CN104277216B - A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer and its preparation method and application - Google Patents
A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer and its preparation method and application Download PDFInfo
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- CN104277216B CN104277216B CN201410524122.0A CN201410524122A CN104277216B CN 104277216 B CN104277216 B CN 104277216B CN 201410524122 A CN201410524122 A CN 201410524122A CN 104277216 B CN104277216 B CN 104277216B
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- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer and its preparation method and application, belong to field of fuel cell technology.With different methoxyl group fragrance dihydric phenols and 1,2 dibromotetrafluoroethanes it is raw material in the present invention, prepares the Trifluorovinyl Aryl Ethers monomer containing methoxyl group；The polymerization of (π of 2 π+2) thermal cyclization is utilized, obtains the perfluorocyclobutanearyl polyarylether polymer containing methoxyl group；Itself and Boron tribromide are acted on, protection ylmethyl is removed, prepares the perfluorocyclobutanearyl polyarylether polymer with different hydroxy radical contents；Using the method for grafting, sulfonation side base is introduced, sulfonated perfluorocarbon cyclobutyl polyarylether polymer is obtained, for preparing PEM.The weightless temperature for the sulfonated perfluorocarbon cyclobutyl polyarylether polymer 5% that the present invention obtains can be to more than 217 DEG C；With low water absorption rate, swelling ratio；Proton conductivity is high, can be as the proton exchange membrane material of fuel cell.
Description
Technical field
The invention belongs to polymer chemistry and Proton Exchange Membrane Fuel Cells field, more particularly to a kind of sulfonated perfluorocarbon ring fourth
Base polyarylether polymer and its preparation method and application.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has high power density, energy conversion efficiency, cold-starting, environment
The advantages that friendly, it is with a wide range of applications in fields such as Aero-Space, military affairs, mobile communication equipment and communications and transportation.Matter
Proton exchange (PEM) is the core component in PEMFC, and it is not merely a kind of diaphragm material, but also be electrolyte and
The substrate of elctro-catalyst, while and can completes the transmission of proton as proton carrier.At present, it is relatively broad for commercial applications
It is that E.I.Du Pont Company producesBut because its relative price is higher, methanol permeability is high and proton conducts in high temperature
The shortcomings of rate is greatly lowered, limit further applying for it.Closely during the last ten years, many new PEM materials are developed,
Wherein be mainly sulfonated aromatic type polymer, such as sulfonated polyether sulphone, sulfonated poly aryl ether ketone, sulfonated polyimide.To sulphur
In the research for changing aroma type polymer, due to being easier to introduce sulfonic group on the aromatic rings of aroma type polymer, so at present
Most research all concentrates on exploitation backbone chain type sulfonated polymer, i.e. sulfonic group is connected directly between on main polymer chain.It is this kind of
Polymer generally requires higher ion exchange capacity (IEC) to reach high proton conductivity, and higher IEC is typically resulted in
The water absorption rate increase of film, then occurs excessively swelling, the dimensional stability of film is deteriorated, the final mechanical performance for destroying film, film
Original performance will be lost, this is the common problem of traditional sulfonation hydrocarbon polymer proton PEM materials.Therefore, how to solve PEM
When with higher proton conductivity be swelled excessively, poor dimensional stability the problem of seem very necessary, this is also to open at present
It is badly in need of the problem solved in hair high performance PE M materials process.
Research is found, by the way that sulfonic acid group to be connected to the end of side chain, prepares sulfonation side chain type aromatic polymer, may
Be solve membrane swelling excessively, a kind of effective ways of poor dimensional stability.Although the sulfonation side chain type fragrance reported at present is poly-
Compound film increases in terms of dimensional stability, but proton conductivity is generally relatively low.One possessed by series membranes
A little excellent properties, it is mainly due to its special structure：The flexibility of polytetrafluoroethylene (PTFE) skeleton and highly acid with strong-hydrophobicity
Side chain, aqueous favoring/hydrophobic phase separation is clearly in its Microphase Structure；More hold in addition, sulfonic group is located on flexible side-chains end
Easily motion, is so advantageous to migration of the proton between sulfonic acid group, so as to improve proton conductivity.It is therefore believed that from
MOLECULE DESIGN angle, design is with the sulfonation side-chain polymer material similar to Nafion structures, it may be possible to solves above-mentioned ask
The effective ways of topic.To realize this imagination, it is necessary first to select a suitable main polymer chain with carbon fluorine structure.
