CN111909409A - Preparation method of azole ring-containing oligosiloxane composite proton exchange membrane - Google Patents

Preparation method of azole ring-containing oligosiloxane composite proton exchange membrane Download PDF

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CN111909409A
CN111909409A CN202010800186.4A CN202010800186A CN111909409A CN 111909409 A CN111909409 A CN 111909409A CN 202010800186 A CN202010800186 A CN 202010800186A CN 111909409 A CN111909409 A CN 111909409A
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oligosiloxane
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pga
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丁会利
刘晓阳
冯怡
任红倩
杨梦洁
夏明龙
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Hebei University of Technology
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Abstract

The invention relates to a preparation method of an oligosiloxane composite proton exchange membrane containing oxazole ring. The method comprises the following steps: adding the first monomer to react with the second monomer to obtain a third monomer; under the action of an initiator, reacting the third monomer with the fourth monomer to obtain the azole ring-containing oligosiloxane nanofiller PGA; mixing PGA with a matrix, casting the obtained mixed solution on a glass plate, and drying to obtain the composite membrane (SPEEK/PGA-X). The proton exchange membrane with high performance and low cost obtained by the invention can be widely applied to fuel cells, and has important significance and key effects on reducing the cost of the fuel cells, perfecting the upstream industrial chain of the fuel cells and promoting the development of new energy fields.

Description

Preparation method of azole ring-containing oligosiloxane composite proton exchange membrane
Technical Field
The invention belongs to the field of preparation of nano composite membranes with high proton conductivity, and particularly relates to an azole ring-containing oligosiloxane composite proton exchange membrane which meets high proton conductivity and excellent dimensional stability.
Background
The proton exchange membrane fuel cell is an environment-friendly energy device with high conversion efficiency and no pollution emission. The proton exchange membrane is one of the core components of the fuel cell, and has the dual functions of separating fuel and oxidant and conducting proton, and the excellent comprehensive performance of the proton exchange membrane is the guarantee of long-term and high-efficiency operation of the fuel cell. To date, there are four major categories of PEMs reported in the literature: (1) the fluorine-containing exchange membrane mainly comprises a Nafion series membrane and a Solvay membrane in Belgium of Dupont in the United states; (2) partially fluorinating a proton exchange membrane, wherein the partial fluorination is generally embodied in perfluoro of a main chain, and a proton exchange group is generally a sulfonic acid group; (3) the novel non-fluorine polymer membrane has electrochemical performance similar to that of Nafion membrane, and the exchange membrane material is sulfonated product of high temperature resistant engineering plastic such as polyaryletherketone, polybenzimidazole and the like;
(4) the proton exchange membrane is mainly a composite or hybrid material prepared by adopting different processes on a polymer matrix and inorganic or organic fillers.
Proton exchange of perfluorosulfonic acid typeThe further development and application of the membrane in the field of fuel cells are seriously hindered by the defects of strong dependence of proton conductivity on water, complex synthesis process, high overall comprehensive cost of the cell and the like of the membrane and part of the fluorine-containing proton exchange membrane. How to balance the relationship of high proton conductivity and dimensional stability of the non-fluorine high-temperature resistant polyethersulfone and ketone engineering resin proton exchange membranes is an important bottleneck for limiting the development of the proton exchange membranes. Theoretically, proton transfer through the PEM follows a carrier mechanism (protons through the formation of hydrate ions such as H)3O+，H5O2 +And H9O4 +And diffuse with water) and the grotthus mechanism (hopping of protons from one proton carrier site to an adjacent one), which together control the proton transfer rate in many cases. For the carrier mechanism, water molecules are generally used as carriers for H + transmission, however, in a high-temperature and low-humidity environment, the water molecules are largely lost in the membrane, so that the proton conductivity in the membrane is greatly reduced. One simple and versatile method is to introduce nanofillers with acidic groups into the membrane to improve the water retention properties of the membrane, the acidic groups giving the membrane a high water absorption, a low chemical potential and a highly bound water content to ensure water loss. The enhanced water retention provides additional hydronium ions to the membrane for carrier transfer. For the jumping mechanism, a novel and effective approach is to develop an acid-base paired composite membrane, which is usually a complex of an acidic polymer and a basic polymer. Wherein, the acidic group is used as a proton donor, the basic group is used as a proton acceptor, and low energy is provided for proton jump by optimizing a proton transfer site. In addition, the acidic groups/basic groups are tightly connected through electrostatic action, so that enthalpy change is greatly reduced, and the dimensional stability of the material is enhanced. However, some inorganic materials are simply functionalized, and when they are doped into a polymer matrix, the inorganic filler may aggregate, thereby causing phase separation of the composite membrane, resulting in a decrease in proton conductivity.
