CN101381455A - Polyarylether material bearing a sulfonic acid group on a pendant group, and preparation method and application thereof - Google Patents
Polyarylether material bearing a sulfonic acid group on a pendant group, and preparation method and application thereof Download PDFInfo
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- CN101381455A CN101381455A CNA2008100512536A CN200810051253A CN101381455A CN 101381455 A CN101381455 A CN 101381455A CN A2008100512536 A CNA2008100512536 A CN A2008100512536A CN 200810051253 A CN200810051253 A CN 200810051253A CN 101381455 A CN101381455 A CN 101381455A
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- resorcinol
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Abstract
The invention discloses a side group sulfonic acid polyarylether material, a method for preparing the same and application thereof, which belong to the technical field of functional polymer materials. In particular, the method comprises the following steps: performing polycondensation reaction of 2, 5-diphenyl-hydroquinone and dual-halogen monomers such as 4, 4'-difluoro-benzophenone, 4, 4'-difluoro-diphenylsulfone, 2, 6-difluoro-benzonitrile and the like as well as other diphenol monomers, and then preparing a series of side group sulfonic acid polyarylether proton exchange membranes with controllable sulfonation point and sulfonation degree by a moderate post-sulfonation method. The proton exchange membranes prepared by the method have the advantages of high thermal stability, good solubility and film-forming property, excellent hot water dimensional stability, low methanol permeability and high proton conductivity. The membrane materials used by the method have the advantages of simple preparation process, mild and controllable reaction, wide application temperature and excellent performance, thus the membrane materials can be applied to proton exchange membrane fuel cells and direct methanol fuel cells.
Description
Technical field
The invention belongs to the technical field of high molecular functional material, relate to high thermal stability side group sulfonic acid type polyarylether polymkeric substance that is used for fuel battery proton exchange film and preparation method thereof.
Background technology
Fuel cell can be converted into electric energy with chemical energy efficiently, is a kind of clean energy with application prospect.Proton exchange membrane is as the key part of pem cell and direct methanol fuel cell system, its development and develop significant.Nafion film with perfluorinated sulfonic acid chemical structure is to use at present and research proton exchange membrane the most widely, but that it exists is expensive, low working temperature (≤80 ℃), high shortcomings such as methanol permeability.Sulfonic acid group is incorporated into the sulfonation material that polymkeric substance with good thermostability and then preparation have good proton conduction characteristic is recognized the proton mould material that might replace Nafion.As the proton exchange membrane material that can select, the sulfonated polyethersulfone, the sulfonated polyetherketone, sulfonated polyethers nitrile, sulfonated polyarylether etc. has all prepared success, but still has some problems at present, as: the simplification of sulfonation reaction and optimization; The three-dimensional controllability of chemical structure, the design by chemical structure realizes the control of sulfonation degree, the selection of sulfonation position, the enhancing of polymer performance, the improvement of microfacies structure etc.The sulfonated membranes of most polyarylethers all is based on the back sulfonation to known polymkeric substance, and back sulfonated method is simple, realizes easily.Yet than the polymkeric substance that the copolymerization of sulfonated monomers obtains, sulfonation degree and sulfonation position all are not easy to be well controlled.
Summary of the invention
The technical problem to be solved in the present invention is, first, preparation can be carried out the starting polymer of sulfonation point and the controlled sulfonation reaction of sulfonation degree under relatively mild condition, by the back method of sulfonating, for preparing a series ofly has higher thermostability, good solubility and a film-forming properties, and the side group of low water-intake rate contains sulfonic performance resins, as the sulfonated polyether-ether-ketone, sulfonated polyethers nitrile, side group sulfonic acid type polyarylether materials such as sulfonated polyethersulfone; The second, with key part---the proton exchange membrane of side group sulfonic acid type polyarylether material as pem cell or direct methanol fuel cell system.
For reaching above-mentioned purpose, the present invention is with 2, and biphenol monomers such as 5-phenylbenzene Resorcinol by condensation reaction, have synthesized a series of full aromatic (co) polymers that has two benzene lateral groups, carries out the back sulfonation afterwards and handles.
