CN103804680B - Crystal type sulfonated polyether ketone, polyetherketoneetherketoneketone and preparation method thereof - Google Patents
Crystal type sulfonated polyether ketone, polyetherketoneetherketoneketone and preparation method thereof Download PDFInfo
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Abstract
Semicrystalline sulfonated polyether ketone, polyetherketoneetherketoneketone and preparation method thereof, belong to functional high molecule material and preparing technical field thereof.The present invention utilizes nucleophilic substitution reaction to prepare semicrystalline sulfonated polyether ketone, polyetherketoneetherketoneketone material.The present invention is based on mechanics and thermal property that crystallization behavior gives PEEK material excellence, from Molecular Structure Design angle, devise the polyetherketone containing many sulfonation side base and polyetherketoneetherketoneketone material, the length strengthening non-sulfonated segment as far as possible increases the crystallization of material, therefore the invention provides local high density sulfonated polyether ketone and polyetherketoneetherketoneketone material, namely the length of hydrophobic segment is added, effectively raise the aggregation extent of sulfonic acid group simultaneously, by the high water swelling behavior of crystalline network restriction sulfonated polyether-ether-ketone material when dry hygrometric state is changed of material internal.
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 because of it, there is suitable proton conductivity, 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, larger water swelling behavior has been there is in film in water (or acid) medium, this directly affects the stability of battery device, often causes film and catalyst layer to depart from, simultaneously because the excessively swelling film that also can cause loses mechanical property.In order to break through the utilisation technology bottleneck of sulfonated polyether material, people research and solve the swelling problem of film by a large amount of.Such as: the sulfonated polyether film that preparation is crosslinked, the sulfonated polyether film of preparation inorganic materials doping, prepares multiple elements design film etc.The exploration work of these effort advances the application paces of sulfonated polyether material, but still there are some problems waiting to solve, as problems such as cost, scale operation and complete processing simplification.
Crystalline polyether-ether-ketofoam (PEEK) material, because its intramolecular crystallization behavior gives mechanics, the thermal property of material excellence.When sulfonic acid group being introduced PEEK segment, because sulfonic acid group destroys piling up in order of molecule segment, obtained sulfonated polyether-ether-ketone (SPEEK) is a kind of amorphous material, therefore, SPEEK material is used as solid electrolyte mould material when dry hygrometric state transforms, and shows larger swelling behavior.
Summary of the invention
In order to the swelling ratio and proton conductivity that solve the existence of traditional sulfonated polyether-ether-ketone material are difficult to the problem of balance, 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 traditional sulfonated polyether-ether-ketone material in high temperature environments because of the swelling problem of extreme occurred that absorbs water.The present invention, from Molecular Structure Design angle, devises the polyetherketone containing many sulfonation side base and polyetherketoneetherketoneketone material.In order to promote the crystallization of material, increase the length of crystallizable segment as far as possible, what therefore the sulfonic acid group of sulfonated polyether ketone prepared by the present invention and polyetherketoneetherketoneketone material was concentrated introduces specific position, defines high-density sulfonation district, and then adds 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 when dry hygrometric state is changed by the crystalline network of material internal.And sulfonated polyether ketone film has higher proton conductivity, meet it as the requirement of proton exchange membrane to conductivity.
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, the polyetherketone material containing hexaphenyl benzene lateral group has been prepared by following two kinds of polymerization approachs
First method is with 4,4 '-difluoro benzophenone, 4,4 '-dihydroxy benzophenone, two fluorine monomers I ((2 containing 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, with basic carbonate (mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate) for salt forming agent, take sulfobenzide as solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; After reaction, discharging is in deionized water, through pulverizing, alcohol extraction removing 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, and 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), thus prepares the polyetherketone (PEK-HP) containing hexaphenyl benzene lateral group.
