CN115057980A - Fluorine-containing sulfonated aromatic polymer, preparation method and application thereof - Google Patents

Fluorine-containing sulfonated aromatic polymer, preparation method and application thereof Download PDF

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CN115057980A
CN115057980A CN202210756448.0A CN202210756448A CN115057980A CN 115057980 A CN115057980 A CN 115057980A CN 202210756448 A CN202210756448 A CN 202210756448A CN 115057980 A CN115057980 A CN 115057980A
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sulfonic acid
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biphenyl
fluorine
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张所波
关佳雨
郑吉富
李胜海
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a fluorine-containing sulfonated aromatic polymer, a preparation method and application thereof, wherein the fluorine-containing sulfonated aromatic polymer contains tertiary carbon and quaternary carbon and has a structure shown in a formula 1; wherein R is 1 Is methyl or phenyl, R 2 Is hydrogen or a protecting group; ar (Ar) 1 Is phenyl or biphenyl, Ar 2 Is at least one sulfonic substituted phenyl group. The method takes trifluoromethyl ketone and sulfonic aldehyde monomers as raw materials and adopts Friedel-crafts type polycondensation reaction to prepare the compoundA fluorinated sulfonated aromatic copolymer. The obtained polymer has an ether-free rigid aryl skeleton, and can endow a polymer film with good thermal stability and oxidation stability. The ionic polymer membrane contains hydrophilic and hydrophobic segments, has good microphase separation and low swelling ratio, and is beneficial to application. The method has mild conditions, post-sulfonation is not needed, and the sulfonation degree can be controlled by regulating and controlling the monomer ratio; can avoid the use of metal catalysis, is environment-friendly and has low cost. The obtained polymer main chain contains tertiary carbon and quaternary carbon, and the tertiary carbon can be post-modified.

Description

Fluorine-containing sulfonated aromatic polymer, preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a fluorine-containing sulfonated aromatic polymer, and a preparation method and application thereof.
Background
The use of traditional energy causes the shortage of energy in modern society, the competition for resources and the overuse of ore energy, the pollution of sulfur and nitrogen oxides discharged by the combustion of ore energy to the environment, and the development of film-based renewable energy and energy storage and conversion devices has the significance of sustainable development. Polymer electrolyte membrane fuel cells, redox flow batteries, and fuel cells are clean and efficient power generation technologies in the 21 st century, and fuel cells are power generation devices that directly convert chemical energy into electrical energy through electrode reactions. The proton exchange membrane serving as a core of the fuel cell has the following characteristics: 1) high proton conductivity; 2) good thermal stability and mechanical properties; 3) high oxidation stability and good anti-swelling capacity; 4) appropriate price to performance ratio, etc.
The polymer electrolytes that can be used as proton exchange membranes are mainly: perfluorosulfonic acid proton exchange membrane, non-fluorosulfonic acid proton exchange membrane, and partial fluorosulfonic acid proton exchange membrane. The PEMFC is divided into two types of perfluoro and non-fluorinated, the perfluoro proton exchange membrane mainly refers to a short-chain perfluorinated sulfonic acid proton exchange membrane represented by Nafion of Dupont, and the non-fluorinated proton exchange membrane comprises aromatic ring or aromatic heterocyclic ring units and engineering resin materials with thermodynamic stability, such as Polyimide (PI), Polysulfone (PS), Polyarylethersulfone (PES), Polyaryletherketone (PEK) and the like. Generally, proton exchange membranes are composed of hydrophilic ionic groups and a hydrophobic polymer backbone, wherein the presence of the hydrophilic groups ensures the proton conductivity of the polymer, while the hydrophobic moieties ensure the mechanical and thermal properties of the polymer membrane.
The most commercialized proton exchange membranes at present are perfluorosulfonic acid type proton exchange membranes, in which the polystyrene main chain structure constitutes the hydrophobic portion, and the hydrophilic portion is constituted by the sulfonic acid group of the side chain. Due to the existence of an obvious hydrophilic-hydrophobic phase separation structure, a hydrophilic side chain is far away from a main chain to form a continuous proton transmission channel, and meanwhile, due to the existence of a super acid structure, the proton exchange membrane has high proton conductivity under complete hydration, but the proton exchange membrane has some defects: 1) the manufacturing cost is high, the cost is high, and the manufacturing process is complex; 2) the fuel permeability is high, and particularly when methanol is used as the fuel, the permeation phenomenon is serious, so that the open-circuit voltage of the battery is sharply reduced, and serious potential safety hazards exist. Namely, commercial perfluorosulfonic acid membranes such as Nafion have excellent thermal stability, chemical properties and high proton conductivity, but have the problems of high manufacturing cost, reduction of proton conductivity due to severe water loss at high temperature, high fuel permeability and the like. Therefore, the development of a sulfonated polymer membrane with low price, good thermal stability, chemical properties and high proton conductivity becomes an important direction for the development of the field, and the development of a novel proton exchange membrane has important significance.