The technical solution adopted in the present invention is:
A kind of side group sulfonic acid type polyarylether material, structure by
Two repeating units are formed,
Wherein, m is〉0 to=1;
Ar is
Or
Or
Or
Or
Ar ' is
Or
Or
Or
Or
Or
Or
Or
When m gets 1, side group sulfonic acid type polyarylether material of the present invention will not contain Ar ', promptly have only a repeating unit to constitute.Concrete structural formula can be enumerated as:
N=1～200 wherein.
The preparation method of side group sulfonic acid type polyarylether material of the present invention comprises synthetic and two processes of back sulfonation of initial polymer;
Said initial polymer synthetic process is, with 2,5-phenylbenzene Resorcinol, other diphenol monomer, etc. two halogen monomers of diphenol monomer integral molar quantity be reactant, 2,5-phenylbenzene Resorcinol and the monomeric mol ratio of other diphenol are m: 1-m, and m is〉0 to=1; The solvent of 3～5 times of Anhydrous potassium carbonate, the reactant quality of 1.03～2.0 times of reactants, two halogen monomer mass and the azeotropy dehydrant of solvent volume 20% are put into the container that water-taker is housed, logical nitrogen, be warmed up to azeotropy dehydrant and reflux, refluxed 1～5 hour, get rid of azeotropy dehydrant, be warming up to 190～220 ℃ and continue reaction 2～48 hours, the polymers soln that obtains is separated out in deionized water, through pulverizing washing, drying obtains initial polymer;
Said back sulfonation process is, adding concentration is 95～98% the vitriol oil or chlorsulfonic acid in initial polymer, consumption is that per 50 gram initial polymer add 0.5～1.5 liter of the vitriol oil or chlorsulfonic acid, and stir process is 2～7 days under the room temperature, obtains side group sulfonic acid type polyarylether material.
Said other diphenol monomer of the present invention is to remove 2, and the diphenol monomer outside the 5-phenylbenzene Resorcinol can be used always, as 4, and monomers such as 4 '-dihydroxy diphenylsulphone.
What the present invention was used contains 2, and the monomer structure of 5-phenylbenzene Resorcinol is as follows:
Its preparation can be, with 2,5-diphenyl-benzoquinone, zinc powder, HCl 1: 4～10: 8～20 mix, and controlled temperature is 75～100 ℃ of reactions 2～24 hours; Product is through heat filtering, and the deionized water repetitive scrubbing oily matter with 0～50 ℃ obtains head product, carries out recrystallization by toluene again, and productive rate is 30～70%.
Among the preparation method of side group sulfonic acid type polyarylether material, described pair of halogen monomer is 4,4 '-difluorodiphenyl sulfone, 4,4 '-difluoro benzophenone, 2,6-difluorobenzonilyile, 4,4 '-dichloro diphenyl sulfone, decafluorobiphenyl, 4,4 '-two-(4 '-fluorobenzene acyl group) biphenyl or 1,4-two-(4 '-fluorobenzene acyl group) benzene etc.; Other diphenol monomer is 4,4 '-dihydroxy diphenylsulphone, Resorcinol, 4,4 '-'-biphenyl diphenol, dihydroxyphenyl propane, bisphenol AF, 3-trifluoromethylbenzene-Resorcinol, 3,5-two trifluoromethylbenzenes-Resorcinol or 4,4 '-dihydroxy benaophenonel etc.; Described solvent is tetramethylene sulfone, N, dinethylformamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone; Described azeotropy dehydrant is toluene, dimethylbenzene or chlorobenzene.
It is as follows that the present invention prepares the reaction process and the chemical equation of side group sulfonic acid type polyarylether material:
The battery proton-conductive films that acts as a fuel needs the certain sulfonation degree of control, i.e. the content of sulfonate radical.The present invention can prepare initial starting material by the method for copolymerization, then the material that obtains having certain sulfonation degree by back sulfonated method.The process for preparing certain sulfonation degree material can be referring to embodiments of the invention, concrete is to utilize synthetic 2,5-phenylbenzene Resorcinol and 4,4 '-dihydroxy diphenylsulphone, Deng 4,4 '-difluorodiphenyl sulfone of bis-phenol integral molar quantity, by changing the ingredient proportion and the feeding method of reactive material, utilize polycondensation to prepare a series of multipolymers, for example: DiPh-SPES-100 (x=1.0); DiPh-SPES-60 (x=0.6); DiPh-SPES-50 (x=0.5); DiPh-SPES-40 (x=0.4).
