CN115044048A - Block type ether bond-free polymer, preparation method thereof, ion exchange membrane, fuel cell or flow battery - Google Patents
Block type ether bond-free polymer, preparation method thereof, ion exchange membrane, fuel cell or flow battery Download PDFInfo
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Abstract
The application provides a block type ether bond-free polymer, a preparation method thereof, an ion exchange membrane, a fuel cell or a flow battery, wherein the block type ether bond-free polymer has a structure shown in a formula 1. The polymer has an obvious hydrophilic-hydrophobic micro-phase structure, good chemical stability, low swelling property and high ionic conductivity. The polymer provided by the invention respectively obtains anion/cation type polymers through super acid catalysis reaction and functionalization post-modification reaction, the structure of the block type ether bond-free polymer can be efficiently and controllably designed, and thenThe grafting reaction expands the application range of the polymer.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a block type ether bond-free polymer, a preparation method thereof, an ion exchange membrane, a fuel cell or a flow battery.
Background
Recently, Hydrogen Energy Fuel Cells (HEFCs) have been rapidly developed as a ring of new energy industries, wherein the HEFCs mainly include proton fuel cells (PEMFCs) and alkaline fuel cells (AEMFCs). The ion exchange membrane is used as a key component of the HEFC, and plays a key role in ion transfer and isolation of fuel and oxidant between an anode and a cathode. In order to satisfy the long-term stable operation of HEFC, an ideal ion exchange membrane material should have high conductivity, excellent chemical stability, appropriate water absorption/swelling ratio, and good mechanical stability. Generally, increasing the Ion Exchange Capacity (IEC) can achieve high conductivity of the membrane, especially for AEMFC, but high IEC also increases the water absorption/swelling ratio of the ionic membrane, affects the dimensional stability and mechanical strength of the membrane, and is not conducive to long-term stable operation of the fuel cell.
The block-structured ionic polymer has the characteristic of a centralized hydrophilic segment-hydrophobic segment distribution rule, the formed microphase separation structure can rapidly transfer water molecules and counter ions, and meanwhile, the block structure is also favorable for reducing the water absorption/swelling ratio of the membrane, so that the membrane can still keep relatively high ionic conductivity under low IEC. At present, the common block-type ion exchange membranes are mainly polyarylethers prepared by polycondensation and polyolefins prepared by active polymerization, and then are ionized by post-modification reaction. However, such ion exchange membranes have difficulty maintaining the chemical stability of the polymer backbone under strong acid/base conditions, especially in the presence of a strong oxidizing environment in the fuel cell. Therefore, the development of a block-type ion exchange membrane with a polymer skeleton with stable chemical and obvious phase separation behavior is a difficult point of the current work. The block copolymer prepared by the current common method adopts polycondensation and active polymerization, strict anhydrous and anaerobic conditions are generally required in the synthesis process, and the preparation cost and complexity are greatly increased.
Researches show that the construction of a polymer skeleton without ether bonds is an effective method for meeting the stability of a membrane material, and the aryl ether bonds in the traditional polyarylether polymers are easily attacked and broken under strong acid/alkali conditions, so that the long-term stability of the ionic membrane is not facilitated. Therefore, in recent years, the wholly aromatic skeleton polymer prepared by super acid catalytic polymerization has the advantages of simple synthesis, high reaction efficiency, mild conditions, easy obtainment of high molecular weight polymer and the like, becomes an important method for preparing the ether-free polymer, and is widely applied to the preparation of polyelectrolyte membranes of fuel cells of acid/alkali and flow batteries. The functionalized polyphenylalkylene polymer is prepared by superacid catalysis, generally an aromatic monomer rich in electrons is selected, and the aromatic monomer and a ketone monomer are synthesized into a polymer under the catalysis of trifluoromethanesulfonic acid, and the polymer is functionalized through a post-modification reaction. In the synthesis process, due to the difficulty in controlling the polymerization duration and the difference of the monomer activity, the prepared polymer is mainly a random polymer, and although a phase separation morphology in a small range can be constructed in the modes of side chain regulation, self-assembly and the like, the long-range ordered and large-range hydrophilic-hydrophobic membrane morphology is difficult to realize.