The aromatic polymer has the characteristics of thermochemical stability, good mechanical property and easy modification due to the structure of a full-rigid main chain, and is widely researched as a potential proton exchange membrane material. However, the aromatic polymer main chain has low hydrophobicity and weak sulfonic acid, so that the IEC value of the sulfonated polymer needs to be increased by increasing the sulfonation degree to obtain high proton conductivity. In addition, the aromatic polymer generally has defects of instability to an oxidizing agent and acid-catalyzed degradation due to heteroatom bonds (such as diaryl ether bonds) contained in the aromatic polymer, so that the design of an excellent sulfonic acid aromatic polymer structure is very important.
For example, Zolotukhin et al synthesize a series of linear, high molecular weight polymers from trifluoromethyl aryl ketones with non-activated aromatic monomers in a one-pot process without metal catalysis; the polymer can be dissolved in common solvents, and the prepared fluorine-containing polymer shows good processing performance, excellent chemical stability and thermal stability [ Macromolecules46(2013)7245-7256 ]. The reaction can directly synthesize high-performance aromatic polymers through simple synthesis conditions, and prepare ionic fluorine-containing polymers by introducing sulfonic acid groups. Introduction of sulfonic acid groups is usually carried out by adding a sulfonation reagent to sulfonate a polymer prepared by a direct sulfonation method, and directly sulfonating the polymer with concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like. Xu bronze et al designed a polymer membrane with intrinsic micropores with a rigid twisted structure in the polymer backbone, containing hydrophobic fluorinated and hydrophilic sulfonic acid functional groups, facilitating proton and cation transport. PIM ionic polymer is synthesized under super acid catalysis, sulfonic acid groups are introduced under the catalysis of chlorosulfonic acid after synthesis, and the sulfonation degree is adjusted by adjusting the concentration of chlorosulfonic acid solution and the reaction time [ Angew 59(2020)9564-9573 ]. Because the direct sulfonation method uses a sulfonation reagent and uses a large excess amount of the sulfonation reagent for sulfonation, the amount of residual acid after sulfonation is large, so that danger is caused, and the aromatic polymer with high sulfonation reaction activity is easy to cause chemical crosslinking, the sulfonation degree is difficult to control, and the sulfonation is not uniform; it is also possible for polymer chains to break during sulfonation.
In addition to the direct sulfonation method, the sulfonated polymer can also be obtained by conducting a polymerization reaction between monomers by an indirect sulfonation method using a monomer unit having a sulfonic acid group structure. The degree of sulfonation of the polymer is controlled by the amount of sulfonated monomer added. Firstly, sulfonated monomers are synthesized, and then sulfonated polymers are prepared by copolymerization of the sulfonated monomers and non-sulfonated monomers. The method is easy to control the sulfonation degree of the polymer, can not cause the degradation of the polymer in the sulfonation process, and avoids the occurrence of crosslinking and other side reactions in the sulfonation process.
In recent five years, the method for preparing aromatic hydrocarbon polymer by stepwise polymerization of fluoroketone and unactivated aromatic hydrocarbon has been widely studied, and the reaction is
Figure BDA0003722660790000032
The polymerization is carried out in a mixture of the super acid TFSA and dichloromethane, and is influenced by reaction conditions such as the activity of reaction monomers and the acidity of a reaction medium. After the polymer backbone is defined, proton conductivity is imparted to the material by introducing sulfonic acid groups. The prior art for preparing the polymer containing sulfonic acid group mainly reflects in the following defects: 1) the sulfonic group is directly connected on the main chain to be not beneficial to inducing phase separation; 2) the residual acid after sulfonation has large amount; sulfonation reactionAromatic polymers that should be highly reactive are susceptible to chemical crosslinking; the sulfonation degree is not easy to control; the sulfonation is not uniform; sulfonated polymer chain scission, and the like. 3) Sulfonated aryl polymers have a high degree of sulfonation and are prone to problems such as reduced dimensional stability and high swelling of membranes. With the wider application of proton exchange membranes in the field of energy sources, developing proton exchange membranes which are easy to prepare and preparing PEMFCs materials with low price have important economic value and research significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the fluorine-containing sulfonated aromatic polymer, the preparation method and the application thereof.
The invention provides a fluorine-containing sulfonated aromatic polymer, which has a structure shown in a formula 1:
Figure BDA0003722660790000031
in the formula 1, R 1 Is methyl or phenyl, R 2 Is hydrogen or a protecting group; ar (Ar) 1 Is phenyl or biphenyl, Ar 2 Is at least one sulfonic substituted phenyl group; x and y are both degrees of polymerization; the fluorosulfonated aromatic polymer contains both tertiary and quaternary carbons.
The fluorine-containing sulfonated polymer with the structure shown in the formula 1 can be a random copolymer or a block copolymer; the structure of the fluorinated aromatic polymer comprises a hydrophobic fluorinated aromatic polymer main chain and an introduced sulfonic acid group. In the present invention, Ar 1 Is phenyl or biphenyl; the polymer has an ether-free rigid aryl skeleton, and can endow a polymer film with good thermal stability and oxidation stability.