Closely during the last ten years, there is researcher always all in a kind of partially fluorinated polymerization for containing perfluorocyclobutanearyl (PFCB) of research and development
Thing.The compound of birdsing of the same feather flock together containing PFCB is usually that aryl trifluoro vinyl ether reacts to obtain by (π of 2 π+2) hot cyclopolymerization.This thermal initiation
Step-growth polymerization, it is not necessary to any catalyst or initiator, and condensation product will not be produced.Furthermore, it is possible to simply lead to
Cross and remove thermal source to control polymerisation, so as to be easier to obtain the polymer of various different molecular weights.
Based on this, the present invention is from MOLECULE DESIGN angle, and design synthesis is based on perfluorocyclobutanearyl aryl-ether polymer
The new polymers of chain, the flexible side-chains containing sulfonation, and this kind of proton exchange polymer membrane and preparation method are provided.
The content of the invention
To overcome shortcoming and deficiency present in prior art, primary and foremost purpose of the invention is to provide a kind of sulfonated perfluorocarbon
Cyclobutyl polyarylether polymer.
Another object of the present invention is to provide the preparation method of above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer.
Another object of the present invention is to provide a kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM.
Another object of the present invention is to provide the system of above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM
Preparation Method.
It is still another object of the present invention to provide answering for above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM
With.
The purpose of the present invention passes through following technical proposals：A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer, its specific knot
Structure formula is as shown in formula I：
Wherein：0≤m≤1,0≤n≤1, and m+n=1；Ar includes the structure shown in formula II：
The preparation method of above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer, including following preparation process：
(1) with different methoxyl group fragrance dihydric phenol and 1,2- dibromotetrafluoroethane for raw material, prepare and a series of contain methoxy
The new Trifluorovinyl Aryl Ethers monomer of base；
(2) (π of 2 π+2) thermal cyclization polymerization of Trifluorovinyl Aryl Ethers monomer described in (1) is utilized, containing the complete of methoxyl group
Fluorine cyclobutyl polyarylether polymer PFCB-OMe；
(3) PFCB-OMe acts on Boron tribromide, removes protection ylmethyl, prepares the perfluor ring with different hydroxy radical contents
(x refers to demethyl degree to butyl polyarylether polymer PFCB-OH-x, if demethyl degree is 50%, x=50；0<x≤100).
(4) using the method for grafting, sulfonation side base is introduced, obtains sulfonated perfluorocarbon cyclobutyl polyarylether polymer S-PFCB-
x。
The preparation method of above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer, specifically includes following preparation process：
1) preparation of intermediate compound 1：
7.0g 5- methoxyl group resorcinols are taken to be added in 200mL dimethyl sulfoxides, stirring makes 5- methoxyl group resorcinols
Dissolving；After depressurizing 30min with oil pump, with nitrogen into solution bubbling 30min to remove the oxygen in solution；Protected in nitrogen
Under, add 48.9g cesium carbonates；With nitrogen after bubbling 30min, 38.9g 1,2- dibromotetrafluoroethanes are added into solution；Heating
To 50 DEG C, stir 2 days；Stop heating, reactant mixture is transferred in 1L beaker, after system is cooled to room temperature, add
200mL water, 10min is stirred, then add 100mL dichloromethane, separate organic phase, organic phase is washed 3 times, uses water every time
50mL；Merge aqueous phase, with n-hexane extraction 3 times, use n-hexane 50mL every time；Merge organic phase, dried with anhydrous magnesium sulfate；Take out
Filter, solvent is removed with Rotary Evaporators；Remaining liquid carries out separating-purifying with column chromatography, obtains 15.1g colourless transparent liquids
Intermediate compound 1；
2) preparation of intermediate compound 2：
Reflux condensing tube is filled in 250mL three neck round bottom, is added in 1.56g zinc granules, the acquisition of 4.98g steps 1)
Between the acetonitrile that newly steams of compound 1 and 100mL, heating reflux reaction 24h；Stop heating, room temperature cooling and standings 1h；The salt of generation sinks
Form sediment in three-necked bottle bottom, pour out supernatant liquor；Remaining mixture adds washing, with n-hexane extraction 3 times, uses n-hexane every time
30mL, organic phase are dried with anhydrous magnesium sulfate；Merge organic phase, solvent, remaining liquid column chromatography are removed with rotary evaporation
Separating-purifying is carried out, obtains 2.13g colourless transparent liquids intermediate compound 2；
3) preparation of the perfluorocyclobutanearyl polyarylether polymer (PFCB-OMe) containing methoxyl group：