Currently, achieving the goals of both good chemical stability and high ionic conductivity is still challenging compared to ion exchange membrane materials that have been commercialized. With the wider application of ion exchange membranes in the fields of water treatment and energy, but at present, an effective and simple method for synthesizing a block type ion exchange membrane without ether bonds is lacked, and the development of a high-performance polyelectrolyte membrane with high chemical stability and simple and convenient synthesis method has important research and economic values.
Disclosure of Invention
In view of the above, the present invention provides a block type ether bond-free polymer, a preparation method thereof, an ion exchange membrane, a fuel cell or a flow battery, which is beneficial to improving the conductivity of the ion exchange membrane and reducing the water absorption swelling property of the ion exchange membrane.
In order to achieve the above purpose, the technical scheme of the invention is a block type ether bond-free polymer, which has a structure shown in formula 1:
wherein n is the degree of polymerization, m is selected from 1 to 10, x is selected from 0.3 to 0.7, y is selected from 0.3 to 0.7, and x + y is 1;
x is selected from halogen or structures (formula X-1) to (formula X-5):
ar is selected from substituted or unsubstituted aromatic groups.
In one embodiment, the block-type ether bond-free polymer has the structure of formula 1. Wherein n is a polymerization degree, preferably 10 or more, and more preferably 20 or more. m is an integer selected from 1 to 10, preferably 2 to 5. x is selected from 0.3-0.7, preferably 0.4; y is selected from 0.3 to 0.7, preferably 0.6, and x + y is 1. X is selected from halogen or structures represented by (formula X-1) to (formula X-5), and halogen is preferably bromine (Br).
In one embodiment, the block-type ether bond-free polymer has the structure of formula 1, wherein Ar is selected from substituted aromatic groups, and the substituted groups are selected from C 1-15 An alkyl group.
In one embodiment, the block-type ether bond-free polymer has the structure of formula 1, wherein Ar is selected from substituted aromatic groups, and the substituted groups are selected from C 1-15 An alkyl group, the aromatic group being selected from biphenyl group or fluorenyl group.
In one embodiment, the block-type ether bond-free polymer has a structure shown in formula 1, wherein Ar is selected from the structures shown in (formula Ar-1) to (formula Ar-4):
wherein a is selected from 1-9.
In the block type ether bond-free polymer provided by the invention, the block type polymer is prepared by connecting two or more polymer chain segments with different properties and certain length together. Experimental results show that the conductivity of the ion exchange membrane prepared from the block-type ether bond-free polymer is higher than that of the random ether bond-free polymer, and meanwhile, the swelling rate of the ion exchange membrane prepared from the block-type ether bond-free polymer is lower than that of the random ether bond-free polymer, so that the ion exchange membrane has an obvious hydrophilic-hydrophobic micro-phase structure, and the stability of the membrane can be effectively improved. The random polymer is a polymer formed by two or more monomers in polymerization reaction and distributed randomly, the ether bond-free ion exchange membrane is used for a high-molecular diaphragm of ion transmission, and the main chain of the polymer does not have carbon ether bonds formed by polycondensation reaction and mainly consists of a full aromatic skeleton. Compared with an ion exchange membrane material containing ether bonds, the ion exchange membrane without ether bonds can maintain more excellent chemical stability.
The invention also provides a preparation method of the block type ether bond-free polymer in the technical scheme, which is characterized by comprising the following steps:
adopting an acid catalyst, taking an aromatic monomer and trifluoroacetone as raw materials, and carrying out polymerization reaction to obtain a polymer intermediate 1;
adopting an acid catalyst, taking a halogenated dialkyl fluorene monomer shown in a formula 6 and trifluoroacetone as raw materials, and carrying out polymerization reaction to obtain a polymer intermediate 2;
wherein m is 1-10;
and (3) carrying out copolymerization reaction on the polymer intermediate 1 and the polymer intermediate 2 to obtain the block-type ether bond-free polymer.
