CN1279092C - Polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film and method for preparing same - Google Patents
Polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film and method for preparing same Download PDFInfo
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- CN1279092C CN1279092C CN 200410068039 CN200410068039A CN1279092C CN 1279092 C CN1279092 C CN 1279092C CN 200410068039 CN200410068039 CN 200410068039 CN 200410068039 A CN200410068039 A CN 200410068039A CN 1279092 C CN1279092 C CN 1279092C
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Abstract
The present invention discloses a proton exchange film with polyether sulphone block polybutadiene sulfonic acid, and a preparation method thereof. A block polymer of polyether sulphone and polybutadiene is dissolved in an organic solvent. Then, acetic anhydride and concentrated sulphuric acid which have the same molar weight react at a low temperature to obtain acetyl sulphonic acid ester processed through calefactive sulfonation. The sulfonated block polymer is obtained after the sulfonated acetyl sulphonic acid ester is precipitated under an alkalescent condition. The constitutional repeating units of the polymer are disclosed in the following formula. The polymer is dissolved in an organic solvent, coated with films, acidified, washed with water and dried to obtain the proton exchange film with polyether sulphone block polybutadiene sulfonic acid. The proton exchange film has the thermal stability of polyether sulphone structure and the high chain block motion capability of polybutadiene. Selectivity sulfonated flexible polybutadiene chain blocks are convenient for sulfonic acid groups to mutually approach and form an ion-enriched channel. The exchange film can provide high proton electric conductivity (2 to 6*10<-2>S/cm, 25 DEG C, 100% R. H.) under the condition of low sulphonation degree (5%-20%), and has wide application prospects in a fuel cell field.
Description
Technical field: the invention belongs to proton exchange membrane that is used for by fuel cell and preparation method thereof, particularly polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film and preparation method thereof.
Background technology: the research of proton conducting polymer is because its application at aspects such as proton exchange membrane has caused extensive interest, though the proton exchange membrane of perfluor has received maximum concerns in this respect, because its factors such as expensive, synthetic difficulty make researcher then go to study other proton exchange membrane based on aromatic structure.In research process, the structural form of discovery proton conducting polymer has determined physical strength, water ratio, the proton conductivity of final film, conducting polymer molecular structure as the perfluor structure has being separated of height, hydrophilic group is able to mutually near forming ionic channel, even make it have high specific conductivity under the situation of relatively low loading capacity.The synthetic of segmented copolymer is a kind of fine approach that forms phase separation structure, regulates the chain link kind and the length of block and can control the phase separation structure of molecule and the size of microphase-separated accurately.Present institute synthetic sulfonating segmented copolymer, as Mokrini, A. be published in " Polymer " the saturated polystyrene of sulfonation-divinyl star block copolymer (HPBS-SH) of introducing among 2001 (42) 9-15, and JinhwanKim is published in " J Membr Sci " sulfonated polystyrene-ethene-butylene block-copolymer (SSEBS) of being introduced among 2002 (207) 129-37, all be that phenyl ring in the sulfonation segment realizes that the proton electricity leads, though can improve specific conductivity by improving sulfonation degree, but increase with sulfonation degree, film just become easy swelling even dissolving, the forfeiture mechanical property has limited and has prepared the proton exchange membrane that high electricity is led.
Summary of the invention: the present invention carries out optionally sulfonation with acetyl sulfonic acid fat to the polybutadiene segments of the segmented copolymer that contains polyether sulphone and polybutadiene configuration; obtain sulfonated polyether sulphone and butadiene block copolymer, prepare polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film then.Not only can reduce the manufacturing cost of proton exchange membrane, and can make film that higher proton conductivity is provided under the situation of lower sulfonation degree.
The used material of preparing of the present invention is sulfonated polyether sulphone and butadiene block copolymer, and the repeated structural unit of its molecular chain is as follows:
Wherein, m
1=1-80, m
2=1-40, p=20-50, n=20-50; The proton exchange film thickness is that 10-100 micron, sulfonation degree are 5%-20%, and proton conductivity is 2～6 * 10 under 25 ℃ of room temperatures, 100% relative humidity
-2S/cm.