Concrete synthesis step reaction formula is as follows:
Have the same base polymer that contains sulfonic acid than Nafion 117 and general main chain by the side chain side group sulfonic acid type polyarylether material of method for preparing and have more excellent thermostability.
Thus, the purposes of side group sulfonic acid type polyarylether material of the present invention is the preparation proton exchange membrane, is used for the membrane electrode assembling of pem cell or methanol fuel-cell system.
Concrete film-forming process can be, side group sulfonic acid type polyarylether material is dissolved in N, in the N-N,N-DIMETHYLACETAMIDE, be poured on after the filtration on the sheet glass of level, sheet glass is placed on the hot platform of level in the device with nitrogen gangway and the hot platform of level, placed 3～4 days for 40～60 ℃, be placed on then in 110～125 ℃ the vacuum drying oven 10～24 hours.
Through the mould material that teeming practice is prepared into, has lower water-swellable rate, lower methanol permeability and good proton conductivity by the polymkeric substance of method for preparing.For example, the conductivity under the DiPh-SPES-60 room temperature is 0.083S/cm, can reach 0.138S/cm at 70 ℃.Can satisfy the act as a fuel basic demand of battery proton exchange membrane of material.
The monomer that the present invention is designed has guaranteed the accurate control of sulfonation position, carries out copolymerization by the control feed ratio, control benzene lateral group amount is controlled sulfonation degree, uses back sulfonated method simultaneously, and sulfonation speed is fast, reflecting point is concrete, has avoided loaded down with trivial details and complicated the synthesizing of sulfonated monomers.Simultaneously, on benzene lateral group, introduce sulfonic group, make polymkeric substance that reasonable thermostability (not having thermolysis below 220 ℃), resistance to hydrolysis and oxidation-resistance be arranged, solved and introduced sulfonic stability problem on the main chain.Therefore, the present invention designs by chemical structure, has obtained side group acid type hydrocarbon polymer proton-conductive films a kind of Applicable temperature wide (0～220 ℃), that other performances are also excellent, and it is having a good application prospect in fuel cell field.
Embodiment
Embodiment 1:2, the preparation of 5-phenylbenzene Resorcinol
With 26 gram (0.1mol) 2, the 5-diphenyl-benzoquinone, 65.4 gram (1.0mol) zinc powders, 200mL water is put into the there-necked flask that mechanical stirring, dropping funnel and reflux condensing tube are housed, and the 160mL concentrated hydrochloric acid splashes into the speed of 0.04mL/ second.Reaction is 8 hours under reflux temperature, and heat filtering obtains product 2,5-phenylbenzene Resorcinol, and recrystallization, productive rate 60%, fusing point are 226 ℃.
Process is the same, and zinc powder adopts batch charging, can be divided into 5 batches, and every batch 13 gram obtains same product, productive rate 65%, 226 ℃ of fusing points.
Embodiment 2: initial polymer---and homopolymer DiPh-PES-100's is synthetic
Will by embodiment 1 method make 2.62 the gram (0.01mol) 2,5-phenylbenzene Resorcinol, 2.54 gram (0.01mol) 4, the Anhydrous potassium carbonate of 4 '-difluorodiphenyl sulfone and 1.8 grams, 20mLN, N-N,N-DIMETHYLACETAMIDE, 30ml toluene is put into the there-necked flask of the 100ml that water-taker is housed, logical nitrogen is warmed up to refluxing toluene and stirs, and refluxes 1.5～2 hours, get rid of toluene, be warmed up to 220 ℃, continue reaction 4～8 hours, polymeric solution is separated out in water, through pulverizing, washing after the drying, obtains initial polymer DiPh-PES-100.