The intermediate compound 2 that 3g steps 2) obtain is added in dry 50mL three neck round bottom, is put into liquid nitrogen frozen,
10min is evacuated, inflated with nitrogen thaws；After circulation three times, 180 DEG C of oil bath heating 12h are put into, then heat to 190 DEG C of heating 24h；
After room temperature cooling, gained solid 30mL chloroforms dissolve, and then add 60mL n-hexanes, filtering, filter cake is in 60 DEG C of vacuum drying
12h, obtain 2.85g solid white polymers PFCB-OMe；
4) preparation of the perfluorocyclobutanearyl polyarylether polymer (PFCB-OH-x) of hydroxyl：
The necks of 250mL tri- that the polymer P FCB-OMe that 3.20g steps 3) obtain is put into the drying equipped with dropping funel are justified
In the flask of bottom, the dissolving of 100mL dichloromethane is added, the 50mL dichloromethane of the Boron tribromide containing 0.13mL is added in dropping funel
Solution；Reaction bulb is put into ice-water bath, Boron tribromide solution is slowly added dropwise, stirs 0.5h after being added dropwise in ice-water bath
Afterwards, 6h is stirred at room temperature；Add 1mL ethanol and reaction, gained mixture room temperature cooling and standings 1h is quenched；Filtering, 3 are washed with dichloromethane
It is secondary, 10mL dichloromethane is used every time；Filter cake is dried in vacuo 12h at 60 DEG C, obtains solid white polymer PFCB-OH-x；
5) preparation of sulfonation 4- fluorine benzophenone
After 10g 4- fluorine benzophenone and 16mL30% oleum are well mixed, 20h are heated at 110 DEG C；Gained
Mixture is cooled to room temperature, is subsequently poured into 120mL frozen water, adds 56gNaCl and obtains white precipitate；Filtering, white is solid
Body is re-dissolved in 120mL water, and resulting solution pH value is adjusted into 6~7 with 2NNaOH；Excessive NaCl is added, obtains white
Precipitation, filtering, filter cake are dried in vacuo 24h at 100 DEG C, obtain white solid；It is 7 with volume ratio:3 first alcohol and water recrystallization, mistake
Filter, filter cake are dried in vacuo 24h at 100 DEG C, obtain 16g white powder sulfonation 4- fluorine benzophenone；
6) preparation of sulfonated perfluorocarbon cyclobutyl polyarylether polymer (S-PFCB-x)
The PFCB- that 3.12g step 4) obtains is added in a three neck round bottom equipped with Dean-Stark water knockout drums
The sulfonation 4- fluorine benzophenone that OH-50,0.081g step 5) obtain, 0.021g Anhydrous potassium carbonate, 20mL dimethylacetamides
Amine and 10mL toluene, with nitrogen bubble, remove the oxygen in mixture；Gained mixture 145 DEG C flow back 24h, then steam
Toluene；Gained residue is heated to 170 DEG C, reacts 20h；Under vigorous stirring, gained mixture is slowly poured into excessive
In 5wt% hydrochloric acid, filtering, it is washed with water, gained solid dries 24h in 100 DEG C of vacuum drying ovens, obtains sulfonated perfluorocarbon cyclobutyl
Polyarylether polymer.
A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM, is gathered by the sulfonated perfluorocarbon cyclobutyl of above-mentioned acquisition
Aryl oxide polymer is prepared.
The preparation method of above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM, is concretely comprised the following steps：
The above-mentioned sulfonated perfluorocarbon cyclobutyl polyarylether polymer prepared is dissolved in dimethyl acetamide (DMAc),
7wt% solution is made into, resulting solution is filtered with 0.45 μm of PTFE filtering head, in culture dish casting film-forming, in 80 DEG C of dryings
24h, 18h then is dried in vacuo at 100 DEG C, after being cooled to room temperature, is stripped in deionized water, film is placed in 2M sulfuric acid
Proton exchange 24h is carried out, then is washed repeatedly until pH=6~7 with deionized water, obtains the polymerization of sulfonated perfluorocarbon cyclobutyl polyarylether
Proton exchange membrane.
The sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM of above-mentioned acquisition is applied in fuel cell.
With methoxyl group fragrance dihydric phenol and 1,2- dibromotetrafluoroethane raw material in the present invention, new trifluoro vinyl virtue is prepared
Base ether monomer；It is polymerize using (π of 2 π+2) thermal cyclization of above-mentioned monomer, prepares the perfluor ring containing methoxyl group with different molecular weight
Butyl polyarylether polymer PFCB-OMe；Deprotection reaction, i.e. PFCB-Me and Boron tribromide (BBr3) effect, preparing has not
With the perfluorocyclobutanearyl polyarylether (PFCB-OH-x) of hydroxy radical content；PFCB-OH-x acts on sulfonation 4- fluorine benzophenone, obtains
The polymer of different sulfonation degrees, i.e., sulfonated perfluorocarbon cyclobutyl polyarylether polymer S-PFCB-x of the present invention.It is all new
The structure of micromolecular compound is confirmed through nuclear magnetic resonance, elementary analysis, mass spectrum.PFCB-OMe, PFCB-OH-x structure warp
Nuclear magnetic resonance and gel chromatography are confirmed, and partial results are shown in specific embodiment part.Have studied S-PFCB-x thermostabilization and
Proton conduction property.
