CN101463129B - Method for synthesizing sulphonation polyetheretherketone for proton exchange membrane by three-step process - Google Patents
Method for synthesizing sulphonation polyetheretherketone for proton exchange membrane by three-step process Download PDFInfo
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- CN101463129B CN101463129B CN2008102039763A CN200810203976A CN101463129B CN 101463129 B CN101463129 B CN 101463129B CN 2008102039763 A CN2008102039763 A CN 2008102039763A CN 200810203976 A CN200810203976 A CN 200810203976A CN 101463129 B CN101463129 B CN 101463129B
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000012528 membrane Substances 0.000 title claims abstract description 20
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 13
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 29
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 239000012965 benzophenone Substances 0.000 claims description 17
- 150000008366 benzophenones Chemical class 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 229910001867 inorganic solvent Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000000655 anti-hydrolysis Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 allyl group dihydroxyphenyl propanes Chemical class 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Polyethers (AREA)
Abstract
The invention relates to a method for preparing sulfonated polyether ether ketone used on a proton exchange membrane by a three-step method. The method comprises the following steps: taking difluorobenzophenone, sulfonated difluorobenzophenone and bisphenol as monomers; and directly polymerizing the sulfonated monomers by a salifying reaction, a prepolymerization reaction and a polymerization reaction to obtain the sulfonated polyether ether ketone. The method has the advantages of low cost, simple operation, high yield, good film forming property of the synthesized sulfonated polyether ether ketone, good mechanical stability and controllable degree of sulfonation.
Description
Technical field
The present invention relates to the synthetic method of a kind of proton exchange membrane with sulfonated polyether-ether-ketone, particularly a kind of three-step approach prepares the method for proton exchange membrane with sulfonated polyether-ether-ketone.
Background technology
Proton exchange membrane (PEM) is as the core of the focus direct methanol fuel cell (DMFC) of energy field research and development at present, and its material must have good proton conductive, and (room-temperature conductivity should reach 10 at least
-2S.cm
-1), and excellent alcohol-rejecting ability, otherwise influence battery efficiency, work-ing life and cause wastage of material; Also to have sufficiently high stability of solution and chemical stability simultaneously, proton exchange membrane is had than the long life in DMFC.
The proton exchange membrane of widespread use at present is a perfluoro sulfonic acid membrane, because the manufacturing cost height, high-temperature behavior is not good enough, and especially the resistance of film alcohol scarce capacity has limited its application in DMFC.Therefore, the PEM of several no fluorine type polymers receives publicity in recent years, wherein sulfonated polyether-ether-ketone (SPEEK) film is all comparatively outstanding at aspects such as chemical stability, hot properties, alcohol-rejecting abilities, and being expected to replace perfluoro sulfonic acid membrane becomes a kind of novel proton exchange membrane material.
The preparation of sulfonated polyether-ether-ketone is divided into back sulfonation and two kinds of approach of sulfonated monomers direct polymerization.Back sulfonation method makes polymkeric substance take place crosslinked or degraded because sulfonation reaction is comparatively violent, and strong sulfonated reagent (as chlorsulfonic acid) can cause side reaction.And there is following problem in sulfonated polymer: it is more that (1) influences the factor of sulfonation degree, and difficult control of the sulfonation degree of polymkeric substance and repeatability are bad, and the reaction meeting is because the raising of sulfonation degree is difficult to control.(2) product that will expect highly sulfonated must adopt strict more condition such as the rising temperature of reaction, improve sulphonating agent concentration etc., but will inevitably cause the generation of some side reactions like this, such as intramolecular crosslinking or degraded, and resulting polymer sizes less stable.(3) the sulfonation position generally is on the higher phenyl ring of the cloud density that links to each other with the bis ether key, and sulfonic anti-hydrolysis ability is descended, and particularly under acidic conditions, has further reduced the chemical stability of this base polymer.(4) along with the raising of sulfonation degree, the variation (swelling phenomenon) of film suction back volume is more and more serious, influences the dimensional stability of film.(5) fragility is bigger under this class film dryness situation, has influenced their mechanical property.And adopt direct copolymerization method that following advantage is arranged: (1) can be by the input amount control sulfonation degree of sulfonated monomers.(2) because each unit contains two sulfonic acid groups, can prepare the more sulfonated polyether-ether-ketone of highly sulfonated.(3) sulfonic acid group has better chemical stability and stronger anti-hydrolysis ability on the phenyl ring that is connected with strong electron-withdrawing group group (carbonyl).
