CN1259358C - Sulphonated polyarylether containing bis-phthalazinyl-ketone and its preparation process and use - Google Patents
Sulphonated polyarylether containing bis-phthalazinyl-ketone and its preparation process and use Download PDFInfo
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- CN1259358C CN1259358C CNB2005100331607A CN200510033160A CN1259358C CN 1259358 C CN1259358 C CN 1259358C CN B2005100331607 A CNB2005100331607 A CN B2005100331607A CN 200510033160 A CN200510033160 A CN 200510033160A CN 1259358 C CN1259358 C CN 1259358C
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Abstract
The present invention relates to sulfonated polyarylether containing bis-phthalazine-ketone, which is represented in a general formula (1), wherein n is 10 to 100. The present invention also relates a method for preparing the polyarylether and the application of the polyarylether and is characterized in that bisphenol monomers containing bis-phthalazine-ketone and sulfonated dihalide monomers generate copolymerization reaction in polar aprotic solvent under the action of potassium carbonate to prepare the sulfonated polyarylether containing bis-phthalazine-ketone. The polyarylether has the advantages of low cost, high stability, high mechanical strength, favorable water absorbability, large capacity of proton exchange, etc. and has potential application value in the field of fuel batteries.
Description
Technical field
The present invention relates to polyarylether and its production and application, especially relate to sulfonated polyether that contains bis-phthalazinyl-ketone and its production and application.
Background technology
Along with the continuous consumption of conventional energy resources and day by day exhausted, equally based on the worry that environment is continued worsen, that various countries research and development personnel turn one's attention to is more efficient, more cleanly utilize the research of the energy to come up.Fuel cell has effciency of energy transfer height (40-60%), and is pollution-free, and advantages such as noiselessness will become the power supply mode of 21 century first-selection.
At present, fuel cell developed into for the 5th generation, it is Proton Exchange Membrane Fuel Cells, it is convenient for carrying except possessing the advantage part of general fuel cell, also having, but room temperature starts fast, no electrolyte loss, longer life, characteristics such as specific power and specific energy height can be applied to mobile power station, automobile, submarine and spacecraft.(Proton ExchangeMembrane is one of critical material of making Proton Exchange Membrane Fuel Cells PEM) to proton exchange membrane, and the performance of PEM directly influences the fuel cell overall performance.At present, the proton exchange membrane of widespread use is the Nafion film of E.I.Du Pont Company in the world, and it is a kind of perfluorinated sulfonic acid type proton exchange membrane.It is stable that the Nafion film has chemical property, thermally-stabilised, the physical strength height, and advantage such as proton conductivity is big, proton conductivity reaches 10 under the saturated condition of suction
-2~10
-1Scm
-1, being assembled in can be in 80 ℃ of following non-stop run up to ten thousand hours the Proton Exchange Membrane Fuel Cells.But there is complex synthetic route in the Nafion film, and the preparation cost height can dehydration when hindering the low and temperature of pure coefficient and being higher than 100 ℃ and cause proton conductivity sharply to descend the degradation deficiency.The research staff of various countries is devoted to seek the better Nafion film substitute of performance now, and wish to obtain cheaply, greater than 100 ℃ high temperature and and less than 0 ℃ low temperature under can both keep good proton conductivity, the proton exchange membrane of satisfactory mechanical property.
Polyarylether is as functional high molecule material, has excellent chemical physics performance and mechanical propertys such as high temperature resistant, creep resistance, high strength, obdurability, in aspect widespread uses such as electronic industry, space flight apparatus and military engineerings.By chemically modified to polyarylether, introduce hydrophilic sulfonic acid group, be expected to make it to become the equivalent material of Nafion film.But it is all shorter work-ing life with the proton exchange membrane of sulfonated polyether preparation at present.
Summary of the invention
The objective of the invention is to synthetic a kind of sulfonated polyether that can be used for the excellent property of proton exchange membrane; Another purpose provides the preparation method cheaply of this polyarylether; Another purpose provides the application of this polyarylether.
Utilization of the present invention contains bis-phthalazinyl ketone biphenol monomer and sulfonation dihalo-monomer carries out copolyreaction in polar aprotic solvent under the effect of salt of wormwood, prepares the sulfonated polyether that contains bis-phthalazinyl-ketone.Advantages such as such polyarylether has that cost is low, stability is high, physical strength is high, good water absorption, proton exchange capacity are big have the potential using value in fuel cell field, thereby have realized purpose of the present invention.