The method comprises the steps of mixing an aromatic monomer and trifluoroacetone serving as a raw material in an aprotic solvent, wherein the molar ratio of the aromatic monomer to the trifluoroacetone is 1: 1.1-1.2, and the aprotic solvent comprises one or more of dichloromethane and chloroform. Under the low-temperature condition, the system adopts an acid catalyst to carry out polymerization reaction, the low temperature is selected from minus 40 ℃ to 10 ℃, preferably 0 ℃, the acid catalyst comprises but is not limited to one or more of trifluoromethanesulfonic acid, methanesulfonic acid and Eton's reagent, and the volume ratio of the super acid to the aprotic solvent is 1: 0.5-2.0; the reaction temperature of the polymerization reaction is room temperature, and the reaction time is 5-40 minutes, so that the polymer intermediate 1 with the structural unit shown in the formula 7 is obtained.
The halogenated dialkyl fluorene monomer with the structure shown in the formula 6 and trifluoroacetone are mixed in an aprotic solvent, wherein the molar ratio of the halogenated dialkyl fluorene monomer with the structure shown in the formula 6 to the trifluoroacetone is 1: 1.1-1.2, and the aprotic solvent comprises one or more of dichloromethane and chloroform. Under the low temperature condition, the system adopts an acid catalyst to carry out polymerization reaction, the low temperature is selected from minus 40 ℃ to 10 ℃, preferably 0 ℃, the acid catalyst comprises one or more of trifluoromethanesulfonic acid, methanesulfonic acid and Eton's reagent, and the volume ratio of the super acid to the aprotic solvent is 1: 0.5-2.0. The reaction temperature of the polymerization reaction is room temperature, and the reaction time is 5-40 minutes, so that the polymer intermediate 2 with the structural unit shown in the formula 8 is obtained.
And mixing the obtained polymer systems of the structural units shown in the formulas 7 and 8 for copolymerization reaction, wherein the reaction temperature is room temperature, the reaction time is 5-40 minutes, after the reaction is finished, pouring the product into ethanol to precipitate a polymer, and washing and drying the polymer to obtain the polymer with the structure shown in the formula 1.
In one embodiment, an aromatic monomer and a trifluoroacetone solution are added into a pressure-resistant bottle containing an aprotic solvent, wherein the molar ratio of the aromatic monomer to the trifluoroacetone is 1: 1.1-1.2, and the aprotic solvent comprises one or more of dichloromethane and chloroform. Adding a super acid as a catalyst at a low temperature, wherein the solid content of the super acid is 20-30%, the low temperature is-40-10 ℃, preferably 0 ℃, the acid catalyst comprises one or more of trifluoromethanesulfonic acid, methanesulfonic acid and Eton's reagent, and the volume ratio of the super acid to the aprotic solvent is 1: 0.5-2.0. And (3) magnetically stirring the mixture to react for 5 to 40 minutes at room temperature to obtain a viscous homopolymer solution containing the structure of the formula 7. And simultaneously adding a halogenated dialkyl fluorene monomer with a structure shown in a formula 6 and a trifluoroacetone solution into a pressure-resistant bottle containing an aprotic solvent, wherein the molar ratio of the halogenated dialkyl fluorene monomer with the structure shown in the formula 6 to the trifluoroacetone is 1: 1.1-1.2, and the aprotic solvent comprises one or more of dichloromethane and chloroform. Adding a super acid as a catalyst at a low temperature, wherein the low temperature is-40-10 ℃, preferably 0 ℃, the acid catalyst comprises but is not limited to one or more of trifluoromethanesulfonic acid, methanesulfonic acid and Eton's reagent, and reacting for 5-40 minutes at room temperature by magnetic stirring to obtain a viscous homopolymer solution containing a structure in formula 8. And (3) completely pouring the viscous homopolymer solution containing the structure of the formula 7 into a viscous homopolymer solution system containing the structure of the formula 8, continuing to react for 5-40 minutes, pouring the product into ethanol to precipitate a polymer, washing and drying to obtain the polymer with the structure shown in the formula 1.
The preparation method of the block type ether bond-free polymer also comprises the following steps: functionalizing the block ether bond-free polymer to obtain a functionalized ionized polymer. The functionalization is in particular: dissolving the polymer with the structure shown in the formula (1) in a polar solvent, wherein the polar solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone. And then carrying out graft copolymerization reaction with 1.0-1.5 equivalent of monomer for ionization, wherein the reaction time is 0-24 h, the reaction temperature is 25-45 ℃, and a product after the reaction is finished is poured into ether to separate out a functionalized ionized polymer, wherein the polymer has a structure shown in a formula 10:
wherein Z includes but is not limited to the structures shown in (formula X-1) to (formula X-5):
wherein, m, x, y, n and Ar are the same as those shown in formula 1, and are not described herein again.