The preparation method of polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film of the present invention following (following all represent) with mass parts:
(1) 15.3 parts of diacetyl oxides added place the reaction vessel of ice bath, and make its remain on 0 ℃ 30 minutes, and then, in ice bath, stirred 4-12 hour 14.7 part of 98% vitriol oil being added drop-wise in the diacetyl oxide slowly, after reaction finishes, generate the acetyl sulphonate;
(2) 1 part of polyether sulphone and butadiene block copolymer are dissolved in the organic solvent of 15-40 part and stir, drip the acetyl sulphonate of 0.5-10 part then, reacted 5-24 hour down at 40 ℃-100 ℃, after reaction finishes, 7-20 part organic solvent is removed in underpressure distillation, then solution is poured in the alcoholic solvent of 100-200 part, solution with 5-20 part 20%NaOH is regulated PH to 7-8, the precipitation that obtains behind the suction filtration is used 20-40 part alcoholic solvent washed twice and vacuum-drying 12-24 hour again, product heats in 80 ℃ of deionized waters and stirred about 2-5 hour the most at last, and suction filtration obtains sulfonated polyether sulphone and butadiene block copolymer;
(3) 1 part of sulfonated polyether sulphone and butadiene block copolymer are dissolved in the organic solvent of 10-20 part, after stirring 4-10 hour under 100 ℃-180 ℃, suction filtration is removed undissolved impurity, the solution that takes out 6-10 part being poured on the glass plate slowly, behind solution nature levelling, with infrared lamp baking 1-8 hour, put into then the dry 12-48 of vacuum drying oven hour, be placed in the 40-80 ℃ of deionized water after dry film takes out and soak, film peels off naturally, the film that takes off shakeouts the back and clamps with filter paper, and apply certain pressure, and put into again the dry 12-48 of vacuum drying oven hour, smooth dry film is taken out the back in the sulfuric acid of 1.5M, soaked 24-48 hour, and then put into deionized water and soaked 24-48 hour, blot with the water of non-dust cloth at last, shakeout and be placed in the two layers of filter paper, and apply certain pressure the film surface, put into again the dry 12-48 of vacuum drying oven hour, and obtained polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film.
The chemical structure of polyether sulphone used in the present invention and butadiene block copolymer is shown below:
Or a bond
Wherein the polymerization degree is respectively n=20-50, m=60-100, p=20-50; Its concrete preparation method following (following all represent) with mass parts:
With 4 of 0.5-2.0 part, the mixed organic solvents that the diphenol monomer of 4 '-dichlorobenzene sulfone and 1 part at room temperature is dissolved in 5-30 part, under nitrogen environment, be warming up to 160 ℃, react after 1-4 hour, rise to 190 ℃ of reactions 14-20 hour again, after reaction finishes, reaction product is cooled to room temperature, behind the B suction filtration, filtrate is poured in 25-70 part alcoholic solvent, stir fast simultaneously, generate precipitation, behind the suction filtration filter cake is placed in 80 ℃ of deionized waters heating and stirred 2-5 hour, suction filtration obtains holding the polyether sulphone of chloro again; With the Poly-s 179 of the end chloro of 5-20 part and 1 part 4-amino phenol, the salt of wormwood of 1-10 part is dissolved in the mixed organic solvents of 100-500 part, at room temperature stir, then under nitrogen environment, be warming up to 150 ℃, react after 15-24 hour, reaction is cooled to room temperature with reaction product after finishing, behind the B suction filtration, filtrate is poured in 500-1500 part alcoholic solvent, and after dripping the hydrochloric acid of 1.5-20 part, generate precipitation, behind the suction filtration filter cake is placed in 80 ℃ of deionized waters heating and stirs, approximately 2-5 hour, suction filtration obtained holding amino polyether sulphone again; 3-15 part carboxy terminated polybutadiene is dissolved in 15-50 part toluene, the thionyl chloride that adds 1 part, reacted 2-6 hour down at 70 ℃ then, rise to 90 ℃ of reactions 2-20 hour again, after reaction is finished, thionyl chloride excessive in the system is removed in underpressure distillation, the carboxy terminated polybutadiene of the chloride that obtains; With 1 part of mixed organic solvents of holding amino polyether sulphone to be dissolved in 5-30 part, the carboxy terminated polybutadiene that adds the chloride of 1-4 part then, reacted 12-36 hour down at 50 ℃, after reaction is finished, product is cooled to room temperature and pours in the alcoholic solvent precipitate, suction filtration, filter cake are placed in 80 ℃ of deionized waters heating and stirred 2-5 hour, and suction filtration obtains polyether sulphone and butadiene block copolymer.