The sulfonated polyether of general formula of the present invention (1) expression:
Formula (1)
The preparation method of the sulfonated polyether of general formula of the present invention (1) expression is characterized in that the bis-phthalazinyl ketone biphenol monomer by general formula (2) expression:
Formula (2)
Sulfonation dihalo-monomer with general formula (3) expression:
Formula (3) in polar aprotic solvent, earlier 140~155 ℃ of reactions, is taken the water that reaction process generates out of by toluene in the presence of salt of wormwood and toluene, continue to be warmed up to 165~180 ℃ then and react the polyarylether that obtains general formula (1), in the described formula (2)
Expression a, b, c, d, e, f, g or h, its definition cotype (1) is described, in the described formula (3)
The bis-phthalazinyl ketone biphenol monomer of described general formula (2) expression adopts prior art to be prepared, as reference: WangS J, Meng Y Z, Hlil A R, Hay S A.Macromolecules, 2004,37:60-65 and Wang S J, Meng Y Z, Tjong S C, Hlil A R, Hay S A.Journal of Polymer Science:Part A:Polymer Chemistry, 2003, vol.41,2481-2490.
Described polar aprotic solvent is N,N-dimethylacetamide, methyl-sulphoxide, N, dinethylformamide or N-Methyl pyrrolidone etc.
Among the described preparation method, the amount of substance of the compound of formula (2) compound and formula (3) equates that the amount of substance of salt of wormwood is 1.1~1.5 times of formula (2) compound, and the toluene consumption is 5~6 times of formula (2) compound mmole number in milliliter; Polar aprotic solvent is counted 4~6 times of amount of formula (2) compound with mmole with milliliter; Entire reaction is carried out under nitrogen protection; induction stirring; earlier 140~155 ℃ of reactions 2~3 hours; take the water that reaction process generates out of by toluene; continuing to be warmed up to 165~180 ℃ then kept 18~21 hours; reaction solution is to precipitate in 1: 1 the methanol aqueous solution in volume ratio, filters, and collects product in 80~110 ℃ of vacuum drying ovens dry 24~48 hours.
The sulfonated polyether that contains bis-phthalazinyl-ketone of the present invention can be used for preparing proton exchange membrane.
The method for preparing proton exchange membrane with the sulfonated polyether that contains bis-phthalazinyl-ketone of the present invention is: with the compound dissolution of described formula (1) at polar aprotic solvent such as N, N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, N, in dinethylformamide or the N-Methyl pyrrolidone, in the aqueous hydrochloric acid of massfraction 8%~10%, precipitate, kept 6~8 hours at 60~80 ℃, the polymkeric substance after the acidifying is removed inorganic salt with dialysis process; Filter, wash three times, 80 ℃ of vacuum-drying 24~48 hours; Again with N,N-dimethylacetamide dissolving, be mixed with massfraction is 5%~20% solution to resulting polymers, and under dustless condition 55~80 ℃, the best is 60 ℃, and solvent flashing obtains proton exchange membrane.
The sulfonated polyether compound with regular structure that contains bis-phthalazinyl-ketone of the present invention, not only can satisfy proton exchange membrane due physical chemistry of institute and the mechanical property of making fuel cell, and the proton exchange membrane that obtains greater than 100 ℃ high temperature and and less than 0 ℃ low temperature under can both keep good proton conductivity.Each repeating unit of sulfonated polyether that contains bis-phthalazinyl-ketone in addition contains two sulfonic groups, has lower equivalent weight (Equivalent Weight per Sulfonic Acid Group, EW value).
Preparation method's productive rate height of the present invention, and utilize industrial chemicals cheap and easy to get, cost is low, and adopt conventional preparation polyarylether route, simple, compare with the general method for preparing the sulfonated polyether material, sulfonic acid group is connected on more inactive aromatic ring, rather than the higher aromatic ring of electron density, thereby avoided the reaction of reversible desulfonation to take place, and making polymer chemistry character more stable, general in addition preparation method is connected sulfonic acid group on the ortho position of ehter bond, owing to sulfonicly hale the fracture that electronic action may cause ehter bond, cause the decomposition of superpolymer, influence the life-span of material, the carbon one nitrogen key that the present invention forms is very stable, has overcome above-mentioned problem.