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process is a monomer with difluoro benzophenone, sulfonation difluoro benzophenone and bis-phenol, adopts sulfonated monomers direct polymerization method to synthesize, and it is characterized in that the concrete steps of this method are:
A. salify: biphenol monomer is dissolved in the solvent, be warming up to 115 ℃～120 ℃ under the inert atmosphere after, add the part catalyzer again, its consumption is 1.0～1.2 times of biphenol monomer mole number, is warming up to 135 ℃～140 ℃ reactions 1～2 hour;
B. pre-polymerization: in step a gained solution, add part difluoro benzophenone and sulfonation difluoro benzophenone and band aqua toluene or dimethylbenzene, and add remaining catalyzer, in 135 ℃～140 ℃ following stirring reactions 2～4 hours, be warming up to 140 ℃～150 ℃ reactions 3～4 hours again;
C. polymerization: add remaining difluoro benzophenone and sulfonation difluoro benzophenone in step b gained solution, 140 ℃～150 ℃ are continued reaction 2～4 hours, are warming up to 180 ℃～200 ℃ reactions 8～10 hours again;
D. the purifying technique of polymerisate: step c gained solution is cooled to 100 ℃～120 ℃, pours in the deionized water, the cooling back is pulverized, is filtered with pulverizer; Boil, filter to remove catalyzer and solvent wherein with methyl alcohol or acetone again; At last, the product of purifying out is placed vacuum drying oven dry 12h～24h under 80 ℃～100 ℃ get the proton exchange membrane sulfonated polyether-ether-ketone;
Described difluoro benzophenone monomer is: 4, and 4 '-difluoro benzophenone or 4,4 '-difluoro, three benzophenones;
Described sulfonation difluoro benzophenone monomer is sulfonation 4,4 '-difluoro benzophenone or sulfonation 4,4 '-difluoro, three benzophenones;
The structural formula of described biphenol monomer is; HO-A---OH, wherein A is:
Or
Wherein R is the straight chained alkyl of C1～C3;
The monomeric mole number sum of described difluoro benzophenone monomer and sulfonation difluoro benzophenone equals the mole number of biphenol monomer, and control sulfonation degree DS is 0～200;
Described catalyzer is anhydrous sodium carbonate or Anhydrous potassium carbonate, and its consumption is 1.2～1.8 times of biphenol monomer mole number;
Described solvent is: dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, N, and dinethylformamide or N,N-dimethylacetamide, and monomeric solid content is 25%～35% in the control reaction system.
Above-mentioned sulfonation difluoro benzophenone monomer needs through 50 ℃～100 ℃ following vacuum drying treatment 8～24 hours.
Above-mentioned catalyzer needs through 80 ℃～120 ℃ following drying treatment 6～24 hours.
Above-mentioned band aqua and solvent need through anhydrous hydride drying treatment.
The monomeric preparation method of above-mentioned sulfonation difluoro benzophenone is: with mol ratio be 1: 1.5～1: 34,4 '-difluoro benzophenone or 4,4 '-difluoro, three benzophenones are with after oleum mixes, under 100 ℃～120 ℃ temperature, stirring reaction 8～10 hours, reaction finish postcooling to room temperature; Pour reaction solution in ice-water bath termination reaction, cooling back regulator solution pH value is 7～8, through the NaCl solid saltout, filter, drying, obtain the sulfonation crude product; This sulfonation crude product is dissolved in the deionized water, is mixed with saturated solution, add ethanol or methyl alcohol again, present a large amount of white flosss to solution, suction filtration was in 80 ℃～100 ℃ following vacuum-dryings 12～24 hours, get white needle-like crystals, be sulfonation difluoro benzophenone.
The inventive method adopts three-step approach to synthesize the sulfonated polyether-ether-ketone of different sulfonation degree, and this method cost is low, simple to operate, the productive rate height, and the sulfonated polyether-ether-ketone good film-forming property, good mechanical stability and the sulfonation degree that are synthesized are controlled.
Embodiment
Embodiment one: the concrete steps of present embodiment are:
One, sulfonated monomers is synthetic: with 20g4,4 '-difluoro benzophenone is dissolved in 50mL oleum (SO
350%) in, be heated to 100 ℃, stirring reaction 10h is cooled to room temperature.Reaction solution is poured in the 500mL frozen water, and adding the sodium hydroxide solution pH value is 7～8, and precipitation is separated out to wherein adding 140 gram NaCl solids in the cooling back, filters, dry thick product.Thick product is dissolved in the deionized water of 4 times of volumes, obtain saturated aqueous solution after, add 6 times of volume of ethanol again, present a large amount of white flosss in the solution, suction filtration is in 90 ℃ of following vacuum-drying 12h～24h.Repeat the aforesaid operations white needle-like crystals 3 of purifying out for 5 times, 3 '-sodium disulfonate-4,4 '-difluoro benzophenone, 34.1 grams, productive rate is 88%.
