CN104151553A - Poly(aromatic (thio)ether sulfone material containing phosphonate group and preparation method and application of poly(aromatic (sulfide)ether sulfone material - Google Patents
Poly(aromatic (thio)ether sulfone material containing phosphonate group and preparation method and application of poly(aromatic (sulfide)ether sulfone material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a poly(aromatic (thio)ether sulfone material containing a phosphonate group. The preparation method comprises the following steps of mixing a monomer containing the phosphonate group and a bis(thio)phenol monomer (or two different bis(thio)phenol monomers) with a dihalide monomer at a certain ratio; in the presence of medium alkali, strong alkali and toluene, under the condition of heating to a certain temperature and in a high-boiling-point non-protonic solvent, firstly carrying out reflux and water diversion for a certain time and then evaporating toluene out, raising the reaction temperature and continuing the reaction for a certain time; after the reaction is completed, pouring the reaction liquid into deionized water, washing the obtained solids with deionized water for three times and carrying out vacuum drying to obtain a novel polymer containing the phosphonate group. The novel polymer containing the phosphonate group is hydrolyzed and neutralized to obtain a polymer containing a phosphonic acid or phosphate group and good nanofiltration/reverse osmosis desalination and proton conductive performances are achieved.
Description
Application obtains the subsidy of Tianjin State Scientific and Technological Commission science and technology support main project (contract number is: 12ZCDZSF07000) and national " 863 " project (project number is: 2012AA03A601).
Technical field
The invention belongs to technical field of polymer materials; relate to nanofiltration, reverse osmosis membrane water treatment and fuel cells applications field of material preparation; be particularly related to synthetic phosphono polyarylether family macromolecule polymkeric substance and preparation method thereof; and the associated novel high polymer material that contains phosphonic acid ester, phosphonic acids, phosphonate groups, and high efficiency preparation method.
Background technology
Fuel cell, as a kind of energy technology, has the advantages such as energy security, supply security and environmental friendliness.Proton exchange membrane is the core component of fuel cell, and efficiently the proton exchange membrane in fuel cell has following characteristics: good mechanical property under high proton conductivity, low electron conductivity, fuel and oxygenant low permeability, low water conductivity, oxidation and stability to hydrolysis, dry/wet condition, can be used for making film battery assembly device and low cost.The Nafion film that DuPont company of the U.S. produces is the proton exchange membrane product of current main flow, have that chemical stability is good, the advantage such as high proton conductivity under high humidity, but also exist expensive, low humidity to bend down the deadly defect such as low mechanical strength under proton-conducting and high temperature.Seek high proton conductivity and resistant to elevated temperatures novel proton exchange membranes material under cheap, low humidity and become one of research direction of fuel cell sciemtifec and technical sphere forefront.
What report was more at present is that sulfonic acid group is incorporated in macromolecular material, sulfonated polyether sulfone film have certain wetting ability, high proton conductivity and optionally ion by effect, but because the conductivity of sulfonated polyether sulfone film intermediate ion is taking water as relying on, when this has just limited taking sulfonated polyether sulfone as proton exchange membrane, service temperature can not too high (100 DEG C).In the application of fuel cell, find that the higher advantage of service temperature is more, temperature is higher, and the resistance to CO ability of Pt electrode is higher, and efficiency is higher, and thermal treatment is more convenient during than low temperature.Therefore, under dry/wet condition, all there is fine conductive novel film materials and become study hotspot.The composite membrane of benzoglyoxaline family macromolecule and phosphoric acid is because its good heat resistance and proton conductivity height are the material systems of current most study, but the shortcoming of this system maximum is that phosphoric acid easily runs off in water, causes operation very unstable.The strongest method that overcomes this defect is exactly to utilize covalent linkage that phosphate group is incorporated into the appropriate location in polymer.Based on this point, the macromolecular compound of phosphoric acid group has attracted research worker's concern, and this family macromolecule compound is high temperature resistant, and antioxidant property is good, under high temperature and dry/wet condition, all have good proton-conducting, low water-absorbent can reduce the swelling of film.Although the candidate material of great use of proton exchange membrane when the polymkeric substance of phosphono is fuel cell high-temperature operation is because the polymkeric substance of the synthetic high phosphono with high conduction performance is more difficult, also relatively less for the research of this type of polymer materials.At present the method for synthetic this base polymer mainly contains two kinds: a kind of is that the polymkeric substance of bromination or lithiumation carries out modification, and this method has obtained reasonable result, but phosphono degree is wayward, macromolecular chain easy fracture in phosphine acylation process; Another kind method is that the monomer that contains phosphonyl group and other suitable monomer are carried out to direct polymerization, but phosphate group is generally positioned on the monomer that the electron density such as aliphatic chain or diphenol is large, and polymericular weight is on the low side.