Embodiment
Following embodiment further specifies of the present invention, is not limitation of the present invention.
Embodiment 1:
With 0.627g is the compound of the formula (2) of 1mmol, wherein
0.422g be the compound of 1mmol formula (3), wherein
Y=F, 0.194g are the 1.4mmol Anhydrous potassium carbonate, 5mL methyl-sulphoxide and 6mL toluene; add in the there-necked flask, under the nitrogen protection, be warmed up to 150 ℃; kept 2 hours under the magnetic agitation, utilize toluene to take the water of generation out of, be warmed up to 175 ℃ then; reacted 20 hours, cooling is constantly stirred down in 1: 1 the methanol aqueous solution of reactant impouring 100mL volume ratio; filter, use distilled water wash three times, 80 ℃ of vacuum-dryings 24 hours; the 0.933g product, i.e. the compound of formula (1), wherein
Productive rate 97%.
Nuclear magnetic resonance spectrum (
1H-NMR): (400MHz, DMSO-d
6) δ=7.20 (d, 8H), 7.66 (d, 2H), 7.71 (d, 4H), 7.80 (m, 4H), 7.86-7.98 (m, 8H), 8.38 (m, 4H).
Ultimate analysis: (C
53H
32N
4O
11S
26H
2O)
n(1073.08)
n: Calcd.C 59.32, and H 4.28, and N 5.22, and S 5.98; Found C 59.25, H 5.15, and N 6.84, S 6.07.
Loading capacity (Ion Exchange Capacity, IEC): test value, 2.04meq/g; Theoretical value, 2.07meq/g
Equivalent weight (Equivalent Weight per Sulfonic Acid Group, EW value): 482
Viscosity (Inherent Viscosity): 1.02dL/g is recording in the 0.5g/dL DMAc solution under 30 ℃ of conditions.
Proton conductivity (Proton Conductivity): 3.5 * 10
-2S cm
-1, Nafion 117 proton conductivities are 2.8 * 10 under the same terms
-2S cm
-1Test condition: instrument is AUTOLAB PGSTAT30, adopts two electrode methods, 21 ℃ of temperature, relative humidity 100%.
Embodiment 2:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, added methyl-sulphoxide is 4mL, 175 ℃ of top temperatures, the compound of the last formula that obtains (1), wherein
Productive rate 99%.
Nuclear magnetic resonance spectrum (
1H-NMR): (400MHz, DMSO-d
6) δ=7.20 (d, 4H), 7.26 (d, 4H), 7.39 (d, 4H), 7.66 (d, 2H), 7.82-7.93 (m, 12H), 8.38 (m, 4H).
Ultimate analysis: (C
56H
32F
6N
4O
11S
26H
2O)
n(1223.10)
n: Calcd.C 54.99, and H 3.63, and N 4.58, and S 5.24; Found C 55.48, H 4.66, and N 6.10, S 5.62.
Loading capacity (Ion Exchange Capacity, IEC): test value, 1.68meq/g; Theoretical value, 1.79meq/g
Equivalent weight (Equivalent Weight per Sulfonic Acid Group, EW value): 559
Viscosity (Inherent Viscosity): 1.22dL/g is recording in the 0.5g/dL DMAc solution under 30 ℃ of conditions.
Proton conductivity (Proton Conductivity): 1.8 * 10
-2S cm
-1, Nafion 117 proton conductivities are 2.8 * 10 under the same terms
-2S cm
-1Test condition: instrument is AUTOLAB PGSTAT30, adopts two electrode methods, 21 ℃ of temperature, relative humidity 100%.
Embodiment 3:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N-Methyl pyrrolidone 6mL, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 85%.
Embodiment 4:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are methyl-sulphoxide 6mL, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 91%.
Embodiment 5:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N,N-dimethylacetamide 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 94%.
Embodiment 6:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N,N-dimethylacetamide 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 96%.
Embodiment 7:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N,N-dimethylacetamide 5mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 94%.
Embodiment 8:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Polar aprotic solvent is methyl-sulphoxide 5mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 97%.
Embodiment 9:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are methyl-sulphoxide 4mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 93%.
Embodiment 10:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are methyl-sulphoxide 4mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 95%.
Embodiment 11:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N-Methyl pyrrolidone 6mL, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 83%.
