CN103804680A - Crystalline sulfonated polyether ketone, polyether ketone ether ketone ketone and preparation method thereof - Google Patents
Crystalline sulfonated polyether ketone, polyether ketone ether ketone ketone and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a crystalline sulfonated polyether ketone, polyether ketone ether ketone ketone and a preparation method thereof, belonging to the technical field of a functional polymer material and preparation thereof. Nucleophilic substitution reaction is utilized to prepare semi-crystalline sulfonated polyether ketone and polyether ketone ether ketone ketone materials. Polyether-ether-ketone (PEEK) material has excellent mechanical and thermal properties based on the crystallization behavior; multi-sulfonated-side-group containing polyether ketone and polyether ketone ether ketone ketone materials are designed from the point of molecular structure design, and the length of the non-sulfonated chain segment is increased as far as possible to increase crystallization of the material, therefore, the locally high-density sulfonated polyether ketone and polyether ketone ether ketone ketone materials are provided, the length of a hydrophobic chain segment is increased, the aggregation extent of sulfonic acid groups is effectively improved, and the high-water-content swelling behavior of the sulfonated polyether ketone material during dry-wet state conversion is limited by a crystallization network inside the material.
Description
Technical field
The invention belongs to functional high molecule material and preparing technical field thereof, be specifically related to a kind of crystal type sulfonated polyether ketone, polyetherketoneetherketoneketone and preparation method thereof.
Background technology
Sulfonated poly aryl ether ketone is because of its good heat-resisting, chemical-resistant stability, excellent physical strength, simultaneously there is suitable proton conductivity because of it, Proton Exchange Membrane Fuel Cells (PEMFC), direct methanol fuel cell (DMFC), all-vanadium flow battery (VRB) etc. field have good application prospect.The technical bottleneck of current existence is: sulfonated polyether material is reaching the applicable conductivity (>10 of battery
-2s/cm) time, there is larger water swelling behavior in film in water (or acid) medium, and this has directly affected the stability of battery device, often causes film and catalyst layer to depart from, simultaneously because the excessively swelling film that also can cause is lost mechanical property.In order to break through the utilisation technology bottleneck of sulfonated polyether material, people are by a large amount of swelling problems of film of researching and solving.For example: prepare crosslinked sulfonated polyether film, the sulfonated polyether film of preparation inorganic materials doping, prepares polynary composite membrane etc.The exploration work of these effort advances the application paces of sulfonated polyether material, but still exists some to wait the problem solving, as problems such as cost, scale operation and complete processing simplification.
Crystallinity polyether-ether-ketone (PEEK) material, because its intramolecular crystallization behavior is given mechanics, the thermal property of material excellence.In the time that sulfonic acid group is introduced to PEEK segment, because sulfonic acid group has destroyed piling up in order of molecule segment, prepared sulfonated polyether-ether-ketone (SPEEK) is a kind of amorphous material, therefore, SPEEK material in the time that dry hygrometric state transforms, shows larger swelling behavior as solid electrolyte mould material.
Summary of the invention
Be difficult to the problem of balance in order to solve swelling ratio that traditional sulfonated polyether-ether-ketone material exists and proton conductivity, the invention provides a kind of crystal type sulfonated polyether ketone proton exchange membrane material, try hard to by the internal crystallization form of polymkeric substance, improve the water-fast and solvent resistance of material, solve the swelling problem of extreme that traditional sulfonated polyether-ether-ketone material occurs because of water suction under hot environment.The present invention, from Molecular Structure Design angle, has designed the polyetherketone and the polyetherketoneetherketoneketone material that contain many sulfonation side group.In order to promote the crystallization of material, increase as far as possible the length of crystallizable segment, therefore the concentrated introducing of the sulfonic acid group of the prepared sulfonated polyether ketone of the present invention and polyetherketoneetherketoneketone material specific position, formed high-density sulfonation district, and then increased the length of hydrophobic segment.Material sulfonated polyether ketone prepared by the present invention and sulfonated polyether ether ketone ketone ketone bill of material reveal obvious crystallization behavior and excellent solvent resistance.Prove to can be good at limiting the high dimensional change of sulfonated polyether-ether-ketone material in the time that dry hygrometric state is changed by the crystalline network of material internal.And sulfonated polyether ketone film has higher proton conductivity, meet its requirement to conductivity as proton exchange membrane.