Disclosure of Invention
The invention aims to provide a preparation method of an azole ring-containing oligosiloxane composite proton exchange membrane aiming at the defects in the prior art. The method comprises the steps of firstly preparing inorganic particles with a cage-shaped structure, namely octavinyl octasilsesquioxane, using the octavinyl octasilsesquioxane as a filler, introducing azole rings on the particles through free radical polymerization reaction, and forming acid-base ion pairs through interaction between the azole rings on the filler and sulfonic acid groups on a matrix to promote protons to jump between interfaces to form a proton transfer channel. The proton exchange membrane with high performance and low cost obtained by the invention can be widely applied to fuel cells, and has important significance and key effects on reducing the cost of the fuel cells, perfecting the upstream industrial chain of the fuel cells and promoting the development of new energy fields.
The technical scheme of the invention is as follows:
a preparation method of an azole ring-containing oligosiloxane composite proton exchange membrane comprises the following steps:
(1) adding a first monomer into a first solvent at the temperature of 10-35 ℃ for uniform dispersion; then adding a second monomer, reacting for 12-24h, and evaporating to remove the solvent to obtain a third monomer;
wherein the mass ratio is that the first monomer: a second monomer ═ 1: 1-2; adding 30-50 g of the first monomer per liter of the first solvent; the first solvent is isopropanol or ethanol;
(2) dispersing a third monomer into a second solvent at the temperature of 30-100 ℃, adding an initiator to start reaction, adding a fourth monomer after the reaction is carried out for 0.5-2.5 hours, precipitating the obtained product in a methanol solution after the reaction is carried out for 5.5-7.5 hours, and then drying in a vacuum oven to obtain the oligosiloxane nanofiller (PGA) containing the oxazole ring;
wherein, 70 to 120 grams of the third monomer is added per liter of the second solvent; the second solvent is specifically deionized water or absolute ethyl alcohol; the mass ratio of the third monomer to the fourth monomer is 80-120: 1; the mass of the initiator is 1-2% of the sum of the mass of the third monomer and the mass of the fourth monomer;
(3) mixing the oligosiloxane nanofiller (PGA) containing azole rings with a matrix, and stirring for 24-72 hours to obtain a mixed solution; casting the obtained mixed solution on a glass plate, drying at 60-120 ℃ for 12-48 hours, and naturally cooling to obtain a composite membrane (SPEEK/PGA-X);
wherein the weight ratio of the oligosiloxane nanofiller PGA containing azole rings to the oligosiloxane nanofiller PGA is as follows: matrix 1-4: 20; the pouring solution of each square centimeter of glass plate is 1.5-2.5 milliliters of pouring mixed solution;
the first monomer in the step (1) is Atri or Tri, and the second monomer is glycidyl methacrylate.
The fourth monomer in the step (2) is octavinyl octasilsesquioxane, and the initiator is AIBN;
the matrix in the step (3) is SPEEK, SPES or SPTES.
An alkene monomer containing an azole ring, which is GMA-Atri and has a molecular formula as follows:
Figure BDA0002627091100000021
the invention has the substantive characteristics that:
the invention prepares the oligosiloxane organic-inorganic compound containing azole ring as the filler; the substance is inorganic particles and has a cage-shaped structure, and the diameter of each cage formed by silicon-oxygen bonds is only 1.5nm and is far smaller than that of silicon dioxide, graphene oxide and the like used in common modification; and each vertex of the inorganic particle cage type has a carbon-carbon double bond, so that the step of introducing functional bonds by functionalizing the inorganic filler is omitted. Compared with the inorganic filler which is used conventionally, the inorganic filler prepared by using the inorganic particles has better compatibility with polymers;
according to the invention, acid-base ion pairs are formed through interaction between azole rings on the filler and sulfonic acid groups on the matrix, so that protons are promoted to jump between interfaces to form a proton transfer channel, the dependence of the membrane on water in the process of transferring protons is reduced, and meanwhile, the dispersibility of the filler among polymer matrixes is increased, so that the membrane obtains high proton conductivity while ensuring the mechanical stability.