Embodiment 3: initial polymer---and multipolymer DiPh-PES-50's is synthetic
Will by embodiment 1 make 2.62 the gram (0.01mol) 2,5-phenylbenzene Resorcinol, 2.50 gram (0.01mol) 4,4 '-dihydroxy diphenylsulphone, 5.08 gram (0.02mol) 4, the Anhydrous potassium carbonate of 4 '-difluorodiphenyl sulfone and 1.8 grams, the 40mL N,N-dimethylacetamide, 30ml toluene is put into the there-necked flask of the 500ml that water-taker is housed, logical nitrogen is warmed up to refluxing toluene and stirs, and refluxes 1.5～2 hours, get rid of toluene, be warmed up to 190 ℃, continue reaction 4～8 hours, polymeric solution is separated out in water, through pulverizing, washing after the drying, obtains initial polymer DiPh-PES-50.Its second-order transition temperature (Tg) is 225 ℃.
Embodiment 4: initial polymer---and multipolymer DiPh-PES-60's is synthetic
With 2 of the foregoing description 3, feeding intake of 5-phenylbenzene Resorcinol changes 0.012mol into, and 4, feeding intake of 4 '-dihydroxy diphenylsulphone changes 0.008mol into, and other condition is identical, obtains another initial polymer DiPh-PES-60.Its second-order transition temperature (Tg) is 219 ℃.
Embodiment 5: initial polymer---and multipolymer DiPh-PES-40's is synthetic
With 2 of the foregoing description 3, feeding intake of 5-phenylbenzene Resorcinol changes 0.008mol into, and 4, feeding intake of 4 '-dihydroxy diphenylsulphone changes 0.012mol into, and other condition is identical, obtains another initial polymer DiPh-PES-40.Its second-order transition temperature (Tg) is 228 ℃.
Embodiment 6: the preparation of side group sulfonic acid type polyarylether polymer DiPh-SPES-50
The DiPh-PES-50 that embodiment 3 is obtained carried out sulfonation 2～7 days with the vitriol oil, through washing, after the drying, obtained being with sulfonic acid lateral group polyarylether polymer DiPh-SPES-50 again.It is 280 ℃ that DSC records second-order transition temperature, and 5% thermal weight loss temperature is 374 ℃ in the air, and molecular formula is as follows:
Embodiment 7: the preparation of side group sulfonic acid type polyarylether polymer DiPh-SPES-60
The DiPh-PES-60 that embodiment 4 is obtained handles with the method for embodiment 6, obtains being with sulfonic acid lateral group polyarylether polymer DiPh-SPES-60.It is 285 ℃ that DSC records second-order transition temperature, and 5% thermal weight loss temperature is 371 ℃ in the air, and molecular formula is as follows:
Embodiment 8: the preparation of side group sulfonic acid type polyarylether polymer DiPh-SPES-40
The DiPh-PES-40 that embodiment 5 is obtained handles with the method for embodiment 6, obtains being with sulfonic acid lateral group polyarylether polymer DiPh-SPES-40.It is 269 ℃ that DSC records second-order transition temperature, and 5% thermal weight loss temperature is 386 ℃ in the air, and molecular formula is as follows:
Embodiment 9: the making of proton exchange membrane
Resulting side group sulfonic acid type polyarylether material in 0.5 gram the foregoing description 6～8 is dissolved in 15 milliliters of N, in the N-N,N-DIMETHYLACETAMIDE, after the filtration, be poured on the sheet glass of level, be placed in the semitight device that has on nitrogen gangway and the hot platform of level, placed 3.5 days for 50 ℃, be placed on then in 120 ℃ the vacuum drying oven 24 hours, promptly make certain thickness proton exchange membrane (～100 μ m).