Sulfonated polyether ketone polymer of the present invention, its structural formula is as follows:
Sulfonated polyether ether ketone ketone ketone polymer of the present invention, its structural formula is as follows:
Concrete technical scheme prepared by crystal type sulfonated polyether ketone material is as follows:
One, prepared by following two kinds of polymerization approachs the polyetherketone material that contains hexaphenyl benzene lateral group
First method is with 4,4 '-difluoro benzophenone, 4,4 '-dihydroxy benzophenone, containing two fluorine monomer I ((2 of hexaphenyl benzene lateral group, 6-difluorophenyl)-[4-(2,3,4,5,6 ,-pentapheneyl) phenyl] benzophenone (J.Mater.Chem.A, 2013,1,1465-1474) be raw material, take basic carbonate (mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate) as salt forming agent, take sulfobenzide as solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; Reaction after discharging in deionized water, through pulverizing, alcohol extraction is removed sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Wherein, fluorochemical monomer (4,4 '-difluoro benzophenone and two fluorine monomer I), 4, the mol ratio of 4 '-dihydroxy benzophenone and salt forming agent is 1:1:1.05~1.2, in fluorochemical monomer, the molar content of two fluorine monomer I is 0~30%, and is not 0; The quality of organic solvent is 2.3~3 times of all reactant quality (not comprising carbonate), thereby prepares the polyetherketone (PEK-HP) containing hexaphenyl benzene lateral group.
Second method is with 4-(4-fluorobenzene carbonyl) phenol, 4,4 '-dihydroxy benzophenone, containing two fluorine monomer I ((2 of hexaphenyl benzene lateral group, 6-difluorophenyl)-[4-(2,3,4,5,6,-pentapheneyl) phenyl] benzophenone) be raw material, take basic carbonate (mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate) as salt forming agent, sulfobenzide are as solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; Reaction after discharging in deionized water, through pulverizing, alcohol extraction is removed sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I and 4, the mol ratio of 4 '-dihydroxy benzophenone is 1:1; The fluorine atom molar content of two fluorine monomer I accounts in reactant 0~30% of total fluorine atom, and is not 0; The molar content of carbonate is 0.52~0.6 times of hydroxyl molar content in total reactant; The quality of organic solvent is 2.3~3 times of all reactant quality (not comprising carbonate), thereby prepares the polyetherketone (PEK-HP) containing hexaphenyl benzene lateral group
Two, the polyetherketoneetherketoneketone material that preparation contains hexaphenyl benzene lateral group
With 1,4-bis-(4-fluorobenzene carbonyl) benzene, 4,4 '-dihydroxy benzophenone, containing two fluorine monomer I ((2,6-difluorophenyl)-[4-(2,3 of hexaphenyl benzene lateral group, 4,5,6 ,-pentapheneyl) phenyl] benzophenone) be raw material, take basic carbonate (mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate) as salt forming agent, sulfobenzide are as solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; Reaction after discharging in deionized water, through pulverizing, alcohol extraction is removed sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Wherein, fluorochemical monomer (Isosorbide-5-Nitrae-bis-(4-fluorobenzene carbonyl) benzene and two fluorine monomer I), 4, the mol ratio of 4 '-dihydroxy benzophenone and salt forming agent is 1:1:1.05~1.2; In fluorochemical monomer, the molar content of two fluorine monomer I is 0~30%, and is not 0; The quality of organic solvent is 2.3~3 times of all reactant quality (not comprising carbonate), thereby prepares the polyetherketoneetherketoneketone (PEKEKK-HP) that contains hexaphenyl benzene lateral group.
Three, containing the polyetherketone of hexaphenyl benzene lateral group with containing the sulfonation of the polyetherketoneetherketoneketone material of hexaphenyl benzene lateral group.
Two class materials prepared in preceding step all have regular segmented structure, are Crystalline plastics.In conventional organic solvent, substantially do not dissolve, in the vitriol oil, have good solvability.Therefore we to choose the vitriol oil be sulfonated reagent, above-mentioned two base polymer materials are carried out to sulfonation.