The preparation method of the block type ether bond-free polymer provided by the invention utilizes super acid catalysis, the obtained polymer has good chemical stability, and the block type ether bond-free main chain polymer with the structure shown in the formula 1 and trimethylamine, 1-methylpiperidine, 1-methylpyrrolidine and the like are used for preparing the block type anion exchange membrane; preparing the block type cation exchange membrane by potassium thioacetate and post-oxidation. The polyelectrolyte membrane prepared by ionizing the block type ether-free main chain polymer has better conductivity, low swelling rate and good stability.
The invention also provides an ion exchange membrane, which comprises the block type ether bond-free polymer in the technical scheme, and the details are not repeated. The anion exchange membrane can be formed by the polymer of the technical scheme through a flow-extension method.
The invention also provides a fuel cell or a flow battery, which comprises the ion exchange membrane in the technical scheme, and the details are not repeated herein. The reagent of the invention can be directly purchased and obtained.
Throughout this disclosure, the meaning of terms is described as follows:
the term "halogen" includes chlorine (Cl), fluorine (F), bromine (Br) and iodine (I).
The term "aromatic group" includes monocyclic, or bicyclic, or polycyclic, for example selected from the group consisting of phenyl, biphenyl or fluorenyl, optionally substituted by one or more C 1-6 Alkyl radical, C 1-6 Alkoxy, halogen, amino or aryl substitution.
The term "C 1-15 Alkyl "includes alkyl or alkylene groups of the specified length in a straight chain, branched chain or cyclic structure. The straight chain alkyl groups may be methyl, ethyl, propyl, butyl, pentyl, hexyl, or their corresponding unsaturated straight chain alkyl groups including, but not limited to, ethylene. The branched alkyl groups may be isopropyl, sec-butyl, tert-butyl, isopentyl, isohexyl, or their corresponding unsaturated branched alkyl groups including, but not limited to, isopropene. The cycloalkyl group may be C 3-15 Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or their corresponding unsaturated cycloalkyl groups including, but not limited to, cyclopropene.
It is to be understood that the compounds of the present invention as described herein can each be substituted with any number of substituents or functional moieties. Generally, the term "(substituted)" (whether or not it follows the term "optionally") and substituents contained in the formulae of the present invention all refer to the replacement of a hydrogen radical in a given structure with the radical of the indicated substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at each position. The term "substituted" as used herein is intended to include substitution with all permissible substituents of organic compounds, any of which are described herein.
For example, substituents include, but are not limited to, the following groups that result in the formation of a stabilizing moiety: alkyl, aromatic, acyl, cyano, isocyano, nitro, hydroxyl, carboxyl, thiol, and halo, and any combination thereof. The present invention encompasses any and all such combinations to obtain stable substituents/moieties.
The invention provides a block type ether bond-free polymer which has a structure shown in a formula 1. The polymer has good chemical stability and low swelling property, has an obvious hydrophilic-hydrophobic micro-phase structure, and can effectively improve the dimensional stability of the membrane and the ionic conductivity. The polymer provided by the invention respectively obtains anionic/cationic polymers through super acid catalysis reaction and functionalization post-modification reaction, the structure of the block type ether bond-free polymer can be efficiently and controllably designed, and the post-grafting reaction expands the application range of the polymer.
Drawings
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. However, the present invention is not limited to the following embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
FIG. 1 is the NMR spectrum of PFA-Br, a block type ether bond-free main chain polymer obtained in example 1;
FIG. 2 is the NMR spectrum of the quaternary ammonium type block ionic cationic polymer PFA-QA obtained in example 8;
FIG. 3 shows the sulfonated block anionic Polymer PFA-SO obtained in example 10 3 Na NMR hydrogen spectrum;
FIG. 4 is a graph of atomic force and small angle scattering for both block and random PFA-QA films.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 invention.