At present, the nanofiltration of the marketization, reverse osmosis membrane product are mainly based on cellulose acetate and aromatic polyamides.But cellulose acetate membrane is subject to the attack of microorganism, yielding under high temperature or condition of high voltage, and be only suitable for narrower potential of hydrogen (pH) scope; Aromatic polyamides composite membrane is exposed to oxygenant as free chlorine to continuing, and demonstrates quite weak resistibility, has therefore increased the technique of water treatment procedure, has also improved the cost of clean water treatment.Novel high molecular polymer containing phosphonyl group not only has good proton-conducting, and there is higher thermal and chemical stability, especially within the scope of wider pH, there is superpower chlorine resistance energy, be therefore also expected to become novel nanofiltration, reverse osmosis water processing mould material.
Summary of the invention
Difficulty based on existing in Proton Exchange Membrane Fuel Cells field above and the new opportunity occurring in nanofiltration and reverse osmosis membrane water treatment field, content of the present invention is intended to first synthesize a series of novel poly aromatic (sulphur) ether sulfone materials containing phosphonate groups, acidified and the neutralizing treatment of polymkeric substance, obtain respectively the novel high polymer material that contains phosphonyl group and phosphonate groups, and be applied in Proton Exchange Membrane Fuel Cells field and membrane for water treatment material.
The invention discloses for achieving the above object following technology contents:
1. novel poly aromatic (sulphur) the ether sulfone material that contains phosphonate groups, its structure is as shown in formula I or (II):
（Ⅰ）
Wherein, (I) R=C
1-3alkyl; Y=oxygen or sulphur; 0<m≤1,0≤n<1, and m+n=1;
（Ⅱ）
Wherein, (II) R=C
1-3alkyl; Y=oxygen or sulphur; 0<m, n, q, r<1, m+q=n+r, and m+q+n+r=1; Ar
1and Ar
3with Ar in formula I
1, but different; Ar
2with Ar in formula I
2.
The present invention further discloses the preparation method who contains phosphonate groups polymkeric substance (I) (II), it is characterized in that being undertaken by following step:
(1) by the monomer that contains phosphonate groups and two (sulphur) phenol monomer HY-Ar
1-YH(or two kind of two (sulphur) phenol monomer HY-Ar
1-YH and HY-Ar
3the mixture of-YH) and dihalide monomer X-Ar
2-X mixes by a certain percentage; Wherein contain monomer and the X-Ar of phosphonate groups
2the mole number sum a of-X equals HY-Ar
1the mole number of-YH or HY-Ar
1-YH and HY-Ar
3the mole number sum b of-YH, i.e. a:b=1:1;
The described monomer that contains phosphonate groups is 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone or 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-dichloro diphenyl sulfone;
(2) under the existence of middle highly basic and toluene, in high boiling point aprotic solvent, be heated under certain temperature, first reflux water-dividing certain hour, then steams toluene, improves temperature of reaction, continues reaction certain hour;
(3) after completion of the reaction,, by reaction solution impouring deionized water, the solid obtaining is used deionized water wash three times again, obtains polymkeric substance I or II through vacuum-drying;
Wherein HY-Ar
1-YH and HY-Ar
3the representative compound that-YH represents is as follows:
Wherein X-Ar
2the representative compound that-X represents is as follows:
In preparation method of the present invention, middle highly basic is wherein sodium carbonate, salt of wormwood, cesium carbonate or potassiumphosphate.
In preparation method of the present invention, high boiling point aprotic solvent is wherein methyl-sulphoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
In preparation method of the present invention, wherein dividing water temp is 130-160 DEG C, and point water time is 4-16 hour.