Take 1g and put into 50mL Erlenmeyer flask containing the polyetherketone (PEK-HP) of hexaphenyl benzene lateral group or containing the polyetherketoneetherketoneketone (PEKEKK-HP) of hexaphenyl benzene lateral group, add the vitriol oil of 10~15mL mass concentration 95~98%, under room temperature, stir the solution that 10~20h obtains Vandyke brown homogeneous, thickness, discharging, in mixture of ice and water, is washed till liquid with deionized water and is neutral.Filtration, 110~140oC vacuum drying obtain crystal type sulfonated polymer of the present invention (PEK-SP or PEKEKK-SP).
Accompanying drawing explanation
Fig. 1: the wide-angle x-ray diffraction (WAXD) of polyetherketone polymkeric substance figure before and after sulfonation;
Fig. 2: the infrared spectrogram of polyetherketone polymkeric substance before and after sulfonation;
Fig. 3: the thermogravimetric curve of polyetherketone polymkeric substance before and after sulfonation;
Fig. 4: the proton conductivity of crystal type sulfonated polyether ketone film varies with temperature curve.
To the prepared polymkeric substance (PEK-HP and PEKEKK-HP) containing hexaphenyl benzene lateral group, the polymkeric substance (PEK-SP and PEKEKK-SP) of sulfonation has carried out the test of solubility property, find that the polymkeric substance before and after prepared sulfonation is all insoluble to conventional organic solvent, as N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), N, N-N,N-DIMETHYLACETAMIDE (DMAc), chloroform, tetrahydrofuran (THF) etc., can be dissolved in the vitriol oil.The superpower solvent resistance of polymkeric substance is because polymkeric substance inside exists physics cross-linking type crystalline network structure.
The crystal habit (accompanying drawing 1) of having observed sulfonation front and back polymkeric substance by WAXD, the polymer P EK-HP-15 before sulfonation is in 2 θ=18, and there is the characteristic diffraction peak of polyetherketone material in 20,22,29 places.And sulfonation post polymerization thing PEK-SP-15 still keeps the crystal diffraction peak of sulfonation prepolymer.Illustrate that sulfonated polyether ketone material that we prepare has the molecular chain structure of crystallization.
Utilize infrared spectra to observe the molecular structure of the polymkeric substance before and after sulfonation, as shown in Figure 2, the polymer P EK-HP-10 before and after sulfonation and PEK-SP-10, PEK-SP-15, PEK-SP-20 are at 1657cm
-1all there is the charateristic avsorption band of carbonyl in wave number place; Polymer P EK-SP-10, PEK-SP-15 after sulfonation, PEK-SP-20 are at 1036cm
-1there is the charateristic avsorption band of sulfonic acid group in wave number place.Digital proof by infrared spectra sulfonic acid group successfully introduced polymkeric substance.
Accompanying drawing 3 has provided the resistance toheat of sulfonation front and back polymkeric substance under nitrogen environment.Can find out from experimental data, the polymkeric substance (PEK-HP-10, PEK-HP-15) before sulfonation has very excellent thermostability, and initial heat decomposition temperature is more than 450oC.There are two zero-g periods in polymkeric substance (PEK-SP-10, PEK-SP-15, the PEK-SP-20) polymkeric substance after sulfonation, respectively at 280~400oC and 500~800oC, and corresponding the inner thermolysis of sulfonic acid group of polymkeric substance and the thermolysis of main polymer chain.The initial heat decomposition temperature of polymkeric substance after sulfonation illustrates that higher than 250oC prepared crystal type sulfonated polyether ketone and sulfonated polyether ether ketone ketone ketone material meet the requirement of polymer dielectric film to material thermal resistance energy completely.
Accompanying drawing 4 has provided the temperature variant curve of proton conductivity of crystal type sulfonated polyether ketone PEK-SP20 and commercial Nafion117 film.As can be seen from the figure, between whole test zone, the proton conductivity of PEK-SP20 film approaches Nafion117 film.Illustrate that crystal type sulfonated polyether ketone film has higher proton conductivity, meet its requirement to conductivity as proton exchange membrane.