Example 1:
the reaction route of the block type ether bond-free polymer PFA-Br is shown as follows:
after 1.97g (4mmol) of bromodihexylfluorene monomer, 0.51g (4.5mmol) of a trifluoroacetone solution and 5mL of dichloromethane were added to a dry pressure-resistant bottle A, the temperature of the system was lowered to 0 ℃. Then 5mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle A, and after the temperature was raised to 25 ℃, the reaction was carried out for 15 minutes with magnetic stirring.
After 0.92g (6mmol) of biphenyl, 0.78g (7mmol) of trifluoroacetone and 3mL of dichloromethane were charged in a pressure bottle B, the temperature of the system was lowered to 0 ℃. Then 3mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle B, and after the temperature was raised to 25 ℃, the reaction was carried out for 15 minutes with magnetic stirring.
And pouring the reaction product in the system B into the system A, continuously stirring for reacting for 30 minutes, and pouring the reaction system into ethanol to separate out polymer solids. And (3) washing the polymer with water, and drying in vacuum to obtain a block ether bond-free main chain polymer PFA-Br (the proportion of the brominated fluorenyl monomer is 40 percent, and x is 0.4).
The nuclear magnetic resonance hydrogen spectrum of the block type ether bond-free main chain polymer PFA-Br is shown in figure 1, figure 1 is the nuclear magnetic resonance hydrogen spectrum of the block type ether bond-free main chain polymer PFA-Br obtained in example 1, 1 chemical shifts of protons on an aromatic ring in an H NMR spectrum are between 7.65 ppm and 7.17ppm, peaks of methylene groups connected with bromine atoms are 3.19ppm, methylene groups on the other 5 chemical environment long alkyl groups are respectively 1.89ppm, 1.58ppm, 1.16ppm, 1.02ppm and 0.64ppm, the integral area ratio is 1:1:1:1, and the ratio is consistent with the theoretical ratio. Two groups of peaks 2.04-1.98 ppm exist in the methyl group on the quaternary carbon connected with the trifluoromethyl group, the integral area ratio is 12:18, the peaks are the methyl group peaks on the polyfluorene and polybiphenyl chain segments respectively, and the proportion of the peaks is consistent with that of the blocks.
Example 2:
the reaction route of the block ether bond-free polymer PFFA-QA is shown as follows:
after 2.46g (5mmol) of bromodihexylfluorene monomer, 0.62g (5.5mmol) of a trifluoroacetone solution and 5mL of dichloromethane were added to a dry pressure-resistant bottle A, the temperature of the system was lowered to 0 ℃. Then 5mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle A, and after the temperature was raised to 25 ℃, the reaction was carried out for 15 minutes with magnetic stirring.
After 1.67g (5mmol) of dihexylfluorene monomer, 0.62g (5.5mmol) of trifluoroacetone and 4mL of dichloromethane were charged in a pressure bottle B, the temperature of the system was lowered to 0 ℃. Then 4mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle B, and after the temperature was raised to 25 ℃, the reaction was carried out for 15 minutes with magnetic stirring.
And pouring the reactant in the system B into the system A, continuously stirring for reacting for 30 minutes, pouring the reaction system into ethanol, and precipitating polymer solids. Washing with water, and vacuum drying to obtain block ether bond-free main chain polymer PFFA-Br (brominated fluorenyl monomer ratio is 50%, x is 0.5).
Example 3:
a block ether bond-free backbone polymer PFA-Br was prepared according to the reaction scheme of example 1, specifically:
after 2.46g (5mmol) of bromodihexylfluorene monomer, 0.62g (5.5mmol) of a trifluoroacetone solution and 5mL of dichloromethane were added to a dry pressure-resistant bottle A, the temperature of the system was lowered to 0 ℃. Then 5mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle A, and after the temperature was raised to 25 ℃, the reaction was carried out for 10 minutes with magnetic stirring.
After 0.77g (5mmol) of biphenyl, 0.62g (5.5mmol) of trifluoroacetone and 3mL of dichloromethane were charged in a pressure bottle B, the temperature of the system was lowered to 0 ℃. Then 3mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle B, and after the temperature was raised to 25 ℃, the reaction was carried out for 10 minutes with magnetic stirring.
