH,160℃) | >70 | >100 | >40 |
| Tensile modulus, MPa (25 ℃ C.) | >700 | >600 | >800 |
| Tensile Strength, MPa (25 ℃ C.) | >50 | >50 | >80 |
| Glass transition temperature (. degree. C.) | >400 | >400 | >400 |
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (25)
1. A preparation method of a crown ether-containing copolymerized polyimide and a phosphoric acid-doped proton exchange membrane thereof is characterized in that the synthesis process, the product structure and the preparation method are as follows:
(1) synthesis of copolymer polyimide containing crown ether:
with dianhydride R1 
And diamine R2H2NR2NH2Synthesizing a diamine monomer A containing imide chain links as a raw material
Dissolving the obtained diamine monomer A and crown ether diamine monomer B in an acid solvent, wherein the mass ratio of the diamine monomer A to the crown ether diamine monomer B is 1:9-9:1, preparing a monomer mixed solution, adding an initiator, and reacting under a protective atmosphere to obtain the copolymer polyimide containing crown ether, wherein the specific reaction is as follows:
in the formula I, R in A1Is dianhydride residue, R in A2Is a diamine residue, R in B3Is a crown ether diamine residue; and n is 9:1-1: 9. The molecular chain of the copolymer polyimide containing crown ether contains troger base and crown ether structure.
(2) Preparing a crown ether-containing copolymerized polyimide phosphoric acid-doped proton exchange membrane:
firstly, the copolymer polyimide containing crown ether obtained in the step (1) is dissolved in an aprotic polar solvent (such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and the like) or a nonpolar solvent (such as trichloromethane, dichloromethane and the like) or trifluoroacetic acid and trifluoromethanesulfonic acid to prepare a polymer solution with a solid content of 1-25 wt.%. And then uniformly coating the polymer solution on flat glass, and adjusting the thickness of the coated solution layer to make the dried thickness of the solution layer be 5-150 micrometers. And then the plate glass coated with the polymer solution is put into an inert atmosphere oven or a vacuum oven for drying, or heat treatment is carried out according to a temperature programming mode of 1-10 hours at 60 ℃, 1-10 hours at 90 ℃, 1-10 hours at 120 ℃ and 1-10 hours at 150 ℃. And after cooling to room temperature, peeling the film from the flat glass to obtain the crown ether-containing copolymerized polyimide film, then soaking the obtained film into 25-85% phosphoric acid solution at 10-90 ℃ for 12-120 hours, taking out the film, drying the film in an inert atmosphere oven or a vacuum oven, and carrying out heat treatment according to a heating mode at 60-120 ℃ for 1-120 hours to obtain the phosphoric acid-doped crown ether-containing copolymerized polyimide proton exchange membrane.
2. The crown ether-containing copolyimide according to claim 1, wherein the copolyimide has a weight average molecular weight of 1 to 100 ten thousand.
3. The crown ether-containing copolymerized polyimide according to claim 1, wherein R in A is R in formula I1Any one selected from the following substituted or unsubstituted groups:
wherein the dotted line represents the position of the group attachment, and when the group contains a substituent as described above, the substituent is selected from any one of methyl, methoxy, halogen, hydroxy, cyano, heteroaryl, heterocycloalkyl, and amino.
4. The crown ether-containing copolymerized polyimide according to claim 1, wherein R in A is R in formula I2Selected from substituted or unsubstitutedAny one of the following substituted groups:
wherein the dotted line represents the position of the group attachment, and when the group contains a substituent as described above, the substituent is selected from any one of methyl, methoxy, halogen, hydroxy, cyano, heteroaryl, heterocycloalkyl, and amino.
5. The crown ether-containing copolymerized polyimide according to claim 1, wherein R in B in formula I3Any one selected from the following substituted or unsubstituted groups:
wherein the dotted line represents the position of the group attachment, and when the group contains a substituent as described above, the substituent is selected from any one of methyl, methoxy, halogen, hydroxy, cyano, heteroaryl, heterocycloalkyl, and amino.
6. The method according to claim 1, wherein the dianhydride R is selected from the group consisting of1One or a combination of at least two selected from pyromellitic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, triptycene-2, 3,6, 7-tetracarboxylic dianhydride, 9' -spirobifluorene-2, 2',3,3' -tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, or 4,4' -dinaphthalene-1, 1',8,8' -tetracarboxylic dianhydride.
7. The process according to claim 1, wherein the diamine R is2Selected from 2, 6-diaminotoluene, 2, 5-dimethyl-1, 4-phenylenediamine, 44' -diamino-3, 3' -dimethylbiphenyl, 1' -binaphthyl-2, 2' -diamine, 1, 5-naphthalenediamine, 9' -spirobi [ 9H-fluorene]-2,2' -diamine, 3' -dimethyl-9, 9' -spirobi [ 9H-fluorene]-2,2' -diamine, 6-amino-2- (3-aminophenyl) benzimidazole, 9-bis (4-amino-3-tolyl) fluorene or 9, 9-bis (4-aminophenyl) fluorene, 4' -diaminodiphenylethane, 4' - (cyclohexane-1, 4-dithiodiphenylamine), 1, 4-bis [ 2-amino-4- (trifluoromethyl) phenyl ] amine]One or a combination of at least two of piperazine, 5' -isopropylidene bis (2-furfuryl amine), 2, 2-bis (4-aminophenyl) norbornane, 3-bis (4-aminophenyl) quinuclidine, 1-bis (4-aminophenyl) -4-methylcyclohexane, 1-bis (4-aminophenyl) cyclohexane, 1,4:3, 6-dianhydro-2, 5-bis-O- (4-aminophenyl) -D-mannitol, or 1, 3-bis (4-aminophenoxymethylene) -1,2, 2-trimethylcyclopentane.
