CN101717504B - Method for modifying sulfonated polyaryetherketone and method for preparing polymer electrolyte material - Google Patents
Method for modifying sulfonated polyaryetherketone and method for preparing polymer electrolyte material Download PDFInfo
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- CN101717504B CN101717504B CN2009102412683A CN200910241268A CN101717504B CN 101717504 B CN101717504 B CN 101717504B CN 2009102412683 A CN2009102412683 A CN 2009102412683A CN 200910241268 A CN200910241268 A CN 200910241268A CN 101717504 B CN101717504 B CN 101717504B
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Abstract
The invention relates to a method for modifying sulfonated polyaryetherketone and a method for preparing a polymer electrolyte material, and belongs to the technical field of the preparation of functional polymer materials. The method comprises the following steps: dissolving the sulfonated polyaryetherketone in a solvent; introducing inert gas and adding a reducing agent with stirring; performing vacuum drying to obtain reduced and modified sulfonated polyaryetherketone; adding a catalyst and a crosslinker into the solution of reduced and modified sulfonated polyaryetherketone under the inert gas, and stirring the mixture to prepare membrane liquor; performing membrane preparation; completing a crosslinking reaction in the process of membrane forming; and performing demoulding and washing for airing to obtain a cross-linked polymer electrolyte membrane material, wherein the crosslinker is polyaldehyde or polybasic carboxylic acid. The modification method has the characteristics of easily obtained raw materials and simple operation; the prepared cross-linked polymer electrolyte material has the advantages of excellent mechanical strength, conductivity, methanol-blocking performance and dimensional stability, can be directly used in the fields of methanol fuel cells, proton exchange membranes of proton exchange membrane fuel cells, ion exchange resin, membrane separation, sensors and the like, and has important application value.
Description
Technical field
The present invention relates to a kind of method of modifying and polymer electrolyte prepared therefrom that contains sulfonic group polyaryletherketone base polymer, belong to the functional high molecule material preparing technical field.
Technical background
Polyaryletherketone is that main chain contains ehter bond and carbonyl one class aromatic polymer, as polyether-ether-ketone, polyether ether ketone ketone, polyetherketone, polyetherketone sulfone etc. is a class engineering plastics with general high-performance, has in fields such as space flight, aviation, machinery, chemical industry, electric apparatus widely to use.Sulfonated poly aryl ether ketone is meant and contains the substituent polymkeric substance of sulfonic acid on the polyaryletherketone aromatic ring, is the new function formed material that developed recently gets up, and has a good application prospect at aspects such as fuel cell, membrane sepn, transmitter, ion exchange resin.
Proton exchange polymer membrane is the critical material of Proton Exchange Membrane Fuel Cells (PEMFC) and direct methanol fuel cell (DMFC), and its performance quality plays crucial effects to the output performance of battery.At present, the proton exchange membrane material that generally adopts among PEMFC and the DMFC is a perfluorinated sulfonic acid class film, this class material has higher proton conductivity, chemistry and mechanical stability, but its temperature tolerance, alcohol-rejecting ability, poor dimensional stability and price and costliness thereof, these shortcomings become and hinder it at one of obstacle of PEMFC and DMFC large-scale application, therefore seek low cost, temperature tolerance, novel proton exchange membranes that alcohol-resistant performance is good is the business-like key of fuel cell.
In recent years, many investigators have prepared the proton exchange membrane material based on sulfonated poly aryl ether ketone, and these sulfonated membranes have higher proton-conducting and alcohol-rejecting ability, are expected to obtain to use in fuel cell.But because the constructional feature of this base polymer itself, there is the contradiction of performances such as proton conductivity and dimensional stability (swell-resistant), physical strength mostly in the sulfonated poly aryl ether ketone proton exchange membrane, promptly, in order to obtain higher proton conductivity, need polymkeric substance to have higher sulfonation degree, but too high sulfonation degree can cause the dimensional stabilizing of film and physical strength not good enough, and this easily causes membrane electrode damage even film rupture DMFC and PEMFC in service, has a strong impact on the battery operation life-span.
Summary of the invention
The present invention discloses a kind of method of modifying of sulfonated poly aryl ether ketone and prepares the method for polymer electrolyte by it.The method of modifying of sulfonated poly aryl ether ketone of the present invention, it is characterized in that sulfonated poly aryl ether ketone is dissolved in appropriate solvent, add an amount of reductive agent, reaction at a certain temperature, make the carbonyl moiety in the sulfonated poly aryl ether ketone be reduced to hydroxyl, obtain preparation liquid at adding linking agent and catalyzer then, remove solvent through thermal treatment, and in film-forming process, finish crosslinking reaction, obtain crosslinked polymer dielectric film material.