Second method is with 4-(4-fluorobenzene carbonyl) phenol, 4,4 '-dihydroxy benzophenone, two fluorine monomers I ((2 containing hexaphenyl benzene lateral group, 6-difluorophenyl)-[4-(2,3,4,5,6,-pentapheneyl) phenyl] benzophenone) be raw material, with basic carbonate (mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate) for salt forming agent, sulfobenzide are for solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; After reaction, discharging is in deionized water, through pulverizing, alcohol extraction removing 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 for 0 ~ 30% of total fluorine atom in reactant, 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), thus prepares the polyetherketone (PEK-HP) containing hexaphenyl benzene lateral group
Two, the polyetherketoneetherketoneketone material of preparation containing hexaphenyl benzene lateral group
With 1,4-bis-(4-fluorobenzene carbonyl) benzene, 4,4 '-dihydroxy benzophenone, two fluorine monomers I ((2,6-difluorophenyl)-[4-(2,3 containing hexaphenyl benzene lateral group, 4,5,6 ,-pentapheneyl) phenyl] benzophenone) be raw material, with basic carbonate (mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate) for salt forming agent, sulfobenzide are for solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; After reaction, discharging is in deionized water, through pulverizing, alcohol extraction removing sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Wherein, fluorochemical monomer (Isosorbide-5-Nitrae-two (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), thus prepares the polyetherketoneetherketoneketone (PEKEKK-HP) containing hexaphenyl benzene lateral group.
Three, containing the polyetherketone of hexaphenyl benzene lateral group and the sulfonation of polyetherketoneetherketoneketone material containing hexaphenyl benzene lateral group.
Two class materials prepared in preceding step all have regular segmented structure, are Crystalline plastics.Substantially do not dissolve in the organic solvent of routine, have good solvability in concentrated sulfuric acid.Therefore we choose the vitriol oil is sulfonated reagent, carries out sulfonation to above-mentioned two base polymer materials.
Take 1g contain the polyetherketone (PEK-HP) of hexaphenyl benzene lateral group or put into 50mL Erlenmeyer flask containing the polyetherketoneetherketoneketone (PEKEKK-HP) of hexaphenyl benzene lateral group, add the vitriol oil of 10 ~ 15mL massfraction 95 ~ 98%, stirred at ambient temperature 10 ~ 20h obtains that Vandyke brown is homogeneous, the solution of thickness, discharging, in mixture of ice and water, is washed till liquid shows neutral with deionized water.Filtration, 110 ~ 140 DEG C of vacuum dryings obtain crystal type sulfonated polymer (PEK-SP or PEKEKK-SP) of the present invention.
Accompanying drawing explanation
Fig. 1: Wide angle X-ray diffraction (WAXD) figure of polyether ketone polymer before and after sulfonation;
Fig. 2: the infrared spectrogram of polyether ketone polymer before and after sulfonation;
Fig. 3: the thermogravimetric curve of polyether ketone polymer 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, polymkeric substance before and after sulfonation prepared by discovery 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)s etc., can dissolve in concentrated sulfuric acid.The superpower solvent resistance of polymkeric substance is because polymeric inner exists physics cross-linking type crystalline network structure.
Observed the crystal habit (accompanying drawing 1) of polymkeric substance before and after sulfonation by WAXD, the polymer P EK-HP-15 before sulfonation in 2 θ=18,20,22, there is the characteristic diffraction peak of polyetherketone material in 29 places.And sulfonation post-consumer polymer 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 the molecular structure of infrared spectra to the polymkeric substance before and after sulfonation to observe, as shown in Figure 2, polymer P EK-HP-10 and PEK-SP-10 before and after sulfonation, 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, PEK-SP-20 after sulfonation are at 1036cm
-1there is the charateristic avsorption band of sulfonic acid group in wave number place.Sulfonic acid group is successfully introduced polymkeric substance by the digital proof of infrared spectra.
Fig. 3 gives polymkeric substance resistance toheat in a nitrogen environment before and after sulfonation.As can be seen from experimental data, the polymkeric substance (PEK-HP-10, PEK-HP-15) before sulfonation has very excellent thermostability, and initial pyrolyzation temperature is more than 450 DEG C.There are two zero-g periods in polymkeric substance (PEK-SP-10, PEK-SP-15, PEK-SP-20) polymkeric substance after sulfonation, respectively at 280 ~ 400 DEG C and 500 ~ 800 DEG C, correspond to the thermolysis of polymeric inner sulfonic acid group and the thermolysis of main polymer chain.Crystal type sulfonated polyether ketone prepared by polymkeric substance initial pyrolyzation temperature after sulfonation illustrates higher than 250 DEG C and sulfonated polyether ether ketone ketone ketone material meet the requirement of polymer dielectric film to material thermal resistance energy completely.