In preparation method of the present invention, wherein improve temperature of reaction to 160-190 DEG C, the reaction times is 12-48 hour.
The present invention further discloses and contain phosphonate groups new polymers in the application of preparing aspect Proton Exchange Membrane Fuel Cells and nanofiltration, reverse osmosis membrane for water treatment, experimental result shows:
(1), at 25 DEG C, under the test condition of relative humidity 100%, high molecular polymer has good proton conductivity for fuel battery proton exchange film material.
(2) at 25 DEG C, 2000 ppm sodium chloride solutions, flow velocity 3.0 L min
-1, under the test condition of pressure 400 psi, high molecular polymer is processed mould material for nanofiltration, reverse osmosis water and is had good desalination rate and water flux.
Brief description of the drawings:
Fig. 1 is the structural formula of novel poly aromatic (sulphur) the ether sulfone material that contains phosphonate groups.
Embodiment
For simple and object clearly, below appropriate omission the description of known technology, in order to avoid unnecessary details affects the description to the technical program.Below in conjunction with comparative example, the present invention is described further.Hydrogen 1 nuclear magnetic resonance spectrum (
1h-NMR), phosphorus 31 nuclear magnetic resonance spectrums (
31p-NMR) all at deuterated dimethyl sulfoxide (DMSO-
d 6) in record.Wherein 4,4
,-difluorodiphenyl sulfone, 4,4
,-dichloro diphenyl sulfone, N-bromo-succinimide, triethyl-phosphite, '-biphenyl diphenol, dihydroxyphenyl propane, two (4-fluorophenyl) phenyl phosphine oxide, two (4-hydroxy phenyl) phenyl phosphine oxide, 4-(4-sulfydryl thiophenyl) raw material such as thiophenol, Binaphthol, salt of wormwood all has commercially available.
Embodiment 1:
3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,the preparation of-difluorodiphenyl sulfone:
(1) 3,3
,-bis-bromo-4,4
,the preparation of-difluorodiphenyl sulfone:
In 250 mL there-necked flasks, add 4,4
,-difluorodiphenyl sulfone 25.4 g(0.1 mol), the 150 mL vitriol oils, mechanical stirring is dissolved, and adds N-bromo-succinimide 39.2 g(0.22 mol in batches), room temperature reaction spends the night, reaction solution is poured in frozen water, separate out solid, filter, washing, toluene recrystallization obtains white crystal 30 g, productive rate 73%.
1H-NMR?(DMSO-
d 6 ):?δ?=?8.46-8.44?(m,?2?H),?8.15-8.11?(m,?2?H),?7.65?(t,?
J?=?8.8?Hz,?2?H)?ppm。
(2) 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,the preparation of-difluorodiphenyl sulfone:
By 3,3
,-bis-bromo-4,4
,-difluorodiphenyl sulfone and triethyl-phosphite feed intake according to the ratio of 1:8.0, N
2protection, 100 DEG C of temperature of reaction, react under illumination condition.TLC monitors, and reaction 30 h disappear to raw material point.Product is carried out to underpressure distillation, and oil bath temperature to 100 DEG C, steams low boiler cut.Residuum column chromatography (V
sherwood oil/ V
ethyl acetate=1:2), obtain yellow oily liquid product, productive rate 83%.
1H-NMR?(CDCl
3):?δ?=?8.42-8.38?(m,?2?H),?8.22-8.16?(m,?2?H),?7.36-7.28?(m,?2?H),?4.28-4.18?(m,?8?H),?1.36?(t,?
J?=?7.2?Hz,?12?H)?ppm;
?31P-NMR?(CDCl
3):?δ?=?9.95?ppm。
Embodiment 2:
3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,the preparation of-dichloro diphenyl sulfone:
(1) 3,3
,-bis-bromo-4,4
,the preparation of-dichloro diphenyl sulfone:
In 250 mL there-necked flasks, add 4,4
,-dichloro diphenyl sulfone 28.7 g(0.1 mol), the 150 mL vitriol oils, mechanical stirring is dissolved, and adds N-bromo-succinimide 39.2 g(0.22 mol in batches), room temperature reaction spends the night, reaction solution is poured in frozen water, separate out solid, filter, washing, toluene recrystallization obtains white crystal 36 g, productive rate 81%.
