CN1195004C - Sulfonated poly phenyl thioether ketone-like ionomer and its preparation method - Google Patents
Sulfonated poly phenyl thioether ketone-like ionomer and its preparation method Download PDFInfo
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- CN1195004C CN1195004C CNB021453144A CN02145314A CN1195004C CN 1195004 C CN1195004 C CN 1195004C CN B021453144 A CNB021453144 A CN B021453144A CN 02145314 A CN02145314 A CN 02145314A CN 1195004 C CN1195004 C CN 1195004C
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Abstract
The present invention provides a sulfonated polyphenyl thioether ketone ionomer and a preparation method thereof. The repeating structural unit of the ionomer is shown in the following picture of a specification. The ionomer uses a sulfonated dihalo (binitro) benzophenone monomer, dihalo (binitro) benzophenone, a dihalo (binitro) diphenyl sulfone monomer, p-(dihalophenyl) phenyl oxyphosphine and an equimolar dimercapto monomer as raw materials, alkali or salt of alkali metal are used as catalysts, and the ionomer is prepared in a copolymerization mode in a polar solvent at high temperature. A diphenyl sulfone structural unit and a triphenylphosphine oxide structural unit in the ionomer disturb the regular arrangement of a macromolecular main chain of the ionomer, the crystallization degree is reduced, and the solubility is improved. Compared with a non fluorine proton exchange membrane which comprises an ether bond, the oxidation resistance of the ionomer is greatly increased, and the ionomer has a favorable application prospect in the fields of a proton exchange membrane fuel battery, etc. M stands for hydrogen ions, sodium ions, potassium ions, rubidium ions, cesium ions and ammonium ions, the sum of m, n, p and q is greater than or equal to 20, m is greater than 0, and n, p and q are greater than or equal to 0.
Description
Technical field: the present invention relates to the proton exchange membrane material of fuel cell, particularly sulfonated polyphenyl thioether ketone ionomer and preparation method thereof.
Background technology: the development of proton exchange membrane material is one of gordian technique of Proton Exchange Membrane Fuel Cells (PEMFC).At present, widely used proton exchange membrane is the Nafion series membranes of DuPont company in the fuel cell.Yet also there are some important disadvantages in perfluor films such as Nafion, as the methanol permeability height, specific conductivity is low when high temperature, low humidity, costs an arm and a leg, and is difficult to processing, can not directly apply to methanol fuel cell etc., so more and more researchers turns to the research of non-fluorine proton exchange membrane.
Human chlorsulfonic acid Direct Sulfonation polysulfones (Udel) such as Quentin have prepared SPSF.The method of human modifications such as Jin has prepared sulfonated polyether-ether-ketone.People such as Ueda have developed the direct condensation method, have prepared the bisphenol A-type sulfonated polyether sulfone.The method of human direct condensation such as Wang Feng has prepared sulfonated polyether ketone.We adopt the method for direct polymerization prepared the poly-naphthyridine ether ketone ketone of sulfonation (the Chinese invention patent application number: 01113257.4) and sulfonation gather naphthyridine ether ketone sulfone (Chinese invention patent application number: 02111491.9).Yet sulfonated polyether ketone (sulfone) macromolecular main chain is formed by connecting by ehter bond etc., and polymkeric substance contains a large amount of ehter bonds.PEMFC is in operational process, and the oxygen that always has minute quantity sees through proton exchange membrane from negative electrode and enters the positive column, generates H with H-H reaction
2O
2H
2O
2Under the catalyst actions such as Pt on the electrode, form hydrogen peroxide free radical (HOO), HOO can cause the chain reaction of sulfonated polyether ketone (sulfone) the base polymer molecular chain of ether-containing key, causes degraded and crosslinked at last.The result of DeR makes the molecular weight and molecular weight of superpolymer, and the material deliquescing becomes sticky, and intensity and film amount descend; Crosslinked the superpolymer hardening is become fragile, elongation descends.The poly-naphthyridine ether ketone ketone of sulfonation and poly-each repeating unit of naphthyridine ether ketone sulfone base polymer of sulfonation have only an ehter bond, than the few ehter bond of sulfonated polyether sulfone (ketone), the ability of anti-peroxide oxidation strengthens, but does not fundamentally solve the problem that ehter bond is degraded by peroxide oxidation in the polymkeric substance.
As everyone knows, thio-ether type compounds energy and peroxidation, making peroxide breakdown is inactive substance, therefore often is used to do to suppress the stabilization of peroxide agent.Such as, Tyox B is oxidized to sulfoxide compound under the effect of peroxidation alcohol, and thioether bond does not rupture, thus effectively avoided ether material oxygenolysis (as shown below) under the effect of superoxide.