More than in preparation polyether sulphone and the butadiene block copolymer, the synthetic employed diphenol monomer of polyaryl ether sulfone block part is 4,4-dihydroxy-diphenyl propane, 4,4-dihydroxyl phenylbenzene HFC-236fa or 4,4-'-biphenyl diphenol; Employed mixed solvent is N-N-methyl-2-2-pyrrolidone N-and toluene or N, N '-N,N-DIMETHYLACETAMIDE and toluene, and its mass ratio is 1.5: 1-4: 1.
Organic solvent used in the present invention is tetrahydrofuran (THF) (THF), N-N-methyl-2-2-pyrrolidone N-(NMP) or N, N '-N,N-DIMETHYLACETAMIDE (DMAc); Described alcoholic solvent is ethanol or methyl alcohol.
The entire reaction equation that the present invention prepares the sulfonated polyether sulphone block polybutadiene copolymer can be expressed as:
The sulfonation degree of the proton exchange membrane for preparing in the embodiment of the invention and the testing method of specific conductivity are as follows:
The sulfonation degree of the prepared film of the present invention (DS), be to convert by loading capacity, at first 1g (m) film is cut into uniform fragment, being immersed in 50mL, the 1mol/LNaCl solution 24 hours, hydrogen proton in the film and the sodium ion in the solution are exchanged, is indicator then with phenolphthalein, carry out titration with 0.01mol/L NaOH, the volume of the NaOH that record is consumed (v), calculate loading capacity (IEC), converse sulfonation degree (DS) then thus according to following formula:
M wherein
SoftBe soft section number-average molecular weight in the segmented copolymer, M
HardNumber-average molecular weight for hard section in the segmented copolymer; The battery tester of people's designs such as the test employing Zawodzinski of film conductivity " J PhysChem 1991 (95-15) 6040-6044 ", at first film is assembled into test pool and was placed in 25 ℃ of deionized waters hydration 2 hours, the frequency response values of using Solartron SI 1260 electric impedance analyzers under the 10mv booater voltage, to test 100-1MHz then, the last specific conductivity that calculates film sample according to following formula:
Wherein l is two interelectrode distances, and R is a resistance value, and d is the thickness of film, and w is the width of film.
The polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film material (SPAES-b-PB) of the present invention's preparation, the polyether sulphone structure of molecular backbone chain provides good thermostability of film and mechanical property, and the soft segment in the selectivity sulfonating segmented copolymer, improved the motor capacity of sulfonic acid group, help the close mutually of sulfonic acid group, form rich ionic channel, prepare the proton exchange membrane that the high electricity of low sulfonation degree is led, therefore it must have wide practical use in the proton exchange membrane field, below be the embodiment of the invention and the sulfonating segmented copolymer introduced in the document in the past the proton exchange membrane conductivity (25 ℃, comparison 100%R.H.):
| The proton exchange membrane material title | Sulfonation degree (%) | Specific conductivity (S/cm) |
| SPAES-b-PB (the present invention) | 11.5 | 0.0302 |
| HPBS-SH | ＞15 | 0.0081 |
| SSEBS | 15 | 0.0013 |
Description of drawings
Figure the-1st, the infrared spectra of embodiment 1 polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film.