1H-NMR?(DMSO-
d 6 ):?δ?=?8.45-8.43?(m,?2?H),?8.06-8.04?(m,?2?H),?7.88?(t,?
J?=?8.4?Hz,?2?H)?ppm。
(2) 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,the preparation of-dichloro diphenyl sulfone:
By 3,3
,-bis-bromo-4,4
,-dichloro diphenyl sulfone and triethyl-phosphite feed intake according to the ratio of 1:8.0, N
2protection, 100 DEG C of temperature of reaction, react under illumination condition.TLC monitors, and reaction 30 h disappear to raw material point.Product is carried out to underpressure distillation, and oil bath temperature to 100 DEG C, steams low boiler cut.Residuum column chromatography (V
sherwood oil/ V
ethyl acetate=1:2), obtain yellow oily liquid product, productive rate 82%.
1H-NMR?(CDCl
3):?δ?=?8.51-8.47?(m,?2?H),?8.06-8.04?(m,?2?H),?7.65-7.62?(m,?2?H),?4.27-4.18?(m,?8?H),?1.39?(t,?
J?=?7.2?Hz,?12?H)?ppm;
?31P-NMR?(CDCl
3):?δ?=?11.06?ppm。
Embodiment 3:
The preparation of phosphonate polymer (I-1):
（Ⅰ-1）
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), '-biphenyl diphenol (3.72 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N,N-dimethylacetamide (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, point water 4 hours, steams toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 11.22 g 100 DEG C of vacuum-dryings again, productive rate 95%, intrinsic viscosity 0.54 dL/g.
Embodiment 4:
The preparation of phosphonate polymer (I-1):
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-dichloro diphenyl sulfone (7.83 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), '-biphenyl diphenol (3.72 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N,N-dimethylacetamide (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, point water 4 hours, steams toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 11.34 g 100 DEG C of vacuum-dryings again, productive rate 96%, intrinsic viscosity 0.53 dL/g.
Embodiment 5:
The preparation of phosphonate polymer (I-1):
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), '-biphenyl diphenol (3.72 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N-Methyl pyrrolidone (NMP, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, divide water 4 hours, steam toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 11.10 g 100 DEG C of vacuum-dryings again, productive rate 94%, intrinsic viscosity 0.52 dL/g.
Embodiment 6:
The preparation of phosphonate polymer (I-2):
（Ⅰ-2）
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), dihydroxyphenyl propane (4.57 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N,N-dimethylacetamide (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, point water 4 hours, steams toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 12.16 g 100 DEG C of vacuum-dryings again, productive rate 96%, intrinsic viscosity 0.50 dL/g.
Embodiment 7:
The preparation of phosphonate polymer (I-3):
（Ⅰ-3）
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), two (4-fluorophenyl) phenyl phosphine oxide (1.88 g, 6.0 mmol), two (4-hydroxy phenyl) phenyl phosphine oxide (6.21 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N, N-N,N-DIMETHYLACETAMIDE (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, divide water 4 hours, steam toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 14.37 g 100 DEG C of vacuum-dryings again, productive rate 98%, intrinsic viscosity 0.56 dL/g.
Embodiment 8:
The preparation of phosphonate polymer (I-4):
（Ⅰ-4）
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), 4-(4-sulfydryl thiophenyl) thiophenol (5.01 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N,N-dimethylacetamide (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, point water 4 hours, steams toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 12.31 g 100 DEG C of vacuum-dryings again, productive rate 94%, intrinsic viscosity 0.49 dL/g.
Embodiment 9:
The preparation of phosphonate polymer (I-5):
（Ⅰ-5）
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), Binaphthol (5.73 g, 20.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N,N-dimethylacetamide (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, point water 4 hours, steams toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 12.99 g 100 DEG C of vacuum-dryings again, productive rate 94%, intrinsic viscosity 0.42 dL/g.