Embodiment 12:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Polar aprotic solvent is methyl-sulphoxide 5mL, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 90%.
Embodiment 13:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N,N-dimethylacetamide 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 93%.
Embodiment 14:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, X=-SO
2-, Y=F, polar aprotic solvent are N,N-dimethylacetamide 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 91%.
Embodiment 15:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are N,N-dimethylacetamide 5mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 83%.
Embodiment 16:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=F, polar aprotic solvent are methyl-sulphoxide 5mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 95%.
Embodiment 17:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are methyl-sulphoxide 5mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 61%.
Embodiment 18:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are N,N-dimethylacetamide 5mL, 175 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 65%.
Embodiment 19:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are methyl-sulphoxide 5mL, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 58%.
Embodiment 20:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are methyl-sulphoxide 5ml, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 59%.
Embodiment 21:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are N-Methyl pyrrolidone 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 71%.
Embodiment 22:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
-SO
2-, Y=Cl, polar aprotic solvent are N-Methyl pyrrolidone 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 63%.
Embodiment 23:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are N-Methyl pyrrolidone 5mL, 170 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 54%.
Embodiment 24:
The preparation method is with embodiment 1, the compound of its Chinese style (2)
The compound of formula (3)
Y=Cl, polar aprotic solvent are methyl-sulphoxide 5mL, 180 ℃ of top temperatures, and the compound of the last formula that obtains (1), wherein
Productive rate 68%.
Embodiment 25: the preparation proton exchange membrane
The product of getting 0.8g exsiccant embodiment 1 is dissolved in the 10mL N,N-dimethylacetamide, precipitates in the aqueous hydrochloric acid of 75mL massfraction 10%, keeps 6 hours at 60 ℃, and this polymkeric substance after the acidifying is removed inorganic salt with dialysis process.Filter, wash three times, 80 ℃ of vacuum-drying 48 hours.Resulting polymers with the dissolving of 10mL N,N-dimethylacetamide, is tiled in dustfree environment on the level and smooth sheet glass and makes smooth whippy proton exchange membrane in 60 ℃ of solvent flashings again.Desolvate for thoroughly removing, resulting film was 110 ℃ of vacuum-dryings 24 hours.
Claims (5)
2. the preparation method of the polyarylether of the described general formula of claim 1 (1) expression is characterized in that the bis-phthalazinyl ketone biphenol monomer by general formula (2) expression:
Formula (2)
Sulfonation dihalo-monomer with general formula (3) expression:
Formula (3)
In the presence of salt of wormwood and toluene, in polar aprotic solvent,, take the water that reaction process generates out of by toluene earlier 140~155 ℃ of reactions, continue to be warmed up to 165~180 ℃ then and react the polyarylether that obtains general formula (1), in the described formula (2)
Expression a, b, c, d, e, f, g or h, its definition cotype (1) is described, in the described formula (3)
Y=F or
Y=F or
Y=Cl.
3. according to the preparation method of the polyarylether of claim 2, it is characterized in that described polar aprotic solvent is N,N-dimethylacetamide, methyl-sulphoxide, N, dinethylformamide or N-Methyl pyrrolidone.
4. according to the preparation method of the polyarylether of claim 2 or 3, it is characterized in that among the described preparation method, the amount of substance of the compound of formula (2) compound and formula (3) equates, the amount of substance of salt of wormwood is 1.1~1.5 times of formula (2) compound, and the toluene consumption is 5~6 times of formula (2) compound mmole number in milliliter; Polar aprotic solvent is counted 4~6 times of amount of formula (2) compound with mmole with milliliter; Entire reaction is carried out under nitrogen protection; induction stirring; earlier 140~155 ℃ of reactions 2~3 hours; take the water that reaction process generates out of by toluene; continuing to be warmed up to 165~180 ℃ then kept 18~21 hours; reaction solution is to precipitate in 1: 1 the methanol aqueous solution in volume ratio, filters, and collects product in 80~110 ℃ of vacuum drying ovens dry 24~48 hours.
5. the polyarylether of the described general formula of claim 1 (1) expression is as the application of preparation proton exchange membrane.
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CN101550094B (en) * | 2009-05-12 | 2012-03-28 | 天津师范大学 | Method for preparing important monomer dihalo-disulfonic acid benzophenone of sulfonated polyetheretherketone and salt thereof |
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