In formula 1 of the present invention, Ar 2 Is phenyl substituted by at least one sulfonic acid group, namely, a sulfonic acid group is connected on a benzene ring. And, R 1 Is methyl (-CH) 3 ) Or phenyl, R 2 Is hydrogen (H) or a protecting group, and contain a triFluoromethyl (-CF) 3 ). The membrane prepared by the polymer of the invention contains hydrophilic and hydrophobic segments, has good micro-phase separation and low swelling ratio.
Specifically, Ar 2 Is sulfonated phenyl with any structure, wherein the structure represents the position of connecting the main chain, and one or more sulfonic acid groups (-SO) can be connected on the benzene ring 3 H) Substituted at the ortho, meta and/or para positions;
Figure BDA0003722660790000041
according to the embodiment of the invention, different sulfonation degrees can be obtained through different proportions of the sulfonation structural unit and the trifluoromethyl structural unit. In a preferred embodiment of the invention, R 2 The hydrogen is sulfonic group ortho-substituted phenyl, sulfonic group meta-substituted phenyl or ortho-and para-disubstituted sulfonated phenyl.
Exemplary, Ar 1 Is phenyl, R 1 Is methyl, R 2 Is H, Ar 2 Is a 2-sulfophenyl group, and the specific structure of the polymer is shown as follows (the polymerization degrees x and y are not shown):
Figure BDA0003722660790000042
the Ubbelohde viscosity of the fluoropolymer containing sulfonic acid groups in the embodiments of the present invention may be from 0.90 to 1.65, as measured with a Ubbelohde viscometer at about 30 ℃. In the invention, the fluorine-containing sulfonated ionic polymer has excellent film forming capacity, mechanical strength and chemical stability. The polymer contains tertiary carbon and quaternary carbon simultaneously, and can carry out post-modification on the tertiary carbon.
In addition, the fluorine-containing sulfonic acid polymer is simple and convenient to prepare, economic and environment-friendly, and is favorable for being used as a proton exchange membrane material to be applied to the field of battery energy.
The embodiment of the invention provides a preparation method of the fluorine-containing sulfonated aromatic polymer, which comprises the following steps:
preparing the fluorine-containing sulfonated aromatic polymer by using aromatic monomers, trifluoromethyl ketones and sulfobenzaldehyde as raw materials through polycondensation; the aromatic monomer is biphenyl or terphenyl; the trifluoromethyl ketone raw material is trifluoromethyl benzophenone or trifluoromethyl ketone; the sulfonic acid benzaldehyde is preferably 2, 4-disulfonic acid benzaldehyde, 2-sulfonic acid benzaldehyde or 3-sulfonic acid benzaldehyde.
In addition to using aromatic monomers of biphenyl or terphenyl, in the embodiment of the invention, trifluoromethyl substituted ketone monomers and sulfonated aromatic aldehyde monomers are used as raw materials, and a super-acid catalyzed Friedel-crafts type polycondensation reaction is adopted to prepare the sulfonated polymer with hydrophilic and hydrophobic segments.
Firstly, the embodiment of the invention adopts a benzaldehyde monomer with sulfonic acid groups as a raw material, and has the structural characteristics that: a sulfonic acid monomer is connected on the benzene ring; more specific structures are shown below, and for the sake of convenience of distinction, are sequentially marked as sulfonic acid aldehyde monomer 1 (2-sulfonic acid benzaldehyde), sulfonic acid aldehyde monomer 2 (3-sulfonic acid benzaldehyde), and sulfonic acid aldehyde monomer 3(2, 4-disulfonic acid benzaldehyde).
Structural formula of Sulfonic aldehyde monomer 1 Sulfonic aldehyde monomer 2 structural formula of Sulfonic aldehyde monomer 3 structural formula
Figure BDA0003722660790000051
Secondly, in the embodiments of the present invention, the structure of trifluoromethyl ketone is not particularly limited, and more specific structures are shown below, wherein trifluoromethyl ketone is represented as trifluoromethyl ketone a monomer, and trifluoromethyl benzophenone is represented as trifluoromethyl ketone B monomer.
Structural formula of trifluoromethyl ketone A monomer structural formula of trifluoromethyl ketone B monomer
Figure BDA0003722660790000052
Thirdly, in the embodiment of the present invention, biphenyl or terphenyl is selected as the aromatic monomer, and the specific structure of the aromatic monomer is as follows:
Figure BDA0003722660790000053
biphenyl;
Figure BDA0003722660790000054
and (3) terphenyl.
The embodiment of the invention has the further key point that proper monomer proportion and monomer concentration are screened out, and super acid such as trifluoromethanesulfonic acid is used as an acid catalyst. Synthesizing the fluorine-containing sulfonated aromatic polymer under the catalysis of super acid. The embodiment of the invention avoids direct sulfonation and can directly prepare the fluorine-containing sulfonated polymer by a one-pot method.
In the embodiment of the invention, the molar concentration ratio of the sulfonic acid benzaldehyde to the trifluoromethyl ketone raw material is 1: (0.5 to 5); the molar concentration ratio of the aromatic monomer to the aldehyde ketone monomer is preferably 1 (1-1.2).