Matrix polymer of the present invention is a polyaryletherketone, is meant the general designation of a class aromatic polymer that contains carbonyl and ehter bond on main polymer chain, and its several typical structures as shown in Figure 1.Sulfonated polymer of the present invention is meant and contains the substituent polyaryletherketone of sulfonic acid on molecular chain, and its sulfonic acid substituting group can be positioned at the aromatic ring adjacent with ehter bond, also can be positioned at aromatic ring that carbonyl links to each other on.The preparation of described sulfonated poly aryl ether ketone both can be by with polyaryletherketone H
2SO
4, SO
3, sulphonating agent sulfonation modifying such as chlorsulfonic acid obtains, also can be by obtaining to contain the substituent monomer direct polymerization of sulfonic acid.
The method of modifying of sulfonated poly aryl ether ketone of the present invention and the preparation process of polymer electrolyte are as follows:
(1) the reduction modification of polymkeric substance
Sulfonated poly aryl ether ketone is dissolved in the suitable solvent, obtains polymers soln; Take by weighing an amount of polymers soln, feed rare gas element, open and stir, under 10-50 ℃ of temperature, slowly add an amount of reductive agent; In inert atmosphere, make reaction system remain on 30-150 ℃ and continue reaction 3-24 hour, after the filtration the concentrated also vacuum-drying of filtrate is obtained reduzate, and be dissolved in suitable solvent, be mixed with solution for standby.
Solvent of the present invention is any one or a few the mixture in acetone, methyl alcohol, ethanol, water, acetonitrile, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), sulfobenzide, tetramethylene sulfone, the N-Methyl pyrrolidone.
Reductive agent of the present invention is zinc powder, magnesium powder, reduced iron powder/HCl, SnCl
2The mixture of any one or a few among/HCl, lithium aluminum hydride, sodium borohydride, the hydrazine hydrate/Pd/C.
The mass ratio of sulfonated poly aryl ether ketone of the present invention and reductive agent is 120: 1-40, and the mass percentage concentration of described sulfonated poly aryl ether ketone in solvent is 3-25%;
(2) the crosslinked system film of polymkeric substance
Get the sulfonated poly aryl ether ketone solution after an amount of reduction modification; under protection of inert gas, add catalyzer and linking agent; wherein the mass ratio of sulfonated poly aryl ether ketone, catalyzer and linking agent is 100: (0-40): (0-50), controlled temperature mixes at 0-50 ℃ and got preparation liquid in 0.5-8 hour.Preparation liquid is applied to makes film on the substrate, handle to remove through 40-180 ℃ of temperature programming and desolvate, and in film process, finish crosslinking reaction.Be chilled to the room temperature demoulding, and soaked 24 hours at dilution heat of sulfuric acid, washing obtains crosslinked polymer dielectric film material after drying repeatedly.
Linking agent of the present invention be polyaldehyde (as oxalic dialdehyde, mda, suceinic aldehyde, glutaraldehyde etc.) or polycarboxylic acid (as oxalic acid, propanedioic acid, Succinic Acid, butene dioic acid, m-phthalic acid, terephthalic acid, trimellitic acid etc.).
Catalyzer of the present invention can be acid catalyst, also can be alkaline catalysts.An acidic catalyst is any one or a few the mixture in hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic, trifluoromethane sulfonic acid, trifluoroacetic acid, the perfluorinated sulfonic acid; Basic catalyst is NaOH, KOH, Na
2CO
3, K
2CO
3, any one or a few the mixture in the pyridine, Trimethylamine, triethylamine.
Described method of modifying has raw material and is easy to get, characteristics simple to operate; Preparation-obtained crosslinking polymer electrolyte has excellent mechanical intensity, electric conductivity, alcohol-rejecting ability and dimensional stability, especially dimensional stability and alcohol-rejecting ability will be much better than the material of Non-crosslinked modification, can be used for the field such as proton exchange membrane, ion exchange resin, membrane sepn, transmitter of direct methanol fuel cell (DMFC), Proton Exchange Membrane Fuel Cells (PEMFC), have significant application value.
Description of drawings
Fig. 1 is several molecular structure exemplary plot of matrix polymer polyaryletherketone.
Embodiment
Below in conjunction with embodiment the present invention is described.
Embodiment:
Example 1: get sulfonation degree and be 75% sulfonated polyether-ether-ketone and be dissolved in the ethanol/water, be configured to per-cent and be 15% solution; Take by weighing 100 parts of polymers solns.Open and stir, under protection of inert gas, behind 2 parts of slow adding reductive agent lithium aluminum hydrides under 25 ℃ of temperature, make reaction system remain on 30-80 ℃ and continue reaction 6 hours, concentrating filtrate also after the filtration, vacuum-drying obtains the reductive sulfonated polyether-ether-ketone; Dried reduzate is dissolved in dimethyl formamide, is mixed with mass percent and is 10% solution for standby.