The invention has the beneficial effects that:
in the fuel cell industry, the perfluorosulfonic acid membrane (Nafion membrane) invented by dupont has the advantages of high proton conductivity, excellent chemical stability and the like, but the problems of low proton conductivity, poor dimensional stability and the like in high-temperature and low-humidity environments become the bottleneck of further development of PEM, and besides high-efficiency proton conductivity, good mechanical properties, moderate water absorption and swelling degree, good dimensional stability is also required. For this purpose, the invention proposes to use as filler an azole ring-containing oligosiloxane polymer, and to obtain high proton conductivity while ensuring mechanical stability of the membrane through the interaction between the azole ring and the sulfonic acid group.
The proton 'jump mechanism' is a more rapid and effective proton transfer mode than the 'carrying mechanism', the transfer of protons in the membrane is a complex process, and in most cases, the jump mechanism and the carrying mechanism exist simultaneously, so that the efficient proton transfer has the following three conditions: proton channels, proton carriers, water molecules. Acidic group (-SO)3H) And basic groups (imidazole groups) may form acid-base pairs. When proton is taken from-SO3Upon dissociation of H, the imidazole group generates an attractive force, promotes dissociation of the proton and accepts proton formation+H3N-; by dissociation of the formed-SO3H can also promote approach+H3The dissociation of the N-group protons and the subsequent joining of the protons, in this way the transfer of the protons between the carriers is promoted by the attractive force and the jump energy barrier is reduced. Therefore, the acid-base pair as a proton carrier can become a novel efficient proton transfer carrier. The object is to design an oligosiloxane organic-inorganic compound containing azole rings as a filler, acid-base ion pairs are formed through the interaction between the azole rings on the filler and sulfonic acid groups on a matrix, so that protons are promoted to jump between interfaces to form a proton transfer channel, the dependence of the membrane on water in the process of transferring the protons is reduced, and meanwhile, the dispersity of the filler among polymer matrixes is increased, so that the membrane obtains high proton conductivity while ensuring the mechanical stability. Experiments prove that the prepared oligosiloxane organic-inorganic composite filler containing the azole ring has been successfully prepared.
After the oligosiloxane organic-inorganic composite filler containing azole rings prepared by the invention is added, the proton conductivity of the composite membrane can exceed that of a SPEEK matrix membrane at high temperature. The application capability of the composite membrane at high temperature is larger than that of an unmodified matrix membrane, the proton conductivity of the SPEEK matrix membrane in the complete water and downward vertical directions is only 26.2mS/cm at 80 ℃, and the proton conductivity of the composite membrane added with the filler reaches 28.4 mS/cm. In addition, the SPEEK matrix film is substantially dissolved in water at 80 ℃, while the composite film can maintain a stable size and have a high water absorption rate.
The invention research of the patent can provide a new thought and method for the preparation of the composite proton exchange membrane, and simultaneously provide theoretical basis and experimental data for the application field of the acid-base amphoteric proton exchange membrane. The preparation of the proton exchange membrane with excellent comprehensive performance realizes the wide application of the proton exchange membrane with high performance and low cost in the fuel cell, and has important significance and key functions for reducing the cost of the fuel cell, perfecting the upstream industrial chain of the fuel cell and promoting the development of the new energy field.
Drawings
FIG. 1 shows SPEEK of example 11A HNMR map;
FIG. 2 is an FTIR plot of GMA and GMA-Atri of example 1;
FIG. 3 is an FTIR plot of GMA-Atti and PGA of example 1;
FIG. 4 is an EDX diagram of PGA nanofillers of example 1, wherein FIG. 4(a) is a content distribution diagram of C element; FIG. 4(b) is a graph showing the distribution of the content of N element; FIG. 4(c) is a diagram showing a distribution of the content of O element; FIG. 4(d) is a distribution diagram of the content of Si element;
fig. 5 is a PEM picture of the membrane of example 1, wherein fig. 5(a) is a PEM picture of SPEEK; FIG. 5(b) is a PEM picture of SPEEK/PGA-10;
fig. 6 is a graph showing the temperature-dependent proton conductivity of SPEEK and the composite membrane of example 1.