In the examples of the present invention, the polycondensation reaction is carried out in a super acid as a catalyst and a low boiling point solvent. Preferably, the catalyst is trifluoromethanesulfonic acid (TFSA) and/or trifluoroacetic acid (TFA), and the low boiling solvent is preferably Dichloromethane (DCM). Preferably, the temperature of the polycondensation reaction is 20-30 ℃; the reaction time is preferably 10 to 100 hours, more preferably 12 to 80 hours.
In particular, the superacids used in some embodiments of the invention are preferably trifluoromethanesulfonic acid (formula CF) having a purity of 99% 3 SO 3 H) (ii) a The solvent is preferably: dichloromethane (DCM); the reaction temperature is preferably: 20 to 30 ℃. In the embodiment of the invention, the monomer raw materials can react at normal temperature and normal pressure, and the reaction rate can be accelerated by heating properly; dichloromethane with strong dissolving capacity and low toxicity is preferably used as a solvent, and reaction raw materials are economical and easy to obtain. In the embodiment of the invention, metal catalysis is not needed, the unactivated aromatic monomer and the functionalized aldehyde ketone monomer are directly polymerized to carry out Friedel-crafts type polyhydroxylated polymerization reaction, the reaction has high regioselectivity, and a copolymerization (or homopolymerization) polymer can be obtained. The obtained polymer contains tertiary carbon and quaternary carbon at the same time, and the polymer can be post-modified.
The embodiment of the invention provides a method for directly preparing a fluorine-containing sulfonated aromatic polymer, which avoids using a hazardous sulfonating reagent (chlorosulfonic acid, concentrated sulfuric acid) which is easy to cause pollution, does not need metal catalysis, and effectively reduces environmental pollution and danger. In the method for directly synthesizing the fluorine-containing sulfonated ionic polymer, Friedel-crafts hydroxyalkylation polymerization reaction is carried out under a superacid catalyst, an aromatic monomer can be non-activated biphenyl, and a sulfonic acid aldehyde monomer can be monosulfonic acid benzaldehyde or disulfonic acid benzaldehyde. The resulting high molecular weight sulfonic acid polymer (molecular weight about 1 to 50 ten thousand) may be a random or block copolymer. The fluorine-containing sulfonic acid polymer avoids post sulfonation, does not need metal catalysis, has mild reaction condition, and has economic and easily obtained raw materials.
Exemplary simplified reaction formulas are shown below:
Figure BDA0003722660790000061
in the embodiment of the invention, through copolymerization (or homopolymerization), a sulfonic acid group is introduced into the hydrophobic fluorinated aromatic polymer, and the regulation and control of the sulfonation degree can be realized by regulating the ratio of the sulfonated aldehyde to the trifluoromethyl ketone monomer; the resulting polymer exhibits excellent film-forming ability and mechanical strength. The method avoids the use of metal catalysis, reduces the environmental pollution and the cost, and realizes the simple preparation of directly constructing the polymer containing the tertiary carbon and the quaternary carbon by one step.
The method is suitable for functional aldehyde ketone monomers with high activity, and a polycondensation method is adopted to prepare the sulfonic acid type polymer. The sulfonic acid monomer has the structural characteristics that: aldoketones containing one or more sulfonic acid groups; the trifluoromethyl ketone structure is not particularly limited; both unactivated biphenyls and terphenyls may participate in the polymerization. The range of substrates has wide applicability and is readily available.
Preparation of fluorosulfonic acid polymers as described hereinbefore in the examples of the present invention: the aromatic monomer (biphenyl or terphenyl), trifluoromethyl ketone (trifluorobenzophenone A or trifluoromethyl ketone B) and sulfonic acid benzaldehyde (2, 4-disulfonic acid benzaldehyde, 2-sulfonic acid benzaldehyde or 3-sulfonic acid benzaldehyde) are used as raw materials, and the aromatic monomer (biphenyl or terphenyl), the trifluoromethyl ketone (trifluorobenzophenone A or trifluoromethyl ketone B) and the sulfonic acid benzaldehyde are prepared by polycondensation in super-strong acid (trifluoromethane sulfonic acid TFSA, trifluoroacetic acid TFA and the like) used as a catalyst and a low-boiling point solvent (dichloromethane). Among them, the sulfonated benzaldehyde monomer is preferably 2, 4-disulfonic acid benzaldehyde or 3-sulfonic acid benzaldehyde, and has an electron-withdrawing sulfonic acid group as a common characteristic.
Further illustratively, the fluorosulfonic acid-containing polymer is prepared by the general process: adding 10ml of TFSA into a round-bottom flask at 25 ℃, then placing sulfonic acid aldehyde monomer 1 or 2 or 3(0.012mol) into super acid and stirring until the sulfonic acid aldehyde monomer is dissolved, dissolving biphenyl monomer (0.01mol) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the round-bottom flask and stirring; adding 10ml of TFSA into another round-bottom flask, then placing trifluoromethyl ketone monomer A or B (0.012mol) into super acid, dissolving biphenyl monomer (0.01mol) in 10ml dichloromethane, adding the dissolved biphenyl monomer into the round-bottom flask, and stirring; polymerizing for a period of time, mixing, and continuously polymerizing and stirring for a period of time. Slowly immersing the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups.