Fig. 4 shows the temperature variant curve of proton conductivity of crystal type sulfonated polyether ketone PEK-SP20 and commercial Nafion 117 film.As can be seen from the figure, between whole test zone the proton conductivity of PEK-SP20 film close to Nafion 117 film.Illustrate that crystal type sulfonated polyether ketone film has higher proton conductivity, meet it as the requirement of proton exchange membrane to conductivity.
Embodiment
Embodiment 1
The preparation (PEK-HP10) of the polyetherketone material of large side base 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, 180 DEG C, reaction 1h; Be warming up to 210 DEG C, reaction 1h; Be warming up to 250 DEG C, reaction 1h; Be warming up to 290 DEG C, reaction 1h; Be warming up to 310 DEG C, react 3 hours.Separated out in deionized water by polymkeric substance, through pulverizing, alcohol extraction 5 removing sulfobenzide solvents, filter after deionized water extrct desalts, 120 DEG C of vacuum-dryings obtain polymkeric substance.
Embodiment 2
The preparation (PEK-HP15) of the polyetherketone material of large side base 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, 180 DEG C, reaction 1h; Be warming up to 210 DEG C, reaction 1h; Be warming up to 250 DEG C, reaction 1h; Be warming up to 290 DEG C, reaction 1h; Be warming up to 310 DEG C, react 3 hours.Separated out in water by polymkeric substance, through pulverizing, alcohol extraction sulfobenzide solvent 5 times, filter after deionized water extrct desalts, 120 DEG C of vacuum-dryings obtain polymkeric substance.
Embodiment 3
The preparation (PEK-HP20) of the polyetherketone material of large side base 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 heats up 180 DEG C, reaction 1h; Be warming up to 210 DEG C, reaction 1h; Be warming up to 250 DEG C, reaction 1h; Be warming up to 290 DEG C, reaction 1h; Be warming up to 310 DEG C, react 3 hours.Separated out in water by polymkeric substance, through pulverizing, alcohol extraction sulfobenzide solvent 5 times, filter after deionized water extrct desalts, 120 DEG C of vacuum-dryings obtain polymkeric substance.
Embodiment 4
The preparation (PEKEKK-HP20) of the polyetherketoneetherketoneketone material of large side base 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 heats up 180 DEG C, reaction 1h; Be warming up to 210 DEG C, reaction 1h; Be warming up to 250 DEG C, reaction 1h; Be warming up to 290 DEG C, reaction 1h; Be warming up to 310 DEG C, react 3 hours.Separated out in water by polymkeric substance, through pulverizing, alcohol extraction sulfobenzide solvent 5 times, filter after deionized water extrct desalts, 120 DEG C of vacuum-dryings obtain polymkeric substance.
Embodiment 5
The not polyetherketone of homonymy base 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 monomers I in embodiment 1 and embodiment 2 between 0<X≤30%, other conditions are constant, all successfully can prepare polyether ketone polymer.
Embodiment 6
Different types of manufacture of carbonates contains polyetherketone and the polyetherketoneetherketoneketone of side base
By the sodium carbonate in embodiment 1 and embodiment 2, replace with salt of wormwood or cesium carbonate or their mixing salt, all successfully obtained polyether ketone polymer.
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 carry out sulfonation to the prepared polyetherketone containing side base and the polyetherketoneetherketoneketone material containing side base, specific experiment process is as follows.Take 1g polymer P EK-HP10 and put into 50mL Erlenmeyer flask, add quality
fraction concentrationthe vitriol oil 15mL of 98%, stirring at room temperature, to after dissolving completely, continues to stir 12h, then by auburn uniform solution discharging in frozen water, separate out bar shaped polymer.Be washed till after neutrality through deionized water, 120 DEG C of vacuum dryings, obtain PEK-SP10 sulfonated polyether ketone material.