FIG. 7 is a temperature-dependent water absorption curve of SPEEK and composite membrane of example 1
FIG. 8 is a temperature-dependent swelling ratio curve of SPEEK and composite membrane of example 1
Detailed Description
The invention will be further illustrated with reference to the following specific examples. In order to prepare the proton exchange membrane with excellent comprehensive performance, a series of research experiments are carried out, and suitable conditions for preparing the composite PEM are summarized. All the chemical reagents used in the examples were analytically pure, ensuring the purity of the prepared samples.
The degree of sulfonation calculation formula of SPEEK is:
Figure BDA0002627091100000041
wherein n is a sulfonation degree of SPEEK, A is an area of a nuclear magnetic resonance spectrum peak corresponding to a hydrogen proton in the SPEEK membrane, and a subscript thereof is a hydrogen atom.
The proton conductivity of the membrane is calculated as:
Figure BDA0002627091100000042
where D is the thickness of the inter-polar film, A is the effective cross-sectional area of the film, and R is the impedance of the film.
The water absorption of the film is calculated by the formula:
Figure BDA0002627091100000043
wherein WwetImmersing a film sample into deionized water at different temperatures for 24h to obtain wet film quality; wdryThe mass in the dry film state.
The swelling degree of the film is calculated by the formula:
Figure BDA0002627091100000044
wherein L iswetImmersing the film sample in deionized water at different temperatures for 24h for a wet film length; l isdryThe length in the dry film state.
Example 1
(1) Adding 3-amino-1, 2, 4-triazole (Atri) into isopropanol at 25 ℃ for uniform dispersion, then adding Glycidyl Methacrylate (GMA), reacting for 24h, and removing the solvent by evaporation to obtain glycidyl methacrylate-3-amino-1, 2, 4-triazole (GMA-Atri);
wherein the mass ratio of the 3-amino-1, 2, 4-triazole (Atri) to the Glycidyl Methacrylate (GMA) is 8: 11; add 34 grams of Atri per liter of isopropanol;
(2) dispersing GMA-Atri in deionized water at 70 ℃, adding an initiator AIBN to start reaction, adding octavinyl octasilsesquioxane (OVPOSS) after reacting for 1 hour, precipitating the obtained product in methanol after reacting for 6 hours, and drying in a vacuum oven to obtain the required oligosiloxane nanofiller PGA containing oxazole rings;
wherein the mass ratio of GMA-Atti to OVPOSS is 90: 1; the mass of the added initiator is 1 percent of the sum of the mass of the monomer 3 and the mass of the monomer 4; adding 75 g of GMA-Atri into each liter of deionized water;
(3) and (3) mixing the product obtained in the step (2) with matrix sulfonated polyether ether ketone (SPEEK) according to the mass ratio of 1:10, stirring for 48 hours by magnetic force, casting the obtained mixed solution onto a horizontal glass plate, casting 2 ml of mixed solution per square centimeter of glass plate, drying for 36 hours at 100 ℃, and naturally cooling to obtain the composite membrane (SPEEK/PGA-X), wherein the thickness of the composite membrane is 0.97 mm.
Characterization test 1 Nuclear magnetism of Sulfonated Polyetheretherketone (SPEEK)1H spectrogram
SPEEK (sulfonated polyether ether ketone) is selected as a matrix material, and the reaction condition is regulated and controlled by adopting a controlled variable method to prepare the SPEEK with proper sulfonation degree. The method comprises the following specific steps: weighing 7g of PEEK (polyether ether ketone) granules, slowly dissolving the PEEK granules in 125ml of concentrated sulfuric acid at normal temperature, preserving the heat for 8 hours in a water bath at 50 ℃ after the PEEK granules are completely dissolved, slowly pouring the reaction solution into an ice-water mixture, washing the product to be neutral by water, air-drying the product for 48 hours, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain the SPEEK.
To measure the sulfonation degree of SPEKK, the sulfonation degree of SPEEK was calculated by using a nuclear magnetic resonance method. The hydrogen at different positions on the SPEEK structural unit is respectively replaced by Ha，Ha’，Hb，Hb’，Hc，Hd，Hd’,He，Hf，Hf’And performing identification. Hydrogen per repeating unit is 12, HcThe position of the benzene ring is uniqueThe number thereof is equivalent to the number of sulfonic acid groups. When n is the number of sulfonic acid groups per repeating unit of SPEEK and the total number of hydrogens at other benzene ring positions (12-2n), n can be obtained by a sulfonation degree calculation formula, i.e., the sulfonation degree is 67.8%.