Example 2: get sulfonation degree and be 75% sulfonated polyether-ether-ketone sulfone and be dissolved in the N,N-DIMETHYLACETAMIDE, be configured to per-cent and be 8% solution; Take by weighing 100 parts of polymers solns.Open and stir, under protection of inert gas, behind 1.5 parts of an amount of reductive agent zinc powders of slow adding under 50 ℃ of temperature, make reaction system remain on 50-100 ℃ and continue reaction 8 hours, concentrating filtrate also after the filtration, vacuum-drying obtains reductive sulfonated polyether-ether-ketone sulfone; Dried reduzate is dissolved in dimethyl sulfoxide (DMSO), is mixed with mass percent and is 8% solution for standby.
Example 3: get per-cent and be 100 parts of 10% sulfonated polyether-ether-ketone reduzate solution, add catalyzer (sulfuric acid/dimethyl formamide solution of 10%) 5 parts, 2 parts of linking agent mdas mixed 0.5 hour in 25 ℃ of room temperatures, the heavy-gravity preparation liquid.Preparation liquid is applied on the clean sheet glass makes film, as for 60 ℃ of baking oven thermal treatments 3 hours, 100 ℃ 4 hours, 150 ℃ 6 hours, be cooled to room temperature, demoulding, and soaked 24 hours at dilution heat of sulfuric acid, washing obtains crosslinked sulfonated polyether-ether-ketone film after drying repeatedly.
Example 4: get per-cent and be 150 parts of 8% sulfonated polyether-ether-ketone sulfone reduzate solution, add 1 part of catalyst n aOH, 2 parts of linking agent oxalic acid mixed 2 hours in 30 ℃, the heavy-gravity preparation liquid.Preparation liquid is applied on the clean sheet glass makes film, as for 50 ℃ of baking oven thermal treatments 3 hours, 80 ℃ 4 hours, 120 ℃ 6 hours, 180 ℃ 6 hours, be cooled to room temperature, demoulding, and dilution heat of sulfuric acid immersion 24 hours, washing obtained crosslinked sulfonated polyether-ether-ketone sulfone film after drying repeatedly.
Example 5: get per-cent and be 100 parts of 15% sulfonated polyether ketone sulfone reduzate solution, add catalyzer (10% trifluoroacetic acid/dimethyl sulfoxide (DMSO) amine aqueous solution) 2 parts, 1.5 parts of linking agent terephthalic aldehydes mixed 2 hours in 50 ℃ of room temperatures, got the heavy-gravity preparation liquid.Preparation liquid is applied on the clean sheet glass makes film, as for 60 ℃ of baking oven thermal treatments 4 hours, 100 ℃ 4 hours, 160 ℃ 4 hours, be cooled to room temperature, demoulding, and dilution heat of sulfuric acid immersion 24 hours, washing obtained crosslinked sulfonated sulfonated polyether ketone sulfone after drying repeatedly.
Claims (7)
1. the method for modifying of a sulfonated poly aryl ether ketone is characterized in that, this method is dissolved in sulfonated poly aryl ether ketone in the solvent, obtains mass percent and be 3～25% solution; Take by weighing polymers soln, feed rare gas element, open and stir, under 10～50 ℃ of temperature, slowly add reductive agent; The mass ratio of described sulfonated poly aryl ether ketone and reductive agent is 120: 1～40; In inert atmosphere, make reaction system remain on 30～150 ℃ and continue reaction 3～24 hours, concentrating filtrate also after the filtration, vacuum-drying obtains reduzate, be dissolved in solvent, being mixed with mass percent is 5～20% solution, obtains reducing sulfonated poly aryl ether ketone solution after the modification;
Described solvent is any one or a few the mixture in acetone, methyl alcohol, ethanol, water, acetonitrile, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), sulfobenzide, tetramethylene sulfone, the N-Methyl pyrrolidone;
Described reductive agent is zinc powder, magnesium powder, reduced iron powder/HCl, SnCl
2Among/HCl, lithium aluminum hydride, sodium borohydride, the hydrazine hydrate/Pd/C any one.