Two, the pretreatment technology of reactant before the polyreaction:
1. with 3,3 '-sodium disulfonate-4,4 '-difluoro benzophenone is in 80 ℃ of following vacuum-drying 12h.
2. with anhydrous sodium carbonate powder 100 ℃ of following dry 10h in vacuum drying oven.
3. the anhydrous hydrolith that adds respectively in N-Methyl pyrrolidone NMP and toluene solvant about 100 grams soaked 6 days, refluxed standby with anhydrous hydrolith again.
Three, polyreaction:
1. salify: in the 250ml three-necked flask that water trap and logical nitrogen pipe are housed, add 7.70 gram allyl group dihydroxyphenyl propanes, 35ml solvent NMP; after under nitrogen protection, progressively being warming up to 120 ℃; the anhydrous sodium carbonate powder that adds 2.65 grams; be warming up to 140 ℃ of reaction 1.5h; the reactant bubbling is not obvious in the system, and allyl group dihydroxyphenyl propane salify is finished.
2. pre-polymerization: in above-mentioned system, add 1.60 grams 4,4 '-difluoro benzophenone, 1.58 grams 3,3 '-sodium disulfonate-4,4 '-difluoro benzophenone, the anhydrous sodium carbonate powder of 12ml toluene, 0.53 gram, in 140 ℃ of following stirring reaction 3h, progressively remove moisture, toluene in the reaction system in the reaction process, progressively be warming up to 150 ℃ of reaction 4h again and finish.
3. polymerization: add remaining 1.60 grams 4,4 '-difluoro benzophenone, 1.58 grams 3,3 '-sodium disulfonate-4,4 '-difluoro benzophenone, 12ml toluene continue reaction 3h under this temperature, progressively remove moisture, toluene in the reaction system in the reaction process.Be warming up to 190 ℃ of reaction 10h at last and finish polymerization.
4. treat to pour in the deionized water when product temperature is reduced to 100 ℃, the cooling back is pulverized, is filtered with pulverizer.Boil, filter with methyl alcohol again, repeat 6 times, remove wherein inorganic salt and solvent.At last, place vacuum drying oven dry 24h under 100 ℃ to get polymer samples.Productive rate is about 94%.
The polymerisate viscosity test: adopt Ubbelohde viscometer, in steady temperature T=25 ± 0.1 (℃) measure the reduced viscosity of polymkeric substance, make solvent with N,N-DIMETHYLACETAMIDE, be made into 0.5g/dL solution, viscosity is calculated as follows:
Reduced viscosity: η sp/C=(η r-1)/C=(t/t
0-1)/C (dL/g)
T, t
0Be respectively solution, the elution time of neat solvent (s), C is strength of solution (g/dL)
Record the reduced viscosity η sp/c=0.7851 (dL/g) of polymerisate.The polymkeric substance of this viscosity can satisfy the requirement of film-forming properties, and film forming properties is good.
Embodiment two: the concrete steps of present embodiment are:
One, sulfonated monomers is synthetic: with 20g4,4 '-difluoro, three benzophenones are dissolved in 50mL oleum (SO
350%) in, be heated to 100 ℃, stirring reaction 10h is cooled to room temperature.Reaction solution is poured in the 500mL frozen water, and adding the sodium hydroxide solution pH value is 7～8, and precipitation is separated out to wherein adding 140 gram NaCl solids in the cooling back, filters, dry thick product.Thick product is dissolved in the deionized water of 4 times of volumes, obtain saturated aqueous solution after, add 6 times of volume of ethanol again, present a large amount of white flosss in the solution, suction filtration is in 90 ℃ of following vacuum-drying 12h～24h.Repeat the aforesaid operations white needle-like crystals 3 of purifying out for 5 times, 3 '-sodium disulfonate-4,4 '-difluoro, three benzophenones, 34.1 grams, productive rate is 88%.
Two, the pretreatment technology of reactant before the polyreaction:
1. with 3,3 '-sodium disulfonate-4,4 '-difluoro, three benzophenones are in 80 ℃ of following vacuum-drying 12h.
2. with anhydrous sodium carbonate powder 100 ℃ of following dry 10h in vacuum drying oven.