Characterization of the Infrared Spectroscopy of tests 2GMA (glycidyl methacrylate) and GMA-Atti (glycidyl methacrylate-3-amino-1, 2, 4-triazole) and GMA-Atti and PGA (Azole-ring-containing oligosiloxane nanofillers)
FIGS. 2 and 3 are infrared spectra of GMA (glycidyl methacrylate) and GMA-Atti (glycidyl methacrylate-3-amino-1, 2, 4-triazole) and GMA-Atti and PGA (oxacyloligosiloxane-containing nanofillers), respectively, which characterize the functional groups of the nanofillers. In FIG. 2, GMA-Atri shows three distinct characteristic absorption peaks in the infrared spectrum at 3317.7cm-1The characteristic peak is the stretching vibration peak of O-H. At 1530.1cm-1And 1564.2cm-1The characteristic bands correspond to C-N stretching and bending vibration peaks, which indicate the successful occurrence of ring-opening polymerization, and GMA-Atti (glycidyl methacrylate-3-amino-1, 2, 4-triazole) is obtained, and the molecular formula is as follows:
Figure BDA0002627091100000051
in FIG. 3, PGA has infrared spectra at 590 and 1111.5cm, compared to GMA-Atri-1Two characteristic peaks are shown, corresponding to the stretching vibration peak of-Si-O-Si-. And 1639.6cm-1The apparent reduction of the peak oscillation of C ═ C indicates a successful reaction of the addition polymerization.
EDX map for characterization of test 3PGA
Fig. 4 is an EDX diagram of PGA, which shows successful preparation of PGA by C, N, O, Si element distribution and uniform distribution of several elements, and its formula is:
Figure BDA0002627091100000061
wherein the broken lines represent GMA-Atri monomers which are subjected to addition polymerization on the figure.
PEM (proton exchange membrane) diagram for characterization test 4SPEEK and composite membrane
Fig. 5 is a PEM image of SPEEK and composite membrane, showing that SPEEK is a transparent membrane, and the membrane prepared after doping with PGA filler is still uniform and transparent, although slightly yellow, indicating that the filler is well compatible with the matrix and there is no significant phase separation.
Characterization test 5SPEEK and proton conductivity performance test of composite membrane
Proton conductivity is the most prominent property of proton exchange membranes and is measured by the ac impedance method, where the ac impedance of the membrane is measured by an electrochemical workstation (compact, IVIUM Tech.) with a sweep frequency of 105-1Hz and a sweep voltage of 0.005V. Before membrane test, the membrane is soaked in 2M hydrochloric acid for 24h and then washed to neutrality by water for standby. In practical application of the proton exchange membrane, H+The transfer path is the distance in the vertical direction through the membrane, so the proton conductivity in the vertical direction can more exactly characterize the proton conductivity of the proton exchange membrane. The test steps are as follows: cutting the membrane into a square membrane of 1cm multiplied by 1cm, clamping the membrane in a fixture of the membrane, pressing the membrane on a platinum electrode, screwing a nut, fixing the membrane, placing the fixture in ultrapure water, measuring impedance R at different temperatures through an electrochemical workstation, and calculating the proton conductivity of the membrane through a formula.
Fig. 6 is a proton conductivity graph of SPEEK and composite membrane, and it is understood from the graph that incorporation of an azole ring-containing oligosiloxane organic-inorganic composite filler is advantageous for improvement of proton conductivity, and although the proton conductivity of the composite membrane before 60 ℃ is lower than that of the SPEEK matrix membrane, the proton conductivity of the composite membrane starts to exceed that of the SPEEK matrix membrane after 60 ℃. The reason why the composite membrane is slightly lower at low temperature may be that the proton conductivity of the composite membrane is higher than that of the SPEEK matrix membrane because the proton carriers in the membrane are less because the basic group of the oxazole ring has no sulfonic acid group and has high water absorption, but the composite membrane can carry out proton jump by acid-base pairs along with the loss of water at high temperature and has low dependence on water.