Human sulphonating agents such as Russell have prepared the ionomer of polyphenylene sulfide ether directly with the polyphenylene sulfide sulfonation, and product is insoluble not molten.Studies show that its sulfide group has been oxidized to sulfuryl, anti-hypochlorous acid (salt) oxidation capacity greatly strengthens, and can be prepared into the strong ion-exchange membrane of oxidation resistance with fluorine material blend such as polyvinylidene difluoride (PVDF).
The sulfonated polyphenyl sulfide ketone is formed by connecting by thioether bond etc., and oxidation resistent susceptibility greatly improves, but its sulfonation degree be still the crystal polymer thing, and solubleness is little in polar solvent commonly used when very high.
Summary of the invention: the objective of the invention is sulfobenzide structural unit, triphenyl phosphinyl structure unit are incorporated in the sulfonated polyphenyl thioether ketone ionomer molecule, upset the regular arrangement of product macromolecular main chain, its degree of crystallinity is descended, solvability increases, when sulfobenzide structural unit or triphenyl phosphinyl structure unit reach when a certain amount of, sulfonated products is an amorphous polymer.This polymkeric substance repeated structural unit is as shown below.
Wherein, M is hydrogen ion, sodium ion, potassium ion, rubidium ion, cesium ion, ammonium ion,
m+n+p+q≥20，
M＞0, and n, p, q 〉=0, p+q＞0.
Sulfonated polyphenyl thioether ketone ionomer under the operational condition of PEMFC, the H of the minute quantity that the sulphur atom of thioether bond is produced in the electrochemical reaction process
2O
2Be oxidized to sulfoxide group, and polymkeric substance is not degraded, improved its work-ing life greatly as proton exchange membrane.
Method for producing polymer of the present invention is as follows: with one of sulfonation dihalo-benzophenone monomer or sulfonation dinitrobenzene benzophenone monomer, dihalo-benzophenone or dinitrobenzene benzophenone monomer and dihalo-sulfobenzide, diphenylsulfone dinitro, two (halogenophenyl) phenyl phosphine oxide three monomers or wherein arbitrary combination, be raw material with equimolar dimercapto monomer again, a certain amount of alkali-metal alkali or an alkali metal salt, solvent, azeotropy dehydrant etc. join in the there-necked flask.Under nitrogen protection, heat temperature raising dehydration after dehydration finishes, is discharged azeotropy dehydrant, heat temperature raising to 140～220 ℃, polymerization 1～32 hour, behind the naturally cooling, precipitation is filtered, drying, repeated multiple times, target product.Test its physical and chemical performance then.
The equation of polyreaction of the present invention can be expressed as:
Wherein, M is hydrogen ion, sodium ion, potassium ion, rubidium ion, cesium ion, ammonium ion,
X is fluorine, chlorine, bromine atoms or nitro,
m+n+p+q≥20，
M＞0, and n, p, q 〉=0, p+q＞0.
The sulfonation dihalo-sulfobenzide monomer that the present invention adopts comprises 4,4 '-two fluoro-3,3 '-sodium disulfonate benzophenone, 3,3 '-two fluoro-4,4 '-sodium disulfonate benzophenone, 2,4 '-two fluoro-5,3 '-sodium disulfonate benzophenone, 4,4 '-two chloro-3,3 '-sodium disulfonate benzophenone, 2,4 '-two chloro-5,3 '-sodium disulfonate benzophenone or 4,4 '-two bromo-3,3 '-sodium disulfonate benzophenone; The sulfonation diphenylsulfone dinitro monomer that the present invention adopts comprises 3,3 '-dinitrobenzene-4,4 '-sodium disulfonate benzophenone or 3,4 '-dinitrobenzene-5,3 '-sodium disulfonate benzophenone.
The dihalo-benzophenone monomer that the present invention adopts comprises 4,4 '-difluoro benzophenone, 3,3 '-difluoro benzophenone, 2,4 '-difluoro benzophenone, 4,4 '-two chloro benzophenones, 2,4 '-two chloro benzophenones or 4,4 '-dibromo benzophenone; The dinitrobenzene benzophenone monomer that the present invention adopts comprises 3,3 '-dinitrobenzene benzophenone or 3,4 '-dinitrobenzene benzophenone.
Dihalo-sulfobenzide monomer, diphenylsulfone dinitro monomer that the present invention adopts comprise 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenyl sulfone or 4,4 '-dibromo sulfobenzide; The diphenylsulfone dinitro monomer that the present invention adopts is 4,4 '-diphenylsulfone dinitro.
Two (halogenophenyl) phenyl phosphine oxide monomer that the present invention adopts comprises two (4-fluorophenyl) phenyl phosphine oxide, two (4-chloro-phenyl-) phenyl phosphine oxide or two (4-bromophenyl) phenyl phosphine oxide.