Figure the-2nd, the nucleus magnetic hydrogen spectrum of embodiment 1 polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
Polyether sulphone and butadiene block copolymer synthetic as follows:
Take by weighing 4,4 '-dichlorobenzene sulfone 6.027g (0.021mol), 4,4-dihydroxy-diphenyl propane 4.560g (0.02mol), salt of wormwood 3.174g (0.023mol), add in the three-necked bottle, be dissolved in it in 40g N-N-methyl-2-2-pyrrolidone N-(NMP) and the 17g toluene and stir, under nitrogen environment, be warming up to 160 ℃ then, react after 4 hours, rise to 190 ℃ of reactions 16 hours again.Reaction is finished postcooling to room temperature, behind the B suction filtration, the liquid that obtains is poured in the 150g dehydrated alcohol, stir fast simultaneously, precipitated in a large number, filter cake is placed in 80 ℃ of deionized waters heating and stirred about three hours, suction filtration obtains holding the polyether sulphone 7.656g of chloro, productive rate 83.9% again; Take by weighing 2.960g (0.00020mol) end chloro polyether sulphone, 0.218g (0.0020mol) 4-amino phenol, 0.317g (0.0023mol) salt of wormwood is in three-necked flask, it is dissolved in 40g N-N-methyl-2-2-pyrrolidone N-and the 17g toluene, at room temperature stir, under nitrogen environment, be warming up to 150 ℃ then, reacted 20 hours.Reaction is cooled to room temperature with reaction solution after finishing, and behind the suction filtration filtrate is poured in the 150g dehydrated alcohol, behind the hydrochloric acid about dropping 3g, precipitation in a large number occurs.Behind the suction filtration filter cake is placed on heating and stirring in 80 ℃ of deionized waters, about 3 hours, suction filtration obtained holding amino Poly-s 179 2.25g, productive rate 75.4% again; Take by weighing carboxy terminated polybutadiene 22.713g (0.0053mol) and be dissolved in the 70g toluene, add thionyl chloride 2.544g (0.021mol), magnetic agitation is reacted 2h down at 70 ℃, rises to 90 ℃ of reaction 18h again.After reaction was finished, thionyl chloride excessive in the system was removed in underpressure distillation, the carboxy terminated polybutadiene of the chloride that obtains; The polyether sulphone 3g amino with end is dissolved in 40gNMP, carries out magnetic agitation in the 14g toluene, after the dissolving, adds the carboxy terminated polybutadiene of 5.1g chloride, reacts 24 hours down at 50 ℃.After reaction is finished, be cooled to room temperature, pour in about 150g dehydrated alcohol and precipitate, the filter cake that obtains with the B suction filtration obtains polyether sulphone and butadiene block copolymer with 80 ℃ of deionization poach suction filtration after 3 hours;
(1) the 15.3g diacetyl oxide added place the reaction vessel of ice bath, and make its remain on 0 ℃ 30 minutes, and then, in ice bath, stirred 6 hours the 14.7g vitriol oil being added drop-wise in the diacetyl oxide slowly, after reaction finishes, generate the acetyl sulphonate;
(2) with 2g by 4; in the tetrahydrofuran (THF) that the polyether sulphone of 4-dihydroxy-diphenyl propane preparation and butadiene block copolymer are dissolved in 44.3g and stir; drip 7.5g acetyl sulphonate then; reacted 12 hours down at 75 ℃; after reaction finishes; product evaporates the 20g tetrahydrofuran (THF) with underpressure distillation; then solution is poured in the ethanol of 230g; NaOH solution 10g with 20% regulates PH to 7-8; the precipitation that obtains behind the suction filtration was used twice of 50g washing with alcohol and vacuum-drying 24 hours again; at last product is heated in 80 ℃ of deionized waters and stirred about 3 hours; suction filtration obtains sulfonated polyether sulphone and butadiene block copolymer 2.8g, and (wherein the polymerization degree is n=31, m
1=69, m
2=9, p=25), productive rate is 84%; Accompanying drawing 1 is the infrared spectra of this embodiment polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film, FT-IR (KBr): 3400 (OH), 2917 (CH
3), 1684 (C=O), 1300,1150 (S=O), 1040 (SO
3), 970 (=CH). accompanying drawing 2 is nucleus magnetic hydrogen spectrums of this embodiment polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film,
1H NMR (DMSO, 400MHz): δ=6.92-7.90 (phenyl ring), 5.5 (CH=CH), 3.3 (CH-SO
3Na), 1.8-2.0 (CH
2), 1.68 (6H, CH
3).