Embodiment
Embodiment 1
The preparation (PEK-HP10) of the polyetherketone material of large side group molar content 10%
Two fluorine monomer I (0.0002mol), 4,4 '-difluoro benzophenone (0.0018mol), 4,4 '-dihydroxy benzophenone (0.002mol), anhydrous sodium carbonate (0.0024mol), sulfobenzide (DPS, 0.012mol) are incorporated with in the there-necked flask of water-taker.Nitrogen atmosphere Gradient heats up, 180oC, reaction 1h; Be warming up to 210oC, reaction 1h; Be warming up to 250oC, reaction 1h; Be warming up to 290oC, reaction 1h; Be warming up to 310oC, react 3 hours.Polymkeric substance is separated out in deionized water, remove sulfobenzide solvent 5 times through pulverizing, alcohol extraction, after deionized water extrct desalts, filter, 120oC vacuum-drying obtains polymkeric substance.
Embodiment 2
The preparation (PEK-HP15) of the polyetherketone material of large side group molar content 15%
Two fluorine monomer I (0.0003mol), 4-(4-fluorobenzene carbonyl) phenol (0.0034mol), 4,4 '-dihydroxy benzophenone (0.0003mol), anhydrous sodium carbonate (0.0024mol), sulfobenzide (DPS) enter to be equipped with in the there-necked flask of water-taker.Nitrogen atmosphere Gradient heats up, 180oC, reaction 1h; Be warming up to 210oC, reaction 1h; Be warming up to 250oC, reaction 1h; Be warming up to 290oC, reaction 1h; Be warming up to 310oC, react 3 hours.Polymkeric substance is separated out in water, through pulverizing, alcohol extraction sulfobenzide solvent 5 times, after deionized water extrct desalts, filter, 120oC vacuum-drying obtains polymkeric substance.
Embodiment 3
The preparation (PEK-HP20) of the polyetherketone material of large side group molar content 20%
Two fluorine monomer I (0.0004mol), 4,4 '-difluoro benzophenone (0.0016mol), 4,4 '-dihydroxy benzophenone (0.002mol), anhydrous sodium carbonate (0.0024mol), sulfobenzide (DPS) enter to be equipped with in the there-necked flask of water-taker.Nitrogen atmosphere Gradient intensification 180oC, reaction 1h; Be warming up to 210oC, reaction 1h; Be warming up to 250oC, reaction 1h; Be warming up to 290oC, reaction 1h; Be warming up to 310oC, react 3 hours.Polymkeric substance is separated out in water, through pulverizing, alcohol extraction sulfobenzide solvent 5 times, after deionized water extrct desalts, filter, 120oC vacuum-drying obtains polymkeric substance.
Embodiment 4
The preparation (PEKEKK-HP20) of the polyetherketoneetherketoneketone material of large side group molar content 20%
Two fluorine monomer I (0.0004mol), 1,4-bis-(4-fluorobenzene carbonyl) benzene (0.0016mol), 4,4 '-dihydroxy benzophenone (0.002mol), anhydrous sodium carbonate (0.0024mol), sulfobenzide (DPS) enter to be equipped with in the there-necked flask of water-taker.Nitrogen atmosphere Gradient intensification 180oC, reaction 1h; Be warming up to 210oC, reaction 1h; Be warming up to 250oC, reaction 1h; Be warming up to 290oC, reaction 1h; Be warming up to 310oC, react 3 hours.Polymkeric substance is separated out in water, through pulverizing, alcohol extraction sulfobenzide solvent 5 times, after deionized water extrct desalts, filter, 120oC vacuum-drying obtains polymkeric substance.
The polyetherketone of different side group molar content and the preparation of polyether ether ketone ketone material
Change the proportioning (in two fluorine monomer I, the content of fluorine atom accounts for the content of total fluorine atom in reaction system) of the two fluorine monomer I in embodiment 1 and embodiment 2 between 0<X≤30%, other conditions are constant, all can successfully prepare polyetherketone polymkeric substance.
Embodiment 6
Different types of manufacture of carbonates is containing polyetherketone and the polyetherketoneetherketoneketone of side group
By the sodium carbonate in embodiment 1 and embodiment 2, replace with salt of wormwood or cesium carbonate or their mixing salt, all successfully make polyetherketone polymkeric substance.