3. the anhydrous hydrolith that adds respectively in dimethyl sulfoxide (DMSO) and xylene solvent about 100 grams soaked 6 days, refluxed standby with anhydrous hydrolith again.
Three, polyreaction:
1. salify: in the 250ml three-necked flask that water trap and logical nitrogen pipe are housed, add 11.4 gram dihydroxyphenyl propanes, 66mlDMSO; after progressively being warming up to 110 ℃ under the nitrogen protection; the anhydrous sodium carbonate powder that adds 5.3 grams; be warming up to 120 ℃ of reaction 2h; the reactant bubbling is not obvious in the system, and the dihydroxyphenyl propane salify is finished.
2. pre-polymerization: in above-mentioned system, add 4.36 grams 4,4 '-difluoro, three benzophenones, 2.11 grams 3,3 '-sodium disulfonate-4,4 '-difluoro, three benzophenones, the anhydrous sodium carbonate powder of 10ml dimethylbenzene, 1.59 grams, in 140 ℃ of following stirring reaction 3.5h, progressively remove moisture, toluene in the reaction system in the reaction process, progressively be warming up to 150 ℃ of reaction 4h again and finish.
3. polymerization: add remaining 4.36 grams 4,4 '-difluoro, three benzophenones, 2.11 grams 3,3 '-sodium disulfonate-4,4 '-difluoro, three benzophenones, 12ml dimethylbenzene continue reaction 3h under this temperature, progressively remove moisture, toluene in the reaction system in the reaction process.Be warming up to 185 ℃ of reaction 10h at last and finish polymerization.
4. treat to pour in the deionized water when product temperature is reduced to 100 ℃, the cooling back is pulverized, is filtered with pulverizer.Boil, filter with methyl alcohol again, repeat 6 times, remove wherein inorganic salt and solvent.At last, place vacuum drying oven dry 24h under 100 ℃ to get polymer samples.Productive rate is about 94%.
The polymerisate viscosity test: adopt Ubbelohde viscometer, in steady temperature T=25 ± 0.1 (℃) measure the reduced viscosity of polymkeric substance, make solvent with N,N-DIMETHYLACETAMIDE, be made into 0.5g/dL solution, viscosity is calculated as follows:
Reduced viscosity: η sp/C=(η r-1)/C=(t/t
0-1)/C (dL/g)
T, t
0Be respectively solution, the elution time of neat solvent (s), C is strength of solution (g/dL)
Record the reduced viscosity η sp/c=0.8317 (dL/g) of polymerisate.The polymkeric substance of this viscosity can satisfy the requirement of film-forming properties, and film forming properties is good.
Embodiment three: the pretreatment technology of the preceding reactant of synthetic and polyreaction of the sulfonated monomers of present embodiment is identical with embodiment two, and the step of polymerization process that different is is:
1. salify: in the 500ml three-necked flask that water trap and logical nitrogen pipe are housed, add the adjacent methyl hydroquinone of 12.4 grams, 116mlDMSO; after progressively being warming up to 110 ℃ under the nitrogen protection; the Anhydrous potassium carbonate powder that adds 16.6 grams; be warming up to 120 ℃ of reaction 2h; the reactant bubbling is not obvious in the system, and the dihydroxyphenyl propane salify is finished.
2. pre-polymerization: in above-mentioned system, add 8.05 grams 4,4 '-difluoro, three benzophenones, 13.15 grams 3,3 '-sodium disulfonate-4,4 '-difluoro, three benzophenones, the Anhydrous potassium carbonate powder of 20ml toluene, 2.76 grams, in 140 ℃ of following stirring reaction 3.5h, progressively remove moisture, toluene in the reaction system in the reaction process, progressively be warming up to 150 ℃ of reaction 4h again and finish.
3. polymerization: add remaining 8.05 grams 4,4 '-difluoro, three benzophenones, 13.15 grams 3,3 '-sodium disulfonate-4,4 '-difluoro, three benzophenones, 25ml toluene continue reaction 3h under this temperature, progressively remove moisture, toluene in the reaction system in the reaction process.Be warming up to 190 ℃ of reaction 10h at last and finish polymerization.
4. treat to pour in the deionized water when product temperature is reduced to 100 ℃, the cooling back is pulverized, is filtered with pulverizer.Boil, filter with methyl alcohol again, repeat 6 times, remove wherein inorganic salt and solvent.At last, place vacuum drying oven dry 24h under 100 ℃ to get polymer samples.Productive rate is about 94%.