(3) 2g sulfonated polyether sulphone and butadiene block copolymer are dissolved in 25g NMP, after stirring 4 hours under 150 ℃, suction filtration is removed undissolved impurity, the solution that takes out 10g being poured on the glass plate slowly, behind solution nature levelling, with infrared lamp baking 4 hours, put into vacuum drying oven then dry 24 hours, be placed in 60 ℃ of deionized waters after dry film takes out and soak, film peels off naturally, the film that takes off shakeouts the back and clamps with filter paper, and apply certain pressure, put into vacuum drying oven drier 12 hours, smooth dry film is taken out the back to be soaked 24 hours in the sulfuric acid of 1.5M, and then put into deionized water and soaked 24 hours, blot with the water of non-dust cloth at last the film surface, shakeout and be placed in the two layers of filter paper, and apply certain pressure, put into vacuum drying oven drier 24 hours, obtain polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film, it is 40 microns that experiment records this proton exchange film thickness, and sulfonation degree is 11.5%, specific conductivity be 0.0402S/cm (25 ℃, 100%R.H.).
Embodiment 2:
Polyether sulphone and butadiene block copolymer synthetic as follows:
Take by weighing 4,4 '-dichlorobenzene sulfone 6.027g (0.021mol), 4,4-dihydroxyl phenylbenzene HFC-236fa 6.720g (0.020mol), salt of wormwood 3.174g (0.023mol), add in the three-necked bottle, it is dissolved in 37gN, in N '-N,N-DIMETHYLACETAMIDE and the 17g toluene and stir, then under nitrogen environment, be warming up to 160 ℃, react after 4 hours, rise to 190 ℃ of reactions 20 hours again.Reaction is finished postcooling to room temperature, behind the B suction filtration, the liquid that obtains is poured in about 230g methyl alcohol, stir fast simultaneously, precipitated in a large number, filter cake is placed in 80 ℃ of deionized waters heating and stirred about three hours, suction filtration obtains holding the polyether sulphone 10.011g of chloro, productive rate 88.7% again; Take by weighing 2.960g (0.00020mol) end chloro polyether sulphone, 0.218g (0.0020mol) 4-amino phenol, 0.317g (0.0023mol) salt of wormwood is in three-necked flask, it is dissolved in 30gN, in N '-N,N-DIMETHYLACETAMIDE and the 17g toluene, at room temperature stir, then under nitrogen environment, be warming up to 150 ℃, reacted 24 hours.Reaction is cooled to room temperature with reaction solution after finishing, and behind the suction filtration filtrate is poured in the 150g methyl alcohol, behind the hydrochloric acid about dropping 2g, precipitation in a large number occurs.Behind the suction filtration filter cake is placed on heating and stirring in 80 ℃ of deionized waters, about 3 hours, suction filtration obtained holding amino Poly-s 179 2.60g, productive rate 87.2% again; Take by weighing carboxy terminated polybutadiene 22.713g (0.0053mol) and be dissolved in the 70g toluene, add thionyl chloride 2.544g (0.021mol), magnetic agitation is reacted 2h down at 70 ℃, rises to 90 ℃ of reaction 18h again.After reaction was finished, thionyl chloride excessive in