8. The process according to claim 1, characterized in that the triamine R is present in the form of a solution3One or a combination of at least two selected from the group consisting of trans bis (aminobenzo) -12-crown-4, cis bis (aminobenzo) -12-crown-4, trans bis (aminobenzo) -15-crown-5, cis bis (aminobenzo) -15-crown-5, trans bis (aminobenzo) -18-crown-6, cis bis (aminobenzo) -18-crown-6, trans bis (aminobenzo) -21-crown-7, cis bis (aminobenzo) -21-crown-7, trans bis (aminobenzo) -24-crown-8, cis bis (aminobenzo) -24-crown-8.
9. The method according to claim 1, wherein the synthesis in (1) is carried out by: dianhydride R1And diamine R2Dissolving in a high boiling point solvent, reacting for 6-24h at 0-90 ℃ under a protective atmosphere, then adding a water-carrying agent, and carrying out reflux reaction for 2-80h at 120-200 ℃ to obtain the diamine monomer A containing the imide chain link.
10. The process according to claim 1, wherein the acidic solvent in (1) is one or a combination of at least two selected from trifluoroacetic acid, polyphosphoric acid, and hydrochloric acid.
11. The production method according to claim 1, wherein the total content of the diamine monomer A and the crown ether diamine monomer B in the monomer mixed solution in (1) is 1 to 25% by weight.
12. The method according to claim 1, wherein the source agent in (1) is one or a combination of at least two selected from the group consisting of formaldehyde, paraformaldehyde, hexamethylenetetramine and dimethoxymethane.
13. The preparation method according to claim 1, wherein the reaction in (1) is carried out at-20 to 50 ℃ for 2 to 144 hours.
14. The production method according to claim 1, wherein the ratio of the amount of the material of the initiator to the total amount of the diamine monomer A and the crown ether diamine B in (1) is 4 to 10: 1.
15. The method according to claim 1, wherein the step (1) further comprises a purification step of: after the reaction is finished, adding alkali liquor into the reaction liquid to separate out a fibrous or powdery solid product, redissolving the obtained fibrous or powdery solid product, pouring the redissolved fibrous or powdery solid product into methanol or ethanol, separating out, washing and drying.
16. The method according to claim 1. The method is characterized in that in the method (2), the aprotic polar solvent is preferably any one or a mixture of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc), or the nonpolar solvent is preferably one or a mixture of trichloromethane and dichloromethane or an acidic solvent of trifluoroacetic acid or methanesulfonic acid. The prepared copolymerization type polyimide solution containing crown ether has the solid content of 1 to 25 weight percent.
17. The method according to claim 1. The method is characterized in that in the method (2), a glass plate or a culture dish is preferably selected as the plate, and the dried thickness of the coated polymer solution layer is controlled to be 5-150 micrometers.
18. The method according to claim 1. The method is characterized in that the flat plate coated with the polymer solution in the method (2) is placed into an inert atmosphere oven or a vacuum oven for drying at 60 ℃ for 1-10 hours, at 90 ℃ for 1-10 hours, at 120 ℃ for 1-10 hours and at 150 ℃ for 1-10 hours.
19. The method according to claim 1. The method is characterized in that the acid doped in the method (2) is phosphoric acid, the soaking temperature is 25-90 ℃, the concentration of the phosphoric acid is 25-85%, and the soaking time is 12-120 hours.
20. The method according to claim 1. The method is characterized in that the membrane soaked with the phosphoric acid is placed in an inert atmosphere oven or a vacuum oven for drying, and the temperature is raised for drying at 60-120 ℃ for 1-120 hours.
21. The method according to claim 9, wherein the high boiling point solvent is selected from one or a combination of at least two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, m-cresol, and dimethylsulfoxide.
22. The preparation method according to claim 9, wherein the water-carrying agent is one or a combination of at least two of toluene, xylene or chlorobenzene.
23. The method of claim 9, wherein the method of synthesizing further comprises a purification step: after the reaction is finished, evaporating the water-carrying agent, adding the reaction solution into the mixed solution of one or the combination of two of methanol and ethanol and water, precipitating a solid product, then dissolving again, pouring into one or the combination of two of methanol and ethanol, precipitating, filtering and drying.
24. The method according to claim 15, wherein the solvent used for the re-dissolution is one or a combination of at least two selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, chloroform, dichloromethane, and acetone.
25. The method of claim 15, wherein the alkali solution is ammonia, sodium carbonate solution or sodium bicarbonate solution.
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