2. a sulfonated poly aryl ether ketone prepares the method for polymer electrolyte, it is characterized in that this method steps is as follows:
(1) the reduction modification of polymkeric substance
Sulfonated poly aryl ether ketone is dissolved in the solvent, obtains mass percent and be 3～25% solution; Take by weighing polymers soln, feed rare gas element, open and stir, under 10～50 ℃ of temperature, slowly add reductive agent; The mass ratio of described sulfonated poly aryl ether ketone and reductive agent is 120: 1～40; Make reaction system remain on 30～150 ℃ in inert atmosphere and continue reaction 3～24 hours, after the filtration the concentrated also vacuum-drying of filtrate is obtained reduzate, and be dissolved in solvent, being mixed with mass percent is 5～20% sulfonated poly aryl ether ketone solution for standby;
Described solvent is any one or a few in acetone, methyl alcohol, ethanol, water, acetonitrile, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), sulfobenzide, tetramethylene sulfone, the N-Methyl pyrrolidone;
Described reductive agent is zinc powder, magnesium powder, reduced iron powder/HCl, SnCl
2The mixture of any one or a few among/HCl, lithium aluminum hydride, sodium borohydride, the hydrazine hydrate/Pd/C;
(2) the crosslinked system film of polymkeric substance
Get the sulfonated poly aryl ether ketone solution after the reduction modification of step (1) preparation, add catalyzer and linking agent under protection of inert gas, the mass ratio of sulfonated poly aryl ether ketone, catalyzer and linking agent is 100: (0-40): (0-50); Controlled temperature mixes at 0～50 ℃ and got preparation liquid in 0.5～8 hour; Preparation liquid is applied to makes film on the substrate, handle to remove through 40～180 ℃ of temperature programmings and desolvate, and in film process, finish crosslinking reaction; Be chilled to the room temperature demoulding, and soaked 24 hours at dilution heat of sulfuric acid, washing obtains crosslinked polymer dielectric film material after drying repeatedly;
Described linking agent is polyaldehyde or polycarboxylic acid; Described catalyzer is acid catalyst or alkaline catalysts.
3. a kind of sulfonated poly aryl ether ketone according to claim 2 prepares the method for polymer electrolyte, it is characterized in that, described polyaldehyde be oxalic dialdehyde, in the mda, suceinic aldehyde, glutaraldehyde any one or a few.
4. a kind of sulfonated poly aryl ether ketone according to claim 2 prepares the method for polymer electrolyte, it is characterized in that described polycarboxylic acid is any one or a few in oxalic acid, propanedioic acid, Succinic Acid, butene dioic acid, m-phthalic acid, terephthalic acid, the trimellitic acid.
5. a kind of sulfonated poly aryl ether ketone according to claim 2 prepares the method for polymer electrolyte, it is characterized in that described an acidic catalyst is any one or a few in hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic, trifluoromethane sulfonic acid, trifluoroacetic acid, the perfluorinated sulfonic acid.
6. a kind of sulfonated poly aryl ether ketone according to claim 2 prepares the method for polymer electrolyte, it is characterized in that, described basic catalyst is NaOH, KOH, Na
2CO
3, K
2CO
3, in the pyridine, Trimethylamine, triethylamine any one or a few.
7. the method for modifying of a kind of sulfonated poly aryl ether ketone according to claim 1 or a kind of sulfonated poly aryl ether ketone according to claim 2 prepare the method for polymer electrolyte, it is characterized in that, described sulfonated polymer is meant and contains the substituent polyaryletherketone of sulfonic acid on molecular chain, its sulfonic acid substituting group be positioned at the aromatic ring adjacent with ehter bond or be positioned at aromatic ring that carbonyl links to each other on; Being prepared as by with polyaryletherketone H of described sulfonated poly aryl ether ketone
2SO
4, SO
3, chlorsulfonic acid sulphonating agent sulfonation modifying obtains, perhaps by obtaining to contain the substituent monomer direct polymerization of sulfonic acid; Described polyaryletherketone typical case molecular structure is as follows:
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| CN103515634B (en) * | 2013-09-27 | 2016-02-03 | 南通汉瑞新材料科技有限公司 | A kind of synthesis of vanadium redox battery amberplex and preparation method |
| CN103805078B (en) * | 2014-02-25 | 2015-09-09 | 黑龙江省科学院石油化学研究院 | A kind of high tenacity, 250 DEG C of life-time service modified cyanic acid ester structural film adhesives and preparation method thereof |
| US9601325B2 (en) * | 2014-06-24 | 2017-03-21 | Rohm And Haas Electronic Materials Llc | Aromatic resins for underlayers |
| CN104311858B (en) * | 2014-11-10 | 2017-10-27 | 中国科学院上海高等研究院 | A kind of covalent pair of cross-linked proton exchange membrane and its preparation method and application |
| CN108479437B (en) * | 2018-04-09 | 2021-01-15 | 南阳师范学院 | Polyelectrolyte, ion exchange membrane and preparation method thereof |
| DE102018119446A1 (en) * | 2018-08-09 | 2020-02-13 | Carl Freudenberg Kg | Crosslinking of polyaryl ether ketones |
| CN112972764B (en) * | 2021-03-19 | 2022-04-26 | 吉林大学 | Polyether-ether-ketone bone repair material with multi-scale holes and preparation method thereof |
| CN114142081B (en) * | 2021-11-30 | 2022-11-29 | 南京信息工程大学 | Ion-selective gel-state electrolyte, preparation method and lithium-sulfur battery |
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