the system was removed in underpressure distillation, the carboxy terminated polybutadiene of the chloride that obtains; The polyether sulphone 3g amino with end is dissolved in 40gNMP, carries out magnetic agitation in the 14g toluene, after the dissolving, adds the carboxy terminated polybutadiene of 5.1g chloride, reacts 24 hours down at 50 ℃.After reaction is finished, be cooled to room temperature, pour in about 150g methyl alcohol and precipitate, the filter cake that obtains with the B suction filtration obtains polyether sulphone and butadiene block copolymer with 80 ℃ of deionization poach suction filtration after 3 hours;
(1) the 15.3g diacetyl oxide is added places the reaction vessel of ice bath, and make it remain on 0 ℃ of for some time, and then, in ice bath, stirred 6 hours, after reaction finishes, generate the acetyl sulphonate the 14.7g vitriol oil being added drop-wise in the diacetyl oxide slowly;
(2) with 2g by 4; among the NMP that the polyether sulphone of 4-dihydroxyl phenylbenzene HFC-236fa preparation and butadiene block copolymer are dissolved in 51g and stir; drip 10g acetyl sulphonate then; reacted 12 hours down at 50 ℃; after reaction finishes; product evaporates 30gNMP with underpressure distillation; then solution is poured in the methyl alcohol of 270g; NaOH solution 15g with 20% regulates PH to 7-8; the precipitation that obtains behind the suction filtration was used twice of 60g methanol wash and vacuum-drying 24 hours again; at last product is heated in 80 ℃ of deionized waters and stirred about 3 hours, suction filtration obtains sulfonated polyether sulphone and butadiene block copolymer 2.9g, and (wherein the polymerization degree is n=34, m
1=70, m
2=8, p=22), productive rate is 90%; FT-IR (KBr): 3400 (OH), 2917 (CH
3), 1684 (C=O), 1300,1150 (S=O), 1040 (SO
3), 1188,737 (C-F), 970 (=CH).
1H NMR (DMSO, 400MHz): δ=6.84-7.90 (phenyl ring), 5.5 (CH=CH), 3.3 (CH-SO
3Na), 1.8-2.0 (CH
2), 1.68 (6H, CH
3).
(3) 2g sulfonated polyether sulphone and butadiene block copolymer are dissolved in 25g NMP, after stirring 4 hours under 150 ℃, suction filtration is removed undissolved impurity, the solution that takes out 10g being poured on the glass plate slowly, behind solution nature levelling, with infrared lamp baking 4 hours, put into vacuum drying oven then dry 24 hours, be placed in 60 ℃ of deionized waters after dry film takes out and soak, film peels off naturally, the film that takes off shakeouts the back and clamps with filter paper, and apply certain pressure, put into vacuum drying oven drier 12 hours, smooth dry film is taken out the back to be soaked 24 hours in the sulfuric acid of 1.5M, and then put into deionized water and soaked 24 hours, blot with the water of non-dust cloth at last the film surface, shakeout and be placed in the two layers of filter paper, and apply certain pressure, put into vacuum drying oven drier 24 hours, obtain polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film, it is 32 microns that experiment records this proton exchange film thickness, and sulfonation degree is 10.8%, specific conductivity be 0.0382S/cm (25 ℃, 100%R.H.).