The invention provides a sulfonic acid type ion exchange membrane which is composed of the fluorine-containing sulfonated aromatic polymer. The specific preparation process is exemplified as follows:
taking the purified fluorine-containing sulfonic acid polymer, preparing 5-10 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying to remove a solvent, carrying out acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify the sulfonic acid film, and washing to obtain the sulfonic acid type ion exchange membrane. Wherein, acidifying a sulfonic acid membrane: the ammonium sulfonate is converted to sulfonate by acidification as the polymer is phase converted by settling in aqueous ammonia.
In some embodiments of the invention, the sulfonic acid-type ion-exchange membrane has a proton conductivity at 80 ℃ of 85mS cm -1 Above, preferably 100mS cm -1 The above. In addition, the invention also provides the application of the sulfonic acid type ion exchange membrane in a fuel cell.
The invention mainly aims to prepare the fluorine-containing sulfonated aromatic copolymer by taking trifluoromethyl ketone and sulfonic aldehyde monomers as raw materials and adopting Friedel-crafts type polycondensation reaction. The prepared polymer has an ether-free rigid aryl framework, and can endow a polymer film with good thermal stability and oxidation stability. The prepared ionic polymer membrane contains hydrophilic and hydrophobic segments, and has good microphase separation and low swelling rate. The method has mild reaction conditions, does not need post-sulfonation, and can control the sulfonation degree by regulating and controlling the monomer ratio. Meanwhile, the method can avoid using metal catalysis, reduce environmental pollution and has low cost. In addition, the resulting polymer backbone contains tertiary and quaternary carbons, which can be post-modified.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum (solvent: DMSO-d6) of a fluorosulfonic acid-containing polymer prepared in example 1;
FIG. 2 is a nuclear magnetic resonance carbon spectrum (solvent: DMSO-d6) of a fluorosulfonic acid-containing polymer prepared in example 1;
FIG. 3 is a photomicrograph of a fluorosulfonic acid polymer film made in example 1;
fig. 4 shows the results of cell performance tests on fluorosulfonic acid polymer membranes prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
Example 1
Adding 10ml TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfonic acid aldehyde monomer 3 (disulfonic acid benzaldehyde; 0.012mol, 3.195g) into super acid, stirring until the sulfonic acid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.01mol, 1.542g) into 10ml dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 24 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottomed flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 96%. The Wye viscosity is: 1.56; the viscosities of the examples are summarized in table 1.
The structural characterization results of the obtained fluorosulfonic acid polymer are shown in fig. 1 and fig. 2; the tertiary hydrogen singlet b of the polymer backbone is shown at 6.69ppm by 1H NMR spectroscopy (FIG. 1), with the chemical shift shifted to the left due to the conjugated resonance with the benzene ring. By 13C NMR spectrum (FIG. 2), 55ppm of the quaternary carbon a to which a trifluoromethyl group is bonded and 50ppm of the tertiary carbon b to which a benzene ring having a sulfonic acid group is bonded were obtained.
The structure of the obtained fluorine-containing block polymer containing sulfonic acid groups is shown as follows:
Figure BDA0003722660790000091
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, carrying out film casting on a glass plate after filtering to form a film, drying to remove a solvent, carrying out acidification treatment for 24 hours by using 2mol/l sulfuric acid solution, and washing by using deionized water to obtain the sulfonic acid type ion exchange membrane, wherein a picture of a real object is shown in figure 3. The transparent film as shown in the figure is prepared by film forming through a casting method, the thickness of the film is 50 mu m, and the mechanical property of the film is good.
The resulting fluorosulfonic acid-containing polymer membranes had water absorption swelling ratios as summarized in table 2 and conductivity test results as summarized in table 3. The applied battery includes: the proton exchange membrane battery core component is provided with a proton exchange membrane at the middle part and cathode and anode catalyst layers attached to the two ends of the proton exchange membrane; in addition, a gas diffusion layer is disposed between the fuel (hydrogen or methanol) and the oxidant (oxygen or air), and the performance test results are shown in fig. 4.
The test method and results are as follows: an electrode was prepared using carbon-supported platinum (Pt/C) as the anode and cathode catalysts, and the Pt/C catalysts were deposited on 3cm by 3cm carbon paper with a catalyst loading of 1.0mg cm on the carbon paper -2 And obtaining the polarization curve of the battery at 60 ℃ in a current step mode. The battery temperature tested by the application is 60 ℃, and the current density is 241.18mA/cm -2 The power density reaches 80.62mW/cm -2 。
Example 2
Adding 10ml TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then putting a sulfoaldehyde monomer 3(0.012mol, 3.195g) and a trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, and stirring until the sulfoaldehyde monomer is dissolved; biphenyl monomer (0.02mol, 3.084g) was dissolved in 20ml of methylene chloride, and the dissolved biphenyl monomer was added to the above eggplant-shaped bottle and reacted for 60 hours under sealed conditions. Slowly immersing the obtained viscous solution into ammonia water to obtain white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing random polymer containing sulfonic acid groups, wherein the yield is 96%. The Wye viscosity is: 1.25.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, filtering, casting the solution on a glass plate to form a film, drying to remove a solvent, carrying out acidification treatment by using 2mol/l sulfuric acid solution for 24 hours, and washing by using deionized water to obtain the sulfonic acid type ion exchange membrane.