The dimercapto monomer that the present invention adopts comprises 4,4 '-dimercapto biphenyl, 4,4 '-dimercapto ditan, 1,4-thioresorcin, 1,3-thioresorcin, 1,2-thioresorcin, 4,4 '-dimercapto phenylbenzene-2,2-propane, 4,4 '-dimercapto diphenylsulfide, 4,4 '-dimercapto diphenyl sulfoxide, 4,4 '-dimercapto sulfobenzide or 4,4 '-dimercapto diphenylketone.
The polymerization solvent that the present invention adopts comprises N-Methyl pyrrolidone, N, dinethylformamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, sulfobenzide and mixed solvent thereof.
Alkali-metal alkali and an alkali metal salt that the present invention adopts comprise sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate or saleratus; Wherein the consumption of sodium hydroxide or potassium hydroxide is 2 times of dimercapto monomer molar amount, and the consumption of sodium bicarbonate or saleratus is 2～4 times of dimercapto monomer molar amount, and the consumption of yellow soda ash or salt of wormwood is 1～2 times of dimercapto monomer molar amount.
The azeotropy dehydrant that the present invention adopts comprises toluene, dimethylbenzene or chlorobenzene.
The product precipitation agent that the present invention adopts comprises water, ethanol or methyl alcohol.
The polymeric film of the present invention's preparation, after the hydrogen peroxide oxidation, its ir data shows, sulfide group wherein has been oxidized to sulfoxide radicals, macromolecular main chain is not degraded, compare with the non-fluorine ion exchange membrane of ether-containing key, scale resistance greatly improves, thereby increases substantially its work-ing life under PEMFC running environment (superoxide environment).By regulating sulfonated monomers, dihalo-sulfobenzide or diphenylsulfone dinitro, two (halogenophenyl) phenyl phosphine oxide monomer, dihalo-benzophenone monomer or the monomeric ratio of dinitrobenzene benzophenone, temperature of reaction and reaction times, the target product that can prepare different sulfonic group content, different viscosity, thereby specific conductivity and other performances of regulating product.This polymkeric substance high comprehensive performance has good prospects for application in fields such as PEMFC.
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: with 0.6757 gram (1.6mmol) 4,4 '-two fluoro-3,3 '-sodium disulfonate benzophenone, 0.3491 gram (1.6mmol) 4,4 '-difluoro benzophenone, 0.2034 gram (0.8mmol) 4,4 '-difluorodiphenyl sulfone, 1.0016 gram (4mmol) 4,4 '-dimercapto diphenyl sulfide and 0.6634 gram (4.8mmol) salt of wormwood, 30ml toluene, 20mlN-methyl-2-pyrrolidone join in the there-necked flask, inserted the water trap of nitrogen, band prolong in the there-necked flask, loaded onto mechanical stirrer.Under nitrogen protection, heat temperature raising dehydration after dehydration finishes, is discharged azeotropy dehydrant toluene, heat temperature raising to 190 ℃; polymerization 20 hours behind the naturally cooling, adds solvent cut, precipitates in water; filter, three times repeatedly, dry under 100 ℃ in vacuum drying oven, get target product.The product reduced viscosity is 1.12dl/g, and the temperature of thermal weight loss 10% is 501.8 ℃, is the crystal polymer thing.
Embodiment 2: with 0.6757 gram (1.6mmol) 4,4 '-two fluoro-3,3 '-sodium disulfonate benzophenone, 0.6102 gram (2.4mmol) 4,4 '-difluorodiphenyl sulfone, 1.0016 gram (4mmol) 4,4 '-dimercapto diphenyl sulfide and 0.6634 gram (4.8mmol) salt of wormwood, 30ml toluene, 20ml N-Methyl pyrrolidone join in the there-necked flask, insert the water trap of nitrogen, band prolong in the there-necked flask, loaded onto mechanical stirrer.Under nitrogen protection, heat temperature raising dehydration after dehydration finishes, is discharged azeotropy dehydrant toluene, heat temperature raising to 190 ℃; polymerization 20 hours behind the naturally cooling, adds solvent cut, precipitates in water; filter, three times repeatedly, dry under 100 ℃ in vacuum drying oven, get target product.The product reduced viscosity is 1.10dl/g, and the temperature of thermal weight loss 10% is 493.5 ℃, is amorphous polymer.
Claims (11)
1. sulfonated polyphenyl thioether ketone ionomer is characterized in that the repeated structural unit of polymkeric substance is:
Wherein, M is hydrogen ion, sodium ion, potassium ion, rubidium ion, cesium ion, ammonium ion,
m+n+p+q≥20，
M＞0, and n, p, q 〉=0, p+q＞0.