Embodiment 3:
Polyether sulphone and butadiene block copolymer synthetic as follows:
Take by weighing 4,4 '-dichlorobenzene sulfone 6.027g (0.021mol), 4,4-'-biphenyl diphenol 3.720g (0.020mol), salt of wormwood 3.174g (0.023mol), add in the three-necked bottle, it is dissolved in 40g N-N-methyl-2-2-pyrrolidone N-, in the 17g toluene and stir, then under nitrogen environment, be warming up to 160 ℃, react after 4 hours, rise to 190 ℃ of reactions 16 hours again.Reaction is finished postcooling to room temperature, behind the B suction filtration, the liquid that obtains is poured in about 150g dehydrated alcohol, stir fast simultaneously, precipitated in a large number, filter cake is placed in 80 ℃ of deionized waters heating and stirred about three hours, suction filtration obtains holding the polyether sulphone 6.646g of chloro, productive rate 80.2% again; Take by weighing 2.960g (0.00020mol) end chloro polyether sulphone, 0.218g (0.0020mol) 4-amino phenol, 0.317g (0.0023mol) salt of wormwood is in three-necked flask, it is dissolved in the 40gN-N-methyl-2-2-pyrrolidone N-, 17g toluene at room temperature stirs, then under nitrogen environment, be warming up to 150 ℃, reacted 20 hours.Reaction is cooled to room temperature with reaction solution after finishing, and behind the suction filtration filtrate is poured in the 150g dehydrated alcohol, behind the hydrochloric acid about dropping 2.5g, precipitation in a large number occurs.Behind the suction filtration filter cake is placed on heating and stirring in 80 ℃ of deionized waters, about 3 hours, suction filtration obtained holding amino Poly-s 179 2.12g, productive rate 71.3% again; Take by weighing carboxy terminated polybutadiene 22.713g (0.0053mol) and be dissolved in the 70g toluene, add thionyl chloride 2.544g (0.021mol), magnetic agitation is reacted 2h down at 70 ℃, rises to 90 ℃ of reaction 18h again.After reaction was finished, thionyl chloride excessive in the system was removed in underpressure distillation, the carboxy terminated polybutadiene of the chloride that obtains; The polyether sulphone 3g amino with end is dissolved in 40gNMP, carries out magnetic agitation in the 14g toluene, after the dissolving, adds the carboxy terminated polybutadiene of 5.1g chloride, reacts 24 hours down at 50 ℃.After reaction is finished, be cooled to room temperature, pour in the dehydrated alcohol of about 150g left and right sides and precipitate, the filter cake that obtains with the B suction filtration obtains polyether sulphone and butadiene block copolymer with 80 ℃ of deionization poach suction filtration after 3 hours;
(1) the 15.3g diacetyl oxide is added places the reaction vessel of ice bath, and make it remain on 0 ℃ of for some time, and then, in ice bath, stirred 6 hours, after reaction finishes, generate the acetyl sulphonate the 14.7g vitriol oil being added drop-wise in the diacetyl oxide slowly;
(2) in the tetrahydrofuran (THF) that 2g is dissolved in 44.3g by the polyether sulphone and the butadiene block copolymer of '-biphenyl diphenol preparation and stir; drip 15g acetyl sulphonate then; reacted 24 hours down at 100 ℃; after reaction finishes; product evaporates the 20g tetrahydrofuran (THF) with underpressure distillation; then solution is poured in the ethanol of 230g; NaOH solution 18g with 20% regulates PH to 7-8; the precipitation that obtains behind the suction filtration was used twice of 50g washing with alcohol and vacuum-drying 24 hours again; at last product is heated in 80 ℃ of deionized waters and stirred about 3 hours; suction filtration obtains sulfonated polyether sulphone and butadiene block copolymer 2.67g, and (wherein the polymerization degree is n=24, m
1=71, m
2=7, p=31), productive rate is 78%; FT-IR (KBr): 3400 (OH), 2917 (CH
3), 1687 (C=O), 1300,1150 (S=O), 1040 (SO
3), 998,965 (C-H), 970 (=CH).
1H NMR (DMSO, 400MHz): δ=6.98-7.86 (phenyl ring), 5.5 (CH=CH), 3.3 (CH-SO
3Na), 1.8-2.0 (CH
2), 1.68 (6H, CH
3).
(3) 2g sulfonated polyether sulphone and butadiene block copolymer are dissolved in 24gDMAc, after stirring 4 hours under 150 ℃, suction filtration is removed undissolved impurity, the solution that takes out 10g being poured on the glass plate slowly, behind solution nature levelling, with infrared lamp baking 4 hours, put into vacuum drying oven then dry 24 hours, be placed in 60 ℃ of deionized waters after dry film takes out and soak, film peels off naturally, the film that takes off shakeouts the back and clamps with filter paper, and apply certain pressure, put into vacuum drying oven drier 12 hours, smooth dry film is taken out the back to be soaked 24 hours in the sulfuric acid of 1.5M, and then put into deionized water and soaked 24 hours, blot with the water of non-dust cloth at last the film surface, shakeout and be placed in the two layers of filter paper, and apply certain pressure, put into vacuum drying oven drier 24 hours, obtain polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film, it is 65 microns that experiment records this proton exchange film thickness, and sulfonation degree is 9.32%, specific conductivity be 0.0246S/cm (25 ℃, 100%R.H.).