Embodiment 10: other initial polymer synthetic
In embodiment 3～5, with 4,4 '-difluoro benzophenone, 2,6-difluorobenzonilyile, 4,4 '-dichloro diphenyl sulfone, decafluorobiphenyl, 4,4 '-two-(4 '-fluorobenzene acyl group) biphenyl or 1,4-two-(4 '-fluorobenzene acyl group) benzene substitutes 4,4 '-difluorodiphenyl sulfone; With Resorcinol, 4,4 '-'-biphenyl diphenol, dihydroxyphenyl propane, bisphenol AF, 3-trifluoromethylbenzene-Resorcinol, 3,5-two trifluoromethylbenzenes-Resorcinol or 4,4 '-dihydroxy benaophenonel substitutes 4,4 '-dihydroxy diphenylsulphone, method with embodiment 6 is handled, and can make the side group sulfonic acid type polyarylether polymer of counter structure equally.Press the method for embodiment 9 again, can make the proton exchange membrane of the membrane electrode assembling that is used for pem cell or methanol fuel-cell system.
Claims (5)
1. side group sulfonic acid type polyarylether material, structure by
Two repeating units are formed,
Wherein, m is〉0 to=1;
Ar is
Or
Or
Or
Or
Ar ' is
Or
Or
Or
Or
Or
Or
Or
2. the preparation method of the side group sulfonic acid type polyarylether material of a claim 1 comprises synthetic and two processes of back sulfonation of initial polymer;
Said initial polymer synthetic process is, with 2,5-phenylbenzene Resorcinol, other diphenol monomer, etc. two halogen monomers of diphenol monomer integral molar quantity be reactant, 2,5-phenylbenzene Resorcinol and the monomeric mol ratio of other diphenol are m: 1-m, and m is〉0 to=1; The solvent of 3～5 times of Anhydrous potassium carbonate, the reactant quality of 1.03～2.0 times of reactants, two halogen monomer mass and the azeotropy dehydrant of solvent volume 20% are put into the container that water-taker is housed, logical nitrogen, be warmed up to azeotropy dehydrant and reflux, refluxed 1～5 hour, get rid of azeotropy dehydrant, be warming up to 190～220 ℃ and continue reaction 2～48 hours, the polymers soln that obtains is separated out in deionized water, through pulverizing washing, drying obtains initial polymer;
Said back sulfonation process is, adding concentration is 95～98% the vitriol oil or chlorsulfonic acid in initial polymer, consumption is that per 50 gram initial polymer add 0.5～1.5 liter of the vitriol oil or chlorsulfonic acid, and stir process is 2～7 days under the room temperature, obtains side group sulfonic acid type polyarylether material.
3. according to the preparation method of the described side group sulfonic acid type of claim 2 polyarylether material, it is characterized in that, described pair of halogen monomer is 4,4 '-difluorodiphenyl sulfone, 4,4 '-difluoro benzophenone, 2,6-difluorobenzonilyile, 4,4 '-dichloro diphenyl sulfone, decafluorobiphenyl, 4,4 '-two-(4 '-fluorobenzene acyl group) biphenyl or 1,4-two-(4 '-fluorobenzene acyl group) benzene; Other diphenol monomer is 4,4 '-dihydroxy diphenylsulphone, Resorcinol, 4,4 '-'-biphenyl diphenol, dihydroxyphenyl propane, bisphenol AF, 3-trifluoromethylbenzene-Resorcinol, 3,5-two trifluoromethylbenzenes-Resorcinol or 4,4 '-dihydroxy benaophenonel; Described solvent is tetramethylene sulfone, N, dinethylformamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone; Described azeotropy dehydrant is toluene, dimethylbenzene or chlorobenzene.
4. the purposes of the side group sulfonic acid type polyarylether material of a claim 1 is the preparation proton exchange membrane, is used for the membrane electrode assembling of pem cell or methanol fuel-cell system.
5. according to the purposes of the described side group sulfonic acid type of claim 4 polyarylether material, it is characterized in that, described preparation proton exchange membrane is, side group sulfonic acid type polyarylether material is dissolved in N, in the N-N,N-DIMETHYLACETAMIDE, be poured on after the filtration on the sheet glass of level, sheet glass be placed on the hot platform of level in the device with nitrogen gangway and the hot platform of level, placed 3～4 days, and in 110～125 ℃ vacuum drying oven, placed 10～24 hours then for 40～60 ℃.
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