Embodiment 10:
The preparation of phosphonate polymer (II-1):
（Ⅱ-1）
Under nitrogen atmosphere, by 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone (7.37 g, 14.0 mmol), 4,4
.-dichloro diphenyl sulfone (1.72 g, 6.0 mmol), '-biphenyl diphenol (1.86 g, 10.0 mmol), dihydroxyphenyl propane (2.28 g, 10.0 mmol), Anhydrous potassium carbonate (3.18 g, 23.0 mmol), N,N-dimethylacetamide (DMAc, 56 mL), toluene (28 mL) Hybrid Heating to 160 DEG C, point water 4 hours, steams toluene, be warming up to 180 DEG C, react 36 hours.Reaction solution is slowly poured in 400 mL deionized waters, obtained white bars shaped polymer, change water, 80 DEG C of constant temperature, poach three times, each 6 hours, dries, after 24 hours, obtain white fiber shaped polymer 11.86 g 100 DEG C of vacuum-dryings again, productive rate 97%, intrinsic viscosity 0.51 dL/g.
Embodiment 11:
Proton exchange membrane performance test:
Getting fibrous polymer (I-1) prepared by embodiment 3 is dissolved in dimethyl sulfoxide (DMSO), add 6 M hydrochloric acid (volume ratio of dimethyl sulfoxide (DMSO) and hydrochloric acid is 4:1), heating reflux reaction 12 hours, by in reaction solution impouring deionized water, the solid obtaining is used deionized water wash three times again, vacuum-drying, obtains faint yellow solid.Get appropriate this solid and be dissolved in DMAc, make the solution that concentration is 5wt%, filter, drive away after bubble, water on clean sheet glass, under 25 DEG C of normal pressures of constant temperature, be dried 24 hours, then in the vacuum drying oven of 120 DEG C of constant temperature, be dried 48 hours, obtain flat sheet membrane.25 DEG C, relative humidity 100%, proton conductivity 0.056 S/cm.
Embodiment 12:
Proton exchange membrane performance test:
Getting fibrous polymer (II-1) prepared by embodiment 10 is dissolved in dimethyl sulfoxide (DMSO), add 6 M hydrochloric acid (volume ratio of dimethyl sulfoxide (DMSO) and hydrochloric acid is 4:1), heating reflux reaction 12 hours, by in reaction solution impouring deionized water, the solid obtaining is used deionized water wash three times again, vacuum-drying, obtains faint yellow solid.Get appropriate this solid and be dissolved in DMAc, make the solution that concentration is 5wt%, filter, drive away after bubble, water on clean sheet glass, under 25 DEG C of normal pressures of constant temperature, be dried 24 hours, then in the vacuum drying oven of 120 DEG C of constant temperature, be dried 48 hours, obtain flat sheet membrane.25 DEG C, relative humidity 100%, proton conductivity 0.052 S/cm.
Embodiment 13:
Reverse osmosis membrane performance test:
Getting fibrous polymer (I-1) prepared by embodiment 3 is dissolved in dimethyl sulfoxide (DMSO), add 6 M hydrochloric acid (volume ratio of dimethyl sulfoxide (DMSO) and hydrochloric acid is 4:1), heating reflux reaction 12 hours, by in reaction solution impouring deionized water, the solid obtaining is used deionized water wash three times again, then in 0.5 M aqueous sodium hydroxide solution soaking at room temperature 6 hours, the solid obtaining deionized water wash three times, filter, vacuum-drying, obtains faint yellow solid.Get this solid and be dissolved in right amount in DMAc, make the solution that concentration is 5wt%, filter, drive away after bubble, water on clean sheet glass, under 25 DEG C of normal pressures of constant temperature, be dried 24 hours, then in the vacuum drying oven of 120 DEG C of constant temperature, be dried 48 hours, obtain flat sheet membrane.Test condition: 25 DEG C, 2000 ppm sodium chloride solutions, flow velocity 3.0 L min
-1, pressure 400 psi.Test result: desalination rate 93%, water flux 1.6 L μ m m
-2h
-1bar
-1.