And pouring the reactant in the system B into the reaction product A, continuously stirring and reacting for 35 minutes, and pouring the reaction system into ethanol to separate out polymer solids. Washing with water, and vacuum drying to obtain block ether bond-free main chain polymer PFA-Br (brominated fluorenyl monomer ratio is 50%, x is 0.5).
Example 4:
a block ether bond-free backbone polymer PFA-Br was prepared according to the reaction scheme of example 1, wherein the reaction times for the A/B systems were each 5 minutes with a subsequent stirring time of 40 minutes.
Example 5:
a block ether bond-free backbone polymer PFA-Br was prepared according to the reaction scheme of example 1, wherein the reaction times for the A/B systems were each 30 minutes with a subsequent stirring time of 15 minutes.
Example 6:
after 1.97g (4mmol) of bromodihexylfluorene monomer, 0.51g (4.5mmol) of a trifluoroacetone solution and 5mL of dichloromethane were added to a dry pressure-resistant bottle A, the temperature of the system was lowered to 0 ℃. Then 5mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle A, and after the temperature was raised to 25 ℃, the reaction was carried out for 15 minutes with magnetic stirring.
After 0.92g (4mmol) of p-terphenyl, 0.51g (4.5mmol) of trifluoroacetone and 3mL of dichloromethane were added to the pressure-resistant bottle B, the temperature of the system was lowered to 0 ℃. Then 3mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle B and reacted for 15 minutes with magnetic stirring.
And pouring the reactant in the system B into the system A, continuously stirring for 30 minutes, and pouring the reaction system into ethanol to precipitate polymer solids. The polymer obtained after washing and vacuum drying has poor solubility in dimethyl sulfoxide and N, N-dimethylacetamide, poor film forming property and brittle film formation (the proportion of the brominated fluorenyl monomer is 50 percent, and x is 0.5).
Example 7:
after 1.97g (4mmol) of bromodihexylfluorene monomer, 0.51g (4.5mmol) of a trifluoroacetone solution and 5mL of dichloromethane were added to a dry pressure-resistant bottle A, the temperature of the system was lowered to 0 ℃. Then 5mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle A, and after the temperature was raised to 25 ℃, the reaction was carried out for 15 minutes with magnetic stirring.
After 0.83g (4mmol) of 9, 9-dimethylfluorene, 0.51g (4.5mmol) of trifluoroacetone and 3mL of dichloromethane were added to the pressure-resistant bottle B, the temperature of the system was lowered to 0 ℃. Then 3mL of trifluoromethanesulfonic acid was quickly poured into pressure bottle B and reacted for 15 minutes with magnetic stirring.
And pouring the reactant in the system B into the reaction product A, continuing stirring for 30 minutes, and pouring the reaction system into ethanol to precipitate polymer solid. The polymer obtained after washing and vacuum drying has poor solubility in dimethyl sulfoxide and N, N-dimethylacetamide and poor film forming property or is brittle (the proportion of the brominated fluorenyl monomer is 50 percent, and x is 0.5).
Example 8:
the reaction route of the block ionic cationic polymer PFA-QA is shown as follows:
2.42g of the brominated block type ether-free main chain polymer PFA-Br prepared in example 1 was dissolved in 20mL of N, N-dimethylacetamide, 3.4mL of trimethylamine aqueous solution (28 wt%) was added and reacted at room temperature for 24 hours, the reacted system was slowly poured into diethyl ether to precipitate flocculent white polymer, and the product was washed with water, desalted and vacuum dried to obtain the quaternized block ionic cationic polymer PFA-QA (x is 0.4).
Blocking after quaternizationThe nuclear magnetic resonance hydrogen spectrum of the cationic polymer PFA-QA is shown in FIG. 2, FIG. 2 is the nuclear magnetic resonance hydrogen spectrum of the quaternary ammonium block ionic cationic polymer PFA-QA obtained in example 8, 1 the peak position of the polyelectrolyte membrane after quaternization in the H NMR spectrum is the same as that before reaction. The proton signal of the 3 methyl groups attached to the nitrogen atom on the quaternary amine was 2.96ppm, with an integrated area to area ratio of the aromatic region of 1:1, consistent with the theoretical fully quaternized ratio. The peak areas of different chemical environments of the high field in the nuclear magnetic spectrum are the same as those before the reaction, so that the quaternization reaction is proved to be smoothly and effectively carried out, and the target polymer is obtained.