Embodiment 7
The preparation of sulfonated polyether ketone (PEK-SP) and sulfonated polyether ether ketone ketone ketone (PEKEKK-SP) material
The employing vitriol oil is sulfonated reagent, and prepared carried out to sulfonation containing the polyetherketone of side group and containing the polyetherketoneetherketoneketone material of side group, and specific experiment process is as follows.Take 1g polymer P EK-HP10 and put into 50mL Erlenmeyer flask, add the vitriol oil 15mL of mass concentration 98%, stirring at room temperature to completely dissolve after, continue stir 12h, then by auburn uniform solution discharging in frozen water, separate out bar shaped polymer.After deionized water is washed till neutrality, 120 ℃ of vacuum dryings, obtain PEK-SP10 sulfonated polyether ketone material.
Embodiment 8
Polymkeric substance in embodiment 7 is replaced with respectively to PEK-HP15, PEK-HP20, PEKEKK-HP20, other conditions are constant, all can successfully make PEK-SP15, PEK-SP20, PEKEKK-SP20 sulfonated polyether ketone material.
Claims (7)
1. a sulfonated polyether ketone polymer, its structural formula is as follows:
3. the preparation method of sulfonated polyether ketone polymer claimed in claim 1, its step is as follows:
(1), with 4,4 '-difluoro benzophenone, 4,4 '-dihydroxy benzophenone, is raw material containing two fluorine monomer I of hexaphenyl benzene lateral group, take basic carbonate as salt forming agent, take sulfobenzide as solvent, carries out nucleophilic substitution reaction under the reaction conditions of protection of inert gas; Reaction after discharging in deionized water, through pulverizing, alcohol extraction is removed sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I are (2,6-difluorophenyl)-[4-(2,3,4,5,6 ,-pentapheneyl) phenyl] benzophenone; Fluorochemical monomer, 4, the mol ratio of 4 '-dihydroxy benzophenone and salt forming agent is 1:1:1.05~1.2, in fluorochemical monomer, the molar content of two fluorine monomer I is 0~30%, and is not 0; The quality of solvent is 2.3~3 times of all reactant quality, thereby prepares the polyetherketone polymkeric substance containing hexaphenyl benzene lateral group;
(2) take the polyetherketone polymkeric substance of 1g containing hexaphenyl benzene lateral group, add wherein the vitriol oil of 10~15mL, mass concentration 95~98%, under room temperature, stir 10~20h, then discharging is in mixture of ice and water, be washed till liquid with deionized water and be neutral, filter final vacuum oven dry and obtain half hitch crystal formation sulfonated polyether ketone polymkeric substance.
4. the preparation method of sulfonated polyether ketone polymer claimed in claim 1, its step is as follows:
(1) with 4-(4-fluorobenzene carbonyl) phenol, 4,4 '-dihydroxy benzophenone, be raw material containing two fluorine monomer I of hexaphenyl benzene lateral group, take basic carbonate as salt forming agent, sulfobenzide is solvent, carries out nucleophilic substitution reaction under the reaction conditions of protection of inert gas; Reaction after discharging in deionized water, through pulverizing, alcohol extraction is removed sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I are (2,6-difluorophenyl)-[4-(2,3,4,5,6 ,-pentapheneyl) phenyl] benzophenone; Two fluorine monomer I and 4, the mol ratio of 4 '-dihydroxy benzophenone is 1:1; The fluorine atom molar content of two fluorine monomer I accounts in reactant 0~30% of total fluorine atom molar weight, and is not 0; The molar content of carbonate is 0.52~0.6 times of hydroxyl molar content in total reactant; The quality of solvent is 2.3~3 times of all reactant quality, thereby prepares the polyetherketone containing hexaphenyl benzene lateral group;
(2) take the polyetherketone polymkeric substance of 1g containing hexaphenyl benzene lateral group, add wherein the vitriol oil of 10~15mL, mass concentration 95~98%, under room temperature, stir 10~20h, then discharging is in mixture of ice and water, be washed till liquid with deionized water and be neutral, filter final vacuum oven dry and obtain half hitch crystal formation sulfonated polyether ketone polymkeric substance.