Embodiment 8
Polymkeric substance in embodiment 7 is replaced with PEK-HP15 respectively, PEK-HP20, PEKEKK-HP20, other conditions are constant, all can successfully obtain PEK-SP15, PEK-SP20, PEKEKK-SP20 sulfonated polyether ketone material.
Claims (7)
1. a sulfonated polyether ketone polymer, its structural formula is as follows:
2. a sulfonated polyether ether ketone ketone ketone polymer, its structural formula is as follows:
3. the preparation method of sulfonated polyether ketone polymer according to claim 1, its step is as follows:
(1) with 4,4 '-difluoro benzophenone, 4, is raw material containing two fluorine monomers I of hexaphenyl benzene lateral group at 4 '-dihydroxy benzophenone, take basic carbonate as salt forming agent, take sulfobenzide as solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; After reaction, discharging is in deionized water, through pulverizing, alcohol extraction removing sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I is (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, and 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, thus prepares the polyether ketone polymer containing hexaphenyl benzene lateral group;
(2) polyether ketone polymer of 1g containing hexaphenyl benzene lateral group is taken, add the vitriol oil of 10 ~ 15mL, massfraction 95 ~ 98% wherein, stirred at ambient temperature 10 ~ 20h, then discharging is in mixture of ice and water, be washed till liquid shows neutral with deionized water, filter final vacuum oven dry and obtain semicrystalline sulfonated polyether ketone polymer.
4. the preparation method of sulfonated polyether ketone polymer according to claim 1, its step is as follows:
(1) with 4-(4-fluorobenzene carbonyl) phenol, 4,4 '-dihydroxy benzophenone, be raw material containing two fluorine monomers I of hexaphenyl benzene lateral group, take basic carbonate as salt forming agent, sulfobenzide is solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; After reaction, discharging is in deionized water, through pulverizing, alcohol extraction removing sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I is (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 for 0 ~ 30% of total fluorine atom molar weight in reactant, 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, thus prepares the polyetherketone containing hexaphenyl benzene lateral group;
(2) polyether ketone polymer of 1g containing hexaphenyl benzene lateral group is taken, add the vitriol oil of 10 ~ 15mL, massfraction 95 ~ 98% wherein, stirred at ambient temperature 10 ~ 20h, then discharging is in mixture of ice and water, be washed till liquid shows neutral with deionized water, filter final vacuum oven dry and obtain semicrystalline sulfonated polyether ketone polymer.
5. the preparation method of the sulfonated polyether ketone polymer as described in claim 3 or 4, is characterized in that: basic carbonate is the mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate.
6. the preparation method of sulfonated polyether ether ketone ketone ketone polymer according to 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 monomers I of hexaphenyl benzene lateral group, take basic carbonate as salt forming agent, sulfobenzide is solvent, under the reaction conditions of protection of inert gas, carry out nucleophilic substitution reaction; After reaction, discharging is in deionized water, through pulverizing, alcohol extraction removing sulfobenzide solvent, then deionized water extrct desalt after filter and vacuum drying; Two fluorine monomer I is (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, thus prepares the polyetherketoneetherketoneketone containing hexaphenyl benzene lateral group;
(2) the polyetherketoneetherketoneketone polymkeric substance of 1g containing hexaphenyl benzene lateral group is taken, add the vitriol oil of 10 ~ 15mL, massfraction 95 ~ 98% wherein, stirred at ambient temperature 10 ~ 20h, then discharging is in mixture of ice and water, be washed till liquid shows neutral with deionized water, filter final vacuum oven dry and obtain semicrystalline sulfonated polyether ether ketone ketone ketone polymer.
7. the preparation method of sulfonated polyether ketone polymer as claimed in claim 6, is characterized in that: basic carbonate is the mixing of one or more in sodium carbonate, salt of wormwood, cesium carbonate.
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| CN101463128A (en) * | 2008-12-30 | 2009-06-24 | 吉林大学 | Polyarylether polymer containing amino-benzene lateral group and method for synthesizing the same |
| 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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| 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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