Example 3
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfonic acid aldehyde monomer 3(0.012mol, 3.195g) into a superacid, stirring until the sulfonic acid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and carrying out sealing reaction for 36 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottomed flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 98%. The Wye viscosity is: 1.35.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, filtering, casting the solution on a glass plate to form a film, drying to remove a solvent, carrying out acidification treatment by using 2mol/l sulfuric acid solution for 24 hours, and washing by using deionized water to obtain the sulfonic acid type ion exchange membrane.
Example 4
Adding 9ml of TFSA and 1ml of TFA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing sulfonic aldehyde monomer 3(0.012mol, 3.195g) into superacid, stirring until the sulfonic aldehyde monomer is dissolved, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 46 hours; adding 9ml of TFSA and 1ml of TFA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottomed flask, and sealing and reacting for 4 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the sealing reaction is continued for 20 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 96%. The Wye viscosity is: 1.06.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, filtering, casting the solution on a glass plate to form a film, drying a solvent, acidizing by using 2mol/l sulfuric acid solution for 24 hours, and washing by using deionized water to obtain the sulfonic acid type ion exchange membrane.
Example 5
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfoacid aldehyde monomer 3(0.008mol, 2.130g) into superacid, stirring until the sulfoacid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.006mol, 1.028g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 24 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.016mol, 1.793g) into superacid, dissolving biphenyl monomer (0.014mol, 2.056g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottom flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 99%. The Wye viscosity is: 1.65.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, filtering, casting the solution on a glass plate to form a film, drying a solvent, acidizing by using 2mol/l sulfuric acid solution for 24 hours, and washing by using deionized water to obtain the sulfonic acid type ion exchange membrane.
Example 6
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfoacid aldehyde monomer 3(0.004mol, 1.065g) into super acid, stirring until the sulfoacid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.003mol, 0.514g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and carrying out sealing reaction for 24 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.020mol, 2.240g) into superacid, dissolving biphenyl monomer (0.017mol, 2.570g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottom flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 98%. The Wye viscosity is: 1.20.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
Example 7
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing sulfonic aldehyde monomer 3(0.016mol, 4.260g) into super acid, stirring until the sulfonic aldehyde monomer is dissolved, dissolving biphenyl monomer (0.014mol, 2.056g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 24 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.008mol, 0.896g) into superacid, dissolving biphenyl monomer (0.006mol, 1.028g) in 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottomed flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 98%. The Wye viscosity is: 1.21.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
Example 8
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing sulfonic aldehyde monomer 3(0.020mol, 5.325g) into superacid, stirring until the sulfonic aldehyde monomer is dissolved, dissolving biphenyl monomer (0.017mol, 2.570g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 24 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.004mol, 0.448g) into superacid, dissolving biphenyl monomer (0.003mol, 0.514g) in 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottom flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 99%. The Wye viscosity is: 1.30.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
Example 9
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfoacid aldehyde monomer 1(0.012mol, 2.234g) into superacid, stirring until the sulfoacid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and carrying out sealed reaction for 54 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottomed flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is sealed and reacts for 20 hours continuously. Slowly immersing the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 95%. The Wye viscosity is: 0.92.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
The structure of the polymer is as follows:
Figure BDA0003722660790000131
example 10
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfonic acid aldehyde monomer 2(0.012mol and 2.234g) into superacid, stirring until the sulfonic acid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.01mol and 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 48 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottomed flask, and sealing and reacting for 2 hours; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacts for 18 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 96%. The Wye viscosity is: 0.98.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
The structure of the polymer is as follows:
Figure BDA0003722660790000141
example 11
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfonic acid aldehyde monomer 3(0.012mol, 3.195g) into a superacid, stirring until the sulfonic acid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 24 hours; adding 10ml of TFSA into another eggplant-shaped bottle, then placing trifluoromethyl ketone monomer B (0.012mol, 2.089g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) in 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottom flask, and sealing and reacting for 1 h; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the sealing reaction is continued for 10 hours. Slowly immersing the obtained viscous solution into ammonia water to obtain white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 96%. The Wye viscosity is: 1.42.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
Example 12
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 25 ℃, then placing a sulfoacid aldehyde monomer 3(0.012mol, 3.195g) into superacid, stirring until the sulfoacid aldehyde monomer is dissolved, dissolving a terphenyl monomer (0.01mol, 2.303g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and sealing and reacting for 12 hours; adding 10ml of TFSA into the other eggplant-shaped bottle, then putting the trifluoromethyl ketone monomer A (0.012mol, 1.344g) into the superacid, dissolving the biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the round-bottom flask, and sealing and reacting for 0.5 h; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is sealed and reacts for 6 hours continuously. Slowly sinking the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 94%. The Wye viscosity is: 1.57.
taking 1g of purified polymer, preparing a 5 wt% casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, filtering, casting the solution on a glass plate to form a membrane, drying the solvent, carrying out acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify the sulfonic acid membrane, and washing by using deionized water to obtain the sulfonic acid type ion exchange membrane.