5. the preparation method of the sulfonated polyether ketone polymer as described in claim 3 or 4, is characterized in that: basic carbonate is one or more the mixing in sodium carbonate, salt of wormwood, cesium carbonate.
6. the preparation method of sulfonated polyether ether ketone ketone ketone polymer claimed in claim 2, its step is as follows:
(1) with 1,4-bis-(4-fluorobenzene carbonyl) benzene, 4,4 '-dihydroxy benzophenone, be raw material containing two fluorine monomer I of hexaphenyl benzene lateral group, take basic carbonate as salt forming agent, sulfobenzide is solvent, carries out nucleophilic substitution reaction under the reaction conditions of protection of inert gas; Reaction after discharging in deionized water, through pulverizing, alcohol extraction is removed sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I are (2,6-difluorophenyl)-[4-(2,3,4,5,6 ,-pentapheneyl) phenyl] benzophenone; Fluorochemical monomer, 4, the mol ratio of 4 '-dihydroxy benzophenone and salt forming agent is 1:1:1.05~1.2; In fluorochemical monomer, the molar content of two fluorine monomer I is 0~30%, and is not 0; The quality of solvent is 2.3~3 times of all reactant quality, thereby prepares the polyetherketoneetherketoneketone that contains hexaphenyl benzene lateral group;
(2) take the polyetherketoneetherketoneketone polymkeric substance of 1g containing hexaphenyl benzene lateral group, add wherein the vitriol oil of 10~15mL, mass concentration 95~98%, under room temperature, stir 10~20h, then discharging is in mixture of ice and water, be washed till liquid with deionized water and be neutral, filter final vacuum oven dry and obtain half hitch crystal formation sulfonated polyether ketone ether ketone ketone polymer.
7. the preparation method of sulfonated polyether ketone polymer as claimed in claim 6, is characterized in that: basic carbonate is one or more the mixing in sodium carbonate, salt of wormwood, cesium carbonate.
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CN104193986A (en) * | 2014-06-30 | 2014-12-10 | 中国科学院上海有机化学研究所 | Polyether-ether-ketone capable of being cured as well as preparation method and application thereof |
CN105130774A (en) * | 2015-09-09 | 2015-12-09 | 吉林大学 | Hexaphenylbenzene structure-containing difluo monomer, preparation method and application of difluo monomer in preparation of polyarylether |
CN106711482A (en) * | 2017-01-18 | 2017-05-24 | 吉林大学 | Crystalline polymer three-dimensional network reinforced sulfonated polyether ether ketone based composite ion exchange membrane and preparation method thereof |
CN111952648A (en) * | 2020-08-25 | 2020-11-17 | 吉林大学 | Enhanced composite polymer electrolyte membrane and preparation method and application thereof |
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CN101463129B (en) * | 2008-12-04 | 2011-02-02 | 上海大学 | Method for synthesizing sulphonation polyetheretherketone for proton exchange membrane by three-step process |
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WO2008067023A2 (en) * | 2006-10-11 | 2008-06-05 | Konarka Technologies, Inc. | Photovoltaic cell with thiazole-containing polymer |
CN101463129B (en) * | 2008-12-04 | 2011-02-02 | 上海大学 | Method for synthesizing sulphonation polyetheretherketone for proton exchange membrane by three-step process |
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CN104193986A (en) * | 2014-06-30 | 2014-12-10 | 中国科学院上海有机化学研究所 | Polyether-ether-ketone capable of being cured as well as preparation method and application thereof |
CN105130774A (en) * | 2015-09-09 | 2015-12-09 | 吉林大学 | Hexaphenylbenzene structure-containing difluo monomer, preparation method and application of difluo monomer in preparation of polyarylether |
CN106711482A (en) * | 2017-01-18 | 2017-05-24 | 吉林大学 | Crystalline polymer three-dimensional network reinforced sulfonated polyether ether ketone based composite ion exchange membrane and preparation method thereof |
CN111952648A (en) * | 2020-08-25 | 2020-11-17 | 吉林大学 | Enhanced composite polymer electrolyte membrane and preparation method and application thereof |
CN111952648B (en) * | 2020-08-25 | 2022-03-11 | 吉林大学 | Enhanced composite polymer electrolyte membrane and preparation method and application thereof |
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