Characterization test 6SPEEK and water absorption and swelling ratio test of composite membrane
Testing the water absorption and swelling degree of the film: drying the membrane with the area of 3 multiplied by 3cm in an oven at 60 ℃ for 24h, weighing the mass of the sample membrane and recording as W after full dryingdryAnd measuring the length of the dry film as Ldry. The membrane was soaked in deionized water at different temperatures (30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃) for 12 hours to fully reach the hydrated state. Taking out the film from water, quickly wiping off the water on the surface of the film, and weighing the mass WwetAnd measuring the length dimension LwetThe water absorption and swelling degree of the film were calculated.
Fig. 7 is a water absorption curve of SPEEK and composite membrane. Fig. 8 is a swelling ratio curve of SPEEK and the composite membrane, and combining the water absorption rate and swelling ratio curve of the membrane, at 80 ℃, the water absorption rate of the composite membrane can reach 194.38%, the swelling ratio is only 26%, and the SPEEK matrix membrane is dissolved at 80 ℃, so that the composite membrane has higher water absorption rate and good dimensional stability compared with the SPEEK matrix membrane, and can be used at high temperature for a long time.
In the research, an oligosiloxane organic-inorganic composite filler containing an azole ring is synthesized, wherein acid-base ion pairs are formed by the interaction between the azole ring and sulfonic acid groups on a matrix, so that protons are promoted to jump between interfaces to form a proton transfer channel, the dependence of the membrane on water in the process of transferring the protons is reduced, and meanwhile, the dispersity of the filler among polymer matrixes is improved, so that the membrane obtains high proton conductivity while the mechanical stability is ensured. Sulfonated poly (ether ketone) (SPEEK) was chosen as the bulk polymer because of its cross-features of low cost and low fuel permeability. The effect of PGA on the performance of composite membranes was investigated by compounding different proportions of PGA into the polymer matrix. Through system test and characterization, the method provides thought and theoretical basis for the performance of the alkaline nano filler reinforced composite membrane and the strengthening of a proton transfer mechanism.
Example 2
The other procedure was the same as in example 1 except that the Atri was changed to Tri (1H-1,2, 4-triazole). The obtained monomer 3 is GMA-Tri (glycidyl methacrylate-1H-1, 2, 4-triazole), and PGT (oligomeric siloxane organic-inorganic composite filler containing azole ring) is finally obtained. The properties of the composite film obtained were close to those of example 1.
Example 3
The other steps are the same as example 1, except that SPEEK is changed into SPES (sulfonated polyarylethersulfone), and finally the obtained composite membrane is SPES/PGA-X. The properties of the composite film obtained were close to those of example 1.
Example 4
The other steps are the same as example 1, except that SPEEK is replaced by SPTES (sulfonated polyarylene sulfide sulfone), and finally the obtained composite membrane is SPTES/PGA-X. The properties of the composite film obtained were close to those of example 1.
The invention is not the best known technology.

Claims (6)

1. A preparation method of an azole ring-containing oligosiloxane composite proton exchange membrane is characterized by comprising the following steps:
(1) adding a first monomer into a first solvent at the temperature of 10-35 ℃ for dispersion; then adding a second monomer, reacting for 12-24h, and evaporating to remove the solvent to obtain a third monomer;
wherein the mass ratio is that the first monomer: a second monomer ═ 1: 1-2; adding 30-50 g of the first monomer per liter of the first solvent;
(2) dispersing a third monomer into a second solvent at the temperature of 30-100 ℃, adding an initiator to start reaction, adding a fourth monomer after the reaction is carried out for 0.5-2.5 hours, precipitating the obtained product in a methanol solution after the reaction is carried out for 5.5-7.5 hours, and then drying in a vacuum oven to obtain the oligosiloxane nanofiller (PGA) containing the oxazole ring;
wherein, 70 to 120 grams of the third monomer is added per liter of the second solvent; the mass ratio of the third monomer to the fourth monomer is 80-120: 1; the mass of the initiator is 1-2% of the sum of the mass of the third monomer and the mass of the fourth monomer;
(3) mixing the oligosiloxane nanofiller (PGA) containing azole rings with a matrix, and stirring for 24-72 hours to obtain a mixed solution; casting the obtained mixed solution on a glass plate, drying at the temperature of 60-120 ℃ for 12-48 hours, and naturally cooling to obtain a composite film;
wherein the weight ratio of the oligosiloxane nanofiller PGA containing azole rings to the oligosiloxane nanofiller PGA is as follows: matrix 1-4: 20; the pouring solution of each square centimeter of glass plate is 1.5-2.5 milliliters of pouring mixed solution;
the first monomer in the step (1) is Atri or Tri, and the second monomer is glycidyl methacrylate; the fourth monomer in the step (2) is octavinyl octasilsesquioxane.