Example 9:
dissolving 2.85g of the brominated block type ether-free main chain polymer PFFA-Br prepared in example 2 in 20mL of N, N-dimethylacetamide, adding 3.5mL of trimethylamine aqueous solution (28 wt%), reacting at room temperature for 24h, slowly pouring the reacted system into diethyl ether to separate out flocculent white polymer, and washing, desalting and vacuum drying to obtain the quaternized block ionic cationic polymer PFFA-QA (x is 0.5).
Example 10:
block ionic anionic polymer PFA-SO 3 The reaction scheme for Na is as follows:
2.42g of the brominated block type ether-free main chain polymer PFA-Br prepared in example 1 was dissolved in dimethyl sulfoxide, 0.63g (1.1eq) of potassium thioacetate was added to the solution and reacted at 60 ℃ for 6 hours, the reaction system was cooled in an ice-water bath, 1.29g of 3-chloroperoxybenzoic acid (1.5eq) was slowly added as an oxidizing agent, and then the reaction system was transferred to a room temperature environment and allowed to continue to react for 2 hours. Pouring the reacted solution into sodium chloride solution, stirring for 1h, filtering, washing with water, desalting, and vacuum drying to obtain sulfonated block ionic anionic polymer PFA-SO 3 Na (x is 0.4).
Quaternized sulfonated block ionic anionic polymer PFA-SO 3 Na nucleusThe magnetic resonance hydrogen spectrum is shown in FIG. 3, FIG. 3 is the sulfonated block ionic type anionic polymer PFA-SO obtained in example 10 3 A hydrogen spectrum of Na Nuclear Magnetic Resonance (NMR), 1 the H NMR spectrum shows that the peak position of the polyelectrolyte membrane after being connected with the sulfonic acid group is the same as that before the reaction. Chemical shifts on methylene attached to sodium sulfonate were 2.52ppm, with d 6 -DMSO solvent peaks overlap. The peak areas of different chemical environments of high fields in the rest nuclear magnetic spectrums are the same as those before the reaction, which proves that the sulfonation reaction is smoothly and effectively carried out, and the target polymer is obtained.
Comparative example 1:
after adding 1.97g (4mmol) of bromodihexylfluorene monomer, 0.92g (6mmol) of biphenyl, 1.24g (11mmol) of a trifluoroacetone solution and 10mL of dichloromethane into a dry pressure-resistant bottle, the temperature of the system was lowered to 0 ℃. Then 10mL of trifluoromethanesulfonic acid is quickly poured into a pressure-resistant bottle, and after the temperature is raised to 25 ℃, the reaction is carried out for 45 minutes by adopting magnetic stirring. The reaction system was poured into ethanol to precipitate a polymer solid. After washing and vacuum drying, the irregular type ether bond-free main chain polymer PFA-Br (brominated fluorenyl monomer proportion is 40 percent, and x is 0.4) is obtained.
Comparative example 2:
2.42g of brominated random ether-free main chain polymer PFA-Br prepared in example 10 was dissolved in 20mL of N, N-dimethylacetamide, 3.4mL of trimethylamine aqueous solution (28 wt%) was added, the mixture was reacted at room temperature for 24 hours, the reacted system was slowly poured into diethyl ether to precipitate flocculent white polymer, and the flocculent white polymer was washed with water, desalted and vacuum dried to obtain a quaternized random ionic cationic polymer PFA-QA (x: 0.4).
Comparative example 3:
after 2.46g (5mmol) of bromodihexylfluorene monomer, 1.67g (5mmol) of biphenyl, 1.24g (11mmol) of a trifluoroacetone solution and 10mL of dichloromethane were charged in a dry pressure-resistant bottle, the temperature of the system was lowered to 0 ℃. Then 10mL of trifluoromethanesulfonic acid was quickly poured into a pressure-resistant bottle, and after the temperature was raised to 25 ℃, the reaction was carried out for 45 minutes with magnetic stirring. The reaction system was poured into ethanol to precipitate a polymer solid. After water washing and vacuum drying, the irregular type ether bond-free main chain polymer PFFA-Br (brominated fluorenyl monomer proportion is 50 percent, and x is 0.5) is obtained.