Claims (3)
1. a polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film is characterized in that with sulfonated polyether sulphone and butadiene block copolymer be material of preparing, and the repeated structural unit of its polymer molecular chain is shown below:
X is
Or---;
Wherein, m
1=1-80, m
2=1-40, p=20-50, n=20-50; The proton exchange film thickness is the 10-100 micron, and sulfonation degree is 5%-20%, and proton conductivity is 2～6 * 10 under 25 ℃ of room temperatures, 100% relative humidity
-2S/cm.
2. the preparation method of polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film according to claim 1 is characterized in that the preparation method is as follows, below all represents with mass parts:
(1) 15.3 parts of diacetyl oxides added place the reaction vessel of ice bath, and make its remain on 0 ℃ 30 minutes, and then, in ice bath, stirred 4-12 hour 14.7 part of 98% vitriol oil being added drop-wise in the diacetyl oxide slowly, after reaction finishes, generate the acetyl sulphonate;
(2) 1 part of polyether sulphone and butadiene block copolymer are dissolved in the organic solvent of 15-40 part and stir, drip the acetyl sulphonate of 0.5-10 part then, reacted 5-24 hour down at 40 ℃-100 ℃, after reaction finishes, 7-20 part organic solvent is removed in underpressure distillation, then solution is poured in the alcoholic solvent of 100-200 part, solution with 5-20 part 20%NaOH is regulated PH to 7-8, the precipitation that obtains behind the suction filtration is used 20-40 part alcoholic solvent washed twice and vacuum-drying 12-24 hour again, product heats in 80 ℃ of deionized waters and stirred 2-5 hour the most at last, and suction filtration obtains sulfonated polyether sulphone and butadiene block copolymer; Wherein organic solvent is tetrahydrofuran (THF), N-N-methyl-2-2-pyrrolidone N-or N, N '-N,N-DIMETHYLACETAMIDE; Alcoholic solvent is ethanol or methyl alcohol;
(3) 1 part of sulfonated polyether sulphone and butadiene block copolymer are dissolved in the organic solvent of 10-20 part, after stirring 4-10 hour under 100 ℃-180 ℃, suction filtration is removed undissolved impurity, the solution that takes out 6-10 part being poured on the glass plate slowly, behind solution nature levelling, with infrared lamp baking 1-8 hour, put into then the dry 12-48 of vacuum drying oven hour, be placed in the 40-80 ℃ of deionized water after dry film takes out and soak, film peels off naturally, the film that takes off shakeouts the back and clamps with filter paper, and apply certain pressure, and put into again the dry 12-48 of vacuum drying oven hour, smooth dry film is taken out the back in the sulfuric acid of 1.5M, soaked 24-48 hour, and then put into deionized water and soaked 24-48 hour, blot with the water of non-dust cloth at last, shakeout and be placed in the two layers of filter paper, and apply certain pressure the film surface, put into again the dry 12-48 of vacuum drying oven hour, and obtained polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film; Wherein organic solvent is tetrahydrofuran (THF), N-N-methyl-2-2-pyrrolidone N-or N, N '-N,N-DIMETHYLACETAMIDE.
3. according to the preparation method of the described polyaryl ether sulfone block polybutadiene sulfonic acid proton exchange film of claim 2, it is characterized in that the repeated structural unit of described polyether sulphone and butadiene block copolymer molecular chain is as follows:
Wherein the polymerization degree is respectively n=20-50, m=60-100, p=20-50.
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