2. The method for preparing proton exchange membrane compounded by oligosiloxane containing oxazole ring as recited in claim 1, wherein the first solvent is isopropanol or ethanol.
3. The method for preparing proton exchange membrane compounded by oligosiloxane containing oxazole ring as recited in claim 1, wherein the second solvent is deionized water or absolute ethyl alcohol.
4. The method for preparing proton exchange membrane compounded by oligosiloxane containing oxazole ring as claimed in claim 1, wherein the matrix in step (3) is SPEEK, SPES or SPTES.
5. The method of claim 1, wherein the initiator is AIBN.
6. An alkene monomer containing an azole ring is characterized in that the monomer is GMA-Atri, and the molecular formula of the monomer is as follows:
Figure FDA0002627091090000011
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060014877A1 (en) * 2004-07-16 2006-01-19 Ralph Taylor-Smith Solid state proton conductor system derived from hybrid composite inorganic-organic multicomponent material
CN1743378A (en) * 2005-07-28 2006-03-08 同济大学 A kind of organic/inorganic nano composite proton electro-conductive material and preparation method thereof
US20090297910A1 (en) * 2008-05-29 2009-12-03 Toyota Motor Engineering & Manufacturing North America, Inc. Proton Exchange Membranes Based on Heterocycles and Acids Through An Organic-Inorganic Hybrid Process
WO2012117786A1 (en) * 2011-02-28 2012-09-07 富士フイルム株式会社 Photosensitive composition, photosensitive solder-resist composition, photosensitive solder-resist film, permanent pattern, method for forming same, and printed circuit board
CN102949943A (en) * 2011-08-19 2013-03-06 东丽纤维研究所（中国）有限公司 Organic-inorganic hybridized sulfonated polyaryletherketone proton exchange membrane and preparation method thereof
CN106008809A (en) * 2016-07-29 2016-10-12 浙江大学 Porous cross-linked polymer containing triazole salt functional group as well as preparation method and application thereof
CN107104242A (en) * 2017-05-03 2017-08-29 武汉理工大学 A kind of polysiloxanes polyphosphonic acid doping universal PEM of SPEEK high/low temperatures and preparation method thereof
CN109037742A (en) * 2018-08-06 2018-12-18 西北工业大学 Ionic block copolymer containing POSS compound proton exchange membrane and preparation method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060014877A1 (en) * 2004-07-16 2006-01-19 Ralph Taylor-Smith Solid state proton conductor system derived from hybrid composite inorganic-organic multicomponent material
CN1743378A (en) * 2005-07-28 2006-03-08 同济大学 A kind of organic/inorganic nano composite proton electro-conductive material and preparation method thereof
US20090297910A1 (en) * 2008-05-29 2009-12-03 Toyota Motor Engineering & Manufacturing North America, Inc. Proton Exchange Membranes Based on Heterocycles and Acids Through An Organic-Inorganic Hybrid Process
WO2012117786A1 (en) * 2011-02-28 2012-09-07 富士フイルム株式会社 Photosensitive composition, photosensitive solder-resist composition, photosensitive solder-resist film, permanent pattern, method for forming same, and printed circuit board
CN102949943A (en) * 2011-08-19 2013-03-06 东丽纤维研究所（中国）有限公司 Organic-inorganic hybridized sulfonated polyaryletherketone proton exchange membrane and preparation method thereof
CN106008809A (en) * 2016-07-29 2016-10-12 浙江大学 Porous cross-linked polymer containing triazole salt functional group as well as preparation method and application thereof
CN107104242A (en) * 2017-05-03 2017-08-29 武汉理工大学 A kind of polysiloxanes polyphosphonic acid doping universal PEM of SPEEK high/low temperatures and preparation method thereof
CN109037742A (en) * 2018-08-06 2018-12-18 西北工业大学 Ionic block copolymer containing POSS compound proton exchange membrane and preparation method

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