Embodiment 14:
Reverse osmosis membrane performance test:
Getting fibrous polymer (II-1) prepared by embodiment 10 is dissolved in dimethyl sulfoxide (DMSO), add 6 M hydrochloric acid (volume ratio of dimethyl sulfoxide (DMSO) and hydrochloric acid is 4:1), heating reflux reaction 12 hours, by in reaction solution impouring deionized water, the solid obtaining is used deionized water wash three times again, then in 0.5 M aqueous sodium hydroxide solution soaking at room temperature 6 hours, the solid obtaining deionized water wash three times, filter, vacuum-drying, obtains faint yellow solid.Get this solid and be dissolved in right amount in DMAc, make the solution that concentration is 5wt%, filter, drive away after bubble, water on clean sheet glass, under 25 DEG C of normal pressures of constant temperature, be dried 24 hours, then in the vacuum drying oven of 120 DEG C of constant temperature, be dried 48 hours, obtain flat sheet membrane.Test condition: 25 DEG C, 2000 ppm sodium chloride solutions, flow velocity 3.0 L min
-1, pressure 400 psi.Test result: desalination rate 94%, water flux 1.5 L μ m m
-2h
-1bar
-1.
After the preferred embodiment describing in detail, being familiar with this technology personage can be well understood to, can carry out various variations and amendment not departing under above-mentioned claim and spirit, any simple modification, equivalent variations and modification that all foundations technical spirit of the present invention is done above embodiment, all belong to the scope of technical solution of the present invention.And the present invention is not also subject to the restriction of example embodiment in specification sheets.
Claims (7)
1. novel poly aromatic (sulphur) the ether sulfone material that contains phosphonate groups, its structure is as shown in formula I or (II):
（Ⅰ）
Wherein, (I) R=C
1-3alkyl; Y=oxygen or sulphur; 0<m≤1,0≤n<1, and m+n=1;
（Ⅱ）
Wherein, (II) R=C
1-3alkyl; Y=oxygen or sulphur; 0<m, n, q, r<1, m+q=n+r, and m+q+n+r=1; Ar
1and Ar
3with Ar in formula I
1, but different; Ar
2with Ar in formula I
2.
2. described in claim 1, contain the preparation method of phosphonate groups polymkeric substance (I) or (II), it is characterized in that being undertaken by following step:
(1) by the monomer that contains phosphonate groups and two (sulphur) phenol monomer HY-Ar
1-YH(or two kind of two (sulphur) phenol monomer HY-Ar
1-YH and HY-Ar
3the mixture of-YH) and dihalide monomer X-Ar
2-X mixes by a certain percentage; Wherein contain monomer and the X-Ar of phosphonate groups
2the mole number sum a of-X equals HY-Ar
1the mole number of-YH or HY-Ar
1-YH and HY-Ar
3the mole number sum b of-YH, i.e. a:b=1:1;
The described monomer that contains phosphonate groups is 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-difluorodiphenyl sulfone or 3,3
,-bis-(diethoxy phosphonium mesitoyl bases)-4,4
,-dichloro diphenyl sulfone;
(2) under the existence of middle highly basic and toluene, in high boiling point aprotic solvent, be heated under certain temperature, first reflux water-dividing certain hour, then steams toluene, improves temperature of reaction, continues reaction certain hour;
(3) after completion of the reaction,, by reaction solution impouring deionized water, the solid obtaining is used deionized water wash three times again, obtains polymkeric substance I or II through vacuum-drying;
Wherein HY-Ar
1-YH and HY-Ar
3the representative compound that-YH represents is as follows:
Wherein X-Ar
2the representative compound that-X represents is as follows:
。
3. preparation method claimed in claim 2, middle highly basic is wherein sodium carbonate, salt of wormwood, cesium carbonate or potassiumphosphate.
4. preparation method claimed in claim 2, high boiling point aprotic solvent is wherein methyl-sulphoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
5. preparation method claimed in claim 2, wherein dividing water temp is 130-160 DEG C, point water time is 4-16 hour.
6. preparation method claimed in claim 2, wherein improves temperature of reaction to 160-190 DEG C, and the reaction times is 12-48 hour.
7. poly aromatic (sulphur) the ether sulfone material that contains phosphonate groups described in claim 1 is in the application of preparing aspect Proton Exchange Membrane Fuel Cells and nanofiltration, reverse osmosis membrane for water treatment.
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