Example 13
Adding 10ml of TFSA into a 50ml eggplant-shaped bottle at the temperature of 30 ℃, then placing a sulfoacid aldehyde monomer 3(0.012mol, 3.195g) into a superacid, stirring until the sulfoacid aldehyde monomer is dissolved, dissolving a biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into the eggplant-shaped bottle, and carrying out sealing reaction for 24 hours; adding 10ml of TFSA into the other eggplant-shaped bottle, then placing trifluoromethyl ketone monomer A (0.012mol, 1.344g) into superacid, dissolving biphenyl monomer (0.01mol, 1.542g) into 10ml of dichloromethane, adding the dissolved biphenyl monomer into a round-bottom flask, and sealing and reacting for 2 h; the two eggplant-shaped bottles are polymerized respectively for a period of time and then mixed, and the mixture is continuously sealed and reacted for 12 hours. Slowly sinking the obtained viscous solution into ammonia water to obtain a white solid, washing and filtering for multiple times, performing soxhlet extraction by methanol, and drying in vacuum to obtain a polymer, namely the fluorine-containing block polymer containing sulfonic acid groups, wherein the yield is 96%. The Wye viscosity is: 1.11.
taking 1g of purified polymer, preparing 5 wt% of casting solution by using dimethyl sulfoxide in a 100ml single-neck flask, casting the solution on a glass plate to form a film after filtering, drying a solvent, performing acidification treatment by using 2mol/l sulfuric acid solution for 24 hours to completely acidify a sulfonic acid film, and washing by using deionized water to obtain the sulfonic acid type ion exchange film.
Viscosity (. eta.) test: 125mg/25mL of the dimethylsulfoxide solutions of the polymers prepared in examples 1 to 13 were prepared and tested at 30 ℃ using an Ubbelohde viscometer. The results are shown in Table 1, where Table 1 is a table of viscosities (. eta.) of the polymers prepared in examples 1 to 13. The results show that the copolymerization polymers with different viscosities can be obtained by changing the concentration and the type of different monomers in the reaction.
And (3) measuring the water absorption swelling ratio:
the acidified polymer films (10mm x 30mm) prepared in examples 1-13 were placed in an 80 ℃ oven for vacuum drying for 48h, and the weight, length and width of the film sample in the dry state were recorded and held for 24 h. The film sample was wiped dry of moisture on the film surface with filter paper and its mass was immediately weighed, followed by measuring the length and width of the film sample with a micrometer.
The water absorption of the film is calculated as follows:
Figure BDA0003722660790000161
wherein: w is a group of Wet Is the weight (g) of the acidified film after it has absorbed sufficient water;W dry is the weight (g) of the acidified dry film.
The swelling ratio of the membrane is calculated as follows:
Figure BDA0003722660790000162
wherein: s Wet Is the product of the length and width (cm) of the wet film 2 )；S dry Is the product of the length and width (cm) of the dry film 2 )。
Proton conductivity test:
the polymer membranes (10mm x 40mm) prepared in examples 1-13 after acidification were tested for proton membrane resistance using an electrochemical workstation. The amplitude of disturbance voltage adopted by the test is 10mv, and the scanning frequency is 0.1-100 KHz. In the test process, deionized water is filled at two sides of the test module, and the conductivity of the membrane is tested at 80 ℃; the test was carried out after 30min of storage in water.
The conductivity σ of the proton exchange membrane can be calculated by the following formula:
Figure BDA0003722660790000163
wherein: l is the distance between the two poles (L is 1cm in this experiment); r is the resistance of the film as measured by the workstation reading; s is the area of the membrane.