The polymerisate viscosity test: adopt Ubbelohde viscometer, in steady temperature T=20 ± 0.1 (℃) measure the reduced viscosity of polymkeric substance, make solvent with N,N-DIMETHYLACETAMIDE, be made into 0.5g/dL solution, viscosity is calculated as follows:
Reduced viscosity: η sp/C=(η r-1)/C=(t/t
0-1)/C (dL/g)
T, t
0Be respectively solution, the elution time of neat solvent (s), C is the reduced viscosity η sp/c=0.7721 (dL/g) that strength of solution (g/dL) records polymerisate.The polymkeric substance of this viscosity can satisfy the requirement of film-forming properties, and film forming properties is good.
Claims (5)
1. the method for a synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process is a monomer with difluoro benzophenone, sulfonation difluoro benzophenone and bis-phenol, adopts sulfonated monomers direct polymerization method to synthesize, and it is characterized in that the concrete steps of this method are:
A. salify: biphenol monomer is dissolved in the solvent, be warming up to 115 ℃～120 ℃ under the inert atmosphere after, add the part catalyzer again, its consumption is 1.0～1.2 times of biphenol monomer mole number, is warming up to 135 ℃～140 ℃ reactions 1～2 hour;
B. pre-polymerization: in step a gained solution, add part difluoro benzophenone and sulfonation difluoro benzophenone and band aqua toluene or dimethylbenzene, and add remaining catalyzer, in 135 ℃～140 ℃ following stirring reactions 2～4 hours, be warming up to 140 ℃～150 ℃ reactions 3～4 hours again;
C. polymerization: add remaining difluoro benzophenone and sulfonation difluoro benzophenone in step b gained solution, 140 ℃～150 ℃ are continued reaction 2～4 hours, are warming up to 180 ℃～200 ℃ reactions 8～10 hours again;
D. the purifying technique of polymerisate: step c gained solution is cooled to 100 ℃～120 ℃, pours in the deionized water, the cooling back is pulverized, is filtered with pulverizer; Boil, filter to remove catalyzer and solvent wherein with methyl alcohol or acetone again; At last, the product of purifying out is placed vacuum drying oven dry 12h～24h under 80 ℃～100 ℃ get the proton exchange membrane sulfonated polyether-ether-ketone;
Described difluoro benzophenone monomer is: 4, and 4 '-difluoro benzophenone or 4,4 '-difluoro, three benzophenones;
Described sulfonation difluoro benzophenone monomer is sulfonation 4,4 '-difluoro benzophenone or sulfonation 4,4 '-difluoro, three benzophenones; The structural formula of described biphenol monomer is; HO-A-OH, wherein A is:
Or
Wherein R is the straight chained alkyl of C1～C3; The monomeric mole number sum of described difluoro benzophenone monomer and sulfonation difluoro benzophenone equals the mole number of biphenol monomer, and control sulfonation degree DS is 0～200;
Described catalyzer is anhydrous sodium carbonate or Anhydrous potassium carbonate, and its consumption is 1.2～1.8 times of biphenol monomer mole number; Described solvent is: dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, N, and dinethylformamide or N,N-dimethylacetamide, and monomeric solid content is 25%～35% in the control reaction system.
2. the method for synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process according to claim 1 is characterized in that described sulfonation difluoro benzophenone monomer needs through 50 ℃～100 ℃ following vacuum drying treatment 8～24 hours.
3. the method for synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process according to claim 1 is characterized in that described catalyzer needs through 80 ℃～120 ℃ following drying treatment 6～24 hours.
4. the method for synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process according to claim 1 is characterized in that described band aqua and solvent need through anhydrous hydride drying treatment.
5. the method for synthesizing sulphonation polyetheretherketonefor for proton exchange membrane by three-step process according to claim 1, it is characterized in that the monomeric preparation method of described sulfonation difluoro benzophenone is: with mol ratio be 1: 1.5～1: 34,4 '-difluoro benzophenone or 4,4 '-difluoro, three benzophenones are with after oleum mixes, under 100 ℃～120 ℃ temperature, stirring reaction 8～10 hours, reaction finish postcooling to room temperature; Pour reaction solution in ice-water bath termination reaction, cooling back regulator solution pH value is 7～8, through the NaCl solid saltout, filter, drying, obtain the sulfonation crude product; This sulfonation crude product is dissolved in the deionized water, is mixed with saturated solution, add ethanol or methyl alcohol again, present a large amount of white flosss to solution, suction filtration was in 80 ℃～100 ℃ following vacuum-dryings 12～24 hours, get white needle-like crystals, be sulfonation difluoro benzophenone.
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