2. the ionomeric preparation method of the described sulfonated polyphenyl thioether of claim 1 ketone, it is characterized in that with sulfonation dihalo-benzophenone monomer or sulfonation dinitrobenzene benzophenone monomer, dihalo-benzophenone or dinitrobenzene benzophenone monomer and dihalo-sulfobenzide, diphenylsulfone dinitro, one of two (halogenophenyl) phenyl phosphine oxide, three monomers or wherein arbitrary combination, be raw material with equimolar dimercapto monomer again, in the reaction medium of polar solvent, with alkali-metal alkali or an alkali metal salt is catalyzer, azeotropic dehydration in the presence of azeotropy dehydrant, after dehydration finishes, under 140～220 ℃ of temperature, polyreaction 1～32 hour, after reaction finishes, add solvent cut in the system, in precipitation agent, precipitate, separate dry, repeated multiple times obtains subject polymer.
3. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that the sulfonation dihalo-benzophenone monomer that adopts comprises 4,4 '-two fluoro-3,3 '-sodium disulfonate benzophenone, 3,3 ,-two fluoro-4,4 '-sodium disulfonate benzophenone, 2,4 '-two fluoro-5,3 '-sodium disulfonate benzophenone, 4,4 '-two chloro-3,3 '-sodium disulfonate benzophenone, 2,4 '-two chloro-5,3 '-sodium disulfonate benzophenone or 4,4 '-two bromo-3,3 '-sodium disulfonate benzophenone; Its feature is that also the sulfonation dinitrobenzene benzophenone monomer that adopts comprises 3,3 '-dinitrobenzene-4,4 '-sodium disulfonate benzophenone or 3,4 '-dinitrobenzene-5,3 '-sodium disulfonate benzophenone;
4. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone, it is characterized in that the dihalo-benzophenone monomer that adopts comprises 4,4 '-difluoro benzophenone, 3,3 '-difluoro benzophenone, 2,4 '-difluoro benzophenone, 4,4 '-two chloro benzophenones, 2,4 '-two chloro benzophenones or 4,4 '-dibromo benzophenone; Its feature is that also the dinitrobenzene benzophenone monomer that adopts comprises 3,3 '-dinitrobenzene benzophenone or 3,4 '-dinitrobenzene benzophenone.
5. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone, it is characterized in that the dihalo-sulfobenzide monomer that adopts comprises 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenyl sulfone, 4,4 '-dibromo sulfobenzide or 4,4 '-diphenylsulfone dinitro; Its feature is that also the diphenylsulfone dinitro monomer that adopts is 4,4 '-diphenylsulfone dinitro.
6. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that two (halogenophenyl) phenyl phosphine oxide monomer that adopts comprises two (4-fluorophenyl) phenyl phosphine oxide, two (4-chloro-phenyl-) phenyl phosphine oxide or two (4-bromophenyl) phenyl phosphine oxide.
7. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that the dimercapto monomer that adopts comprises 4,4 '-dimercapto biphenyl, 4,4 '-dimercapto ditan, 1,4-thioresorcin, 1,3-thioresorcin, 1,2-thioresorcin, 4,4 '-dimercapto phenylbenzene-2,2-propane, 4,4 '-dimercapto diphenylsulfide, 4,4 '-dimercapto diphenyl sulfoxide, 4,4 '-dimercapto sulfobenzide or 4,4 '-dimercapto diphenylketone.
8. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that reaction solvent comprises N-Methyl pyrrolidone, N, dinethylformamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, sulfobenzide and mixed solvent thereof.
9. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that catalyzer comprises sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate or saleratus; Wherein the consumption of sodium hydroxide or potassium hydroxide is 2 times of dimercapto monomer molar amount, and the consumption of sodium bicarbonate or saleratus is 2～4 times of dimercapto monomer molar amount, and the consumption of yellow soda ash or salt of wormwood is 1～2 times of dimercapto monomer molar amount.
10. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that azeotropy dehydrant comprises toluene, dimethylbenzene or chlorobenzene.
11. the ionomeric preparation method of the described sulfonated polyphenyl thioether of root a tree name claim 2 ketone is characterized in that precipitation agent comprises water, methyl alcohol or ethanol.
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| CN100336845C (en) * | 2005-01-13 | 2007-09-12 | 上海交通大学 | Sulfonated aryl sulfoether containing triphenyl phosphinyl structure unit and its preparation method |
| CN100347222C (en) * | 2005-01-13 | 2007-11-07 | 上海交通大学 | Sulfonated polyaryl sulfoether containing triphenyl biketone structure unit and preparing process thereof |
| CN108641168A (en) * | 2018-05-28 | 2018-10-12 | 无锡上美纸制品有限公司 | One kind easily tearing noresidue environment-friendly type brown paper adhesive protecting film and preparation method thereof |
| CN108976421A (en) * | 2018-07-26 | 2018-12-11 | 四川中科兴业高新材料有限公司 | A kind of preparation method of film-grade PPS resin |
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