Table 1 results of viscosity tests of fluorosulfonic acid polymers prepared in examples 1-13
Figure BDA0003722660790000164
Figure BDA0003722660790000171
[η]XXXXX dL/g(XXX％solution in XXX at 30.0(0.1℃)
Table 2 results of water absorption swelling ratio test of fluorosulfonic acid polymer membranes prepared in examples 1 to 13
Serial number Water absorption (80 ℃ C.)/(%) Swelling ratio (80 ℃ C.)/(%)
Example 1 30 29
Example 2 26 30
Example case 3 23 39
Example 4 20 35
Example 5 9 6
Example 6 5 4
Example 7 62 55
Example 8 80 60
Example 9 12 10
Example 10 16 20
Example 11 36 40
Example 12 50 36
Example 13 32 40
Table 3 results of conductivity tests of fluorosulfonic acid polymer membranes prepared in examples 1-13
Serial number Proton conductivity (80 ℃ C.)/(mS cm -1 )
Example 1 220
Example 2 200
Example 3 205
Example 4 180
Example 5 140
Example 6 85
Example 7 325
Example 8 396
Example 9 140
Example 10 150
Example 11 200
Example 12 180
Example 13 220
As can be seen from the above, the embodiments of the present invention provide a method for directly synthesizing a fluorinated sulfonated ionic polymer, in which friedel-crafts hydroxyalkylation polymerization is performed in the presence of an acid catalyst, so that the aromatic monomer can be non-activated biphenyls, and the sulfonic acid aldehyde monomer can be monosulfonic acid benzaldehyde or disulfonic acid benzaldehyde. The fluorine-containing sulfonic acid polymer avoids post sulfonation, does not need metal catalysis, has mild reaction condition, and has economic and easily obtained raw materials.
Some embodiments may use commercial biphenyl, trifluoroacetone, sulfonated aldehyde monomers to prepare fluorosulfonic acid polymers by friedel-crafts type polycondensation reactions by superacid catalyzed polymerization without metals. The IEC (different sulfonic acid group contents are regulated and controlled by controlling the proportion of the sulfonic acid aldehyde and the fluoroketone monomer and the polymerization process, and the IEC is the amount of ions which can be exchanged by the ion exchange material in unit volume or mass and is also the number of sulfonic acid groups in unit mass), the polymerization sites have strong regioselectivity, and the polymer can not be crosslinked by reaction at normal temperature and normal pressure. The polymer containing both tertiary carbon and quaternary carbon is prepared by the method, and the tertiary carbon can be post-modified. The method avoids using dangerous sulfonating reagent, has no crosslinking phenomenon, has simple post-treatment, high polymerization rate and no need of metal catalysis, and has wide practical application prospect.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.

Claims (10)

1. A fluorosulfonated aromatic polymer, comprising both tertiary and quaternary carbons, having a structure of formula 1:
Figure FDA0003722660780000011
wherein R is 1 Is methyl or phenyl, R 2 Is hydrogen or a protecting group; ar (Ar) 1 Is phenyl or biphenyl, Ar 2 Is at least one sulfonic substituted phenyl group; x and y are both degrees of polymerization.
2. The fluorosulfonated aromatic polymer of claim 1, wherein R is 2 Is hydrogen, Ar 2 Is a group of any one of the following structures:
Figure FDA0003722660780000012
3. the method for producing a fluorosulfonated aromatic polymer as claimed in claim 1 or 2, comprising the steps of:
preparing the fluorine-containing sulfonated aromatic polymer by using aromatic monomers, trifluoromethyl ketones and sulfobenzaldehyde as raw materials through polycondensation;
the aromatic monomer is biphenyl or terphenyl; the trifluoromethyl ketone raw material is trifluoromethyl benzophenone or trifluoromethyl ketone; the sulfonic acid benzaldehyde is preferably 2, 4-disulfonic acid benzaldehyde, 2-sulfonic acid benzaldehyde or 3-sulfonic acid benzaldehyde.
4. The method according to claim 3, wherein the molar concentration ratio of the sulfonic acid benzaldehyde to the trifluoromethyl ketone is 1: (0.5-5).
5. The method for preparing fluorosulfonated aromatic polymer according to claim 3, wherein the polycondensation is performed in a super acid as a catalyst and a low-boiling solvent.
6. The method for preparing a fluorosulfonated aromatic polymer compound of claim 5, wherein the catalyst is trifluoromethanesulfonic acid and/or trifluoroacetic acid, and the low-boiling solvent is preferably dichloromethane.
7. The method of claim 5, wherein the polycondensation is carried out at a temperature of 20 to 30 ℃ for 10 to 100 hours.
8. A sulfonic acid type ion exchange membrane comprising the fluorinated sulfonated aromatic polymer according to claim 1 or 2.
9. The sulfonic acid-type ion-exchange membrane according to claim 8, wherein the sulfonic acid-type ion-exchange membrane has a proton conductivity of 85 mS-cm at 80 ℃ -1 Above, preferably 100mS cm -1 The above.
10. Use of the sulfonic acid type ion exchange membrane according to claim 8 or 9 in a fuel cell.
CN202210756448.0A 2022-06-30 2022-06-30 Fluorine-containing sulfonated aromatic polymer, preparation method and application thereof Pending CN115057980A (en)

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Citations (2)

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CN113150344A (en) * 2021-04-21 2021-07-23 常州大学 Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof
CN113150248A (en) * 2021-04-01 2021-07-23 中国长江三峡集团有限公司 Ether-bond-free aryl sulfonated non-fluorine ionomer and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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CN113150248A (en) * 2021-04-01 2021-07-23 中国长江三峡集团有限公司 Ether-bond-free aryl sulfonated non-fluorine ionomer and preparation method and application thereof
CN113150344A (en) * 2021-04-21 2021-07-23 常州大学 Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof

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