Comparative example 4:
2.85g of brominated random ether-free main chain polymer PFFA-Br prepared in example 13 is dissolved in 20mL of N, N-dimethylacetamide, 3.5mL of trimethylamine aqueous solution (28 wt%) is added, reaction is carried out at room temperature for 24h, the reacted system is slowly poured into ether, flocculent white polymer is separated out, and quaternized random ionic cationic polymer PFFA-QA (x is 0.5) is obtained after water washing, salt removal and vacuum drying.
The ionic polymers obtained in example 8, example 9, comparative example 2 and comparative example 4 were formed into an anion exchange membrane (33 μm) by a flow extension method, and the conductivity and swelling ratio of the anion exchange membrane at different temperatures were measured, and the results are shown in tables 1 and 2, where table 1 shows the hydroxide conductivity of the block type and random type polymers PFA-QA at different temperatures, and table 2 shows the swelling ratio of the block type and random type polymers PFA-QA at different temperatures.
TABLE 1 hydroxide conductivity of Block and random Polymer PFA-QA at different temperatures
TABLE 2 swell ratio of block and random polymers PFA-QA at different temperatures
Experimental results show that the random type and block type polymers have larger difference in comprehensive performance, and the block type polymer provided by the invention can improve the conductivity of an anion exchange membrane, reduce the swelling rate and improve the stability.
Atomic force of the block-type PFA-QA membrane obtained in example 8 and the random-type PFA-QA membrane obtained in comparative example 2 is observed by an atomic force microscope, and small-angle scattering analysis is performed, and as a result, referring to FIG. 4, FIG. 4 shows the atomic force and small-angle scattering diagram of the block-type and random-type PFA-QA membranes, the difference in conductivity and swelling ratio of the anion exchange membrane is mainly caused by the micro-morphology of the membranes, the block-type PFA-QA membrane has more obvious hydrophilic-hydrophobic phase separation behavior, and the formed ion cluster and bicontinuous phase structure are favorable for ion transmission.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A block-type ether bond-free polymer having the structure of formula 1:
wherein n is the degree of polymerization, m is selected from 1 to 10, x is selected from 0.3 to 0.7, y is selected from 0.3 to 0.7, and x + y is 1;
x is selected from halogen or structures (formula X-1) to (formula X-5):
ar is selected from substituted or unsubstituted aromatic groups.
2. The block ether linkage free polymer of claim 1, wherein Ar is selected from substituted aromatic groups selected from C 1-15 An alkyl group.
3. The block-type ether linkage free polymer according to claim 2, wherein the aromatic group is selected from biphenyl group or fluorenyl group.
4. The block-type ether bond-free polymer according to claim 3, wherein Ar is selected from the structures represented by (formula Ar-1) to (formula Ar-4):
wherein a is selected from 1-9.
5. A method for preparing the block type ether bond-free polymer according to any one of claims 1 to 4, which comprises the following steps:
adopting an acid catalyst, taking an aromatic monomer and trifluoroacetone as raw materials, and carrying out polymerization reaction to obtain a polymer intermediate 1;
adopting an acid catalyst, taking a halogenated dialkyl fluorene monomer shown in a formula 6 and trifluoroacetone as raw materials, and carrying out polymerization reaction to obtain a polymer intermediate 2;
wherein m is 1-10;
and (3) carrying out copolymerization reaction on the polymer intermediate 1 and the polymer intermediate 2 to obtain the block-type ether bond-free polymer.
6. The method of claim 5, further comprising: functionalizing the block ether bond-free polymer.
7. The method for preparing the block-type ether bond-free polymer according to claim 5, wherein the molar ratio of the aromatic monomer to the trifluoroacetone is 1: 1.1-1.2, and the molar ratio of the halogenated dialkyl fluorene monomer to the trifluoroacetone is 1: 1.1-1.2.
8. The method according to claim 5, wherein the acid catalyst is one or more selected from the group consisting of trifluoromethanesulfonic acid, methanesulfonic acid and Eton's reagent.
9. An ion exchange membrane comprising the block-type ether bond-free polymer according to any one of claims 1 to 4.
10. A fuel cell or flow battery comprising the ion exchange membrane of claim 9.
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