The present invention is had the following advantages relative to prior art and effect：
The present invention from MOLECULE DESIGN aspect, have selected the dihydric phenol of fragrance containing methoxyl group, 1,2- dibromotetrafluoroethanes and
4- fluorine benzophenone is main initial feed, utilizes the typical itineraries of perfluorocyclobutanearyl aryl-ether Macroscopic single crystal and the side of grafting
Method, it is prepared for the regulatable sulfonated perfluorocarbon cyclobutyl polyarylether polymer S-PFCB-x of molecule amount and sulfonation degree.With showing
There is technology to compare, preparation method of the invention is simple, and raw material is easy to get, and cost is low.
S-PFCB-x prepared by present invention structure is confirmed through hydrogen nuclear magnetic resonance and fluorine nmr；Thermogravimetric analysis table
Bright, the weightless temperature of such polymer (sour form) 5% can be to more than 217 DEG C；Compared with commercialized Nafion115 films, profit
There is low water absorption rate, swelling ratio with the films prepared of the S-PFCB-x obtained by the present invention；Proton conductivity, which is tested, to be shown, such film
Material at 85 DEG C its proton conductivity up to 0.143S/cm.S-PFCB-x prepared by these as shown by data present invention can conduct
The proton exchange membrane material of fuel cell.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrum of the S-PFCB-50 that step 6) obtains in embodiment 1；
The fluorine nmr spectrum that Fig. 2 is the S-PFCB-50 that step 6) obtains in embodiment 1；
Fig. 3 is that thermogravimetric analysis of the S-PFCB-50 (sour form) of step 6) acquisition in embodiment 1 in air atmosphere is bent
Line；
The water absorption rate curve that Fig. 4 is the S-PFCB-50 films and Nafion115 obtained in embodiment 1；
The swelling ratio curve that Fig. 5 is the S-PFCB-50 films and Nafion115 obtained in embodiment 1；
The proton conductivity curve that Fig. 6 is the S-PFCB-50 films and Nafion115 obtained in embodiment 1.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
By following examples to the present invention it is further appreciated that but not being limitation the scope of the present invention.
1) preparation of intermediate compound 1：
5- methoxyl groups resorcinol (7.0g, 0.05mol) and dimethyl sulfoxide (200mL) are added in 500mL three-necked bottles, is stirred
Mixing dissolves benzenediol；After depressurizing 30min with oil pump, with nitrogen into solution bubbling 30min to remove the oxygen in solution；
Under nitrogen protection, cesium carbonate (48.9g, 0.15mol) is added；With nitrogen after bubbling 30min, 1,2- dibromos four are added into solution
Fluoroethane (38.9g, 0.15mol)；50 DEG C are warming up to, is stirred 2 days；Stop heating, reactant mixture is transferred to 1L beaker
In, after system is cooled to room temperature, water (200mL) is added, stirs 10min, dichloromethane (100mL) is then added, has separated
Machine phase, organic phase are washed with water (50mL × 3)；Merge aqueous phase, with n-hexane extraction (50mL × 3)；Merge organic phase, use is anhydrous
Magnesium sulfate is dried；Filter, solvent is removed with Rotary Evaporators；Remaining liquid carries out separating-purifying (n-hexane) with column chromatography,
Obtain 15.1g colourless transparent liquids (intermediate compound 1), yield 61%.
Intermediate compound 1：1HNMR(400MHz,CDCl3):δ6.71(s,3H),3.82(s,3H).13C NMR(100MHz,
CDCl3):δ161.1,149.8,115.8(tt,–CF2Br),113.4(tt,–OCF2),107.5,106.3,56.0.19F NMR
(376MHz,CDCl3):δ–67.9(t,–OCF2),–86.0(t,–CF2Br).MS(EI):m/z500,498,
496.Anal.Calcd for C11H6Br2F8O3:C, 26.53%；H, 1.21%.Found:C, 26.47%；H, 1.17%.
2) preparation of intermediate compound 2：
Reflux condensing tube is filled in 250mL three neck round bottom, adds zinc granule (1.56g, 0.024mol), compound 1
(4.98g, 0.010mol) and the acetonitrile (100mL) newly steamed, heating reflux reaction 24h；Stop heating, room temperature cooling and standings 1h；
The salt of generation is deposited in three-necked bottle bottom, pours out supernatant liquor.Remaining mixture adds washing, with n-hexane extraction (30mL
× 3), organic phase is dried with anhydrous magnesium sulfate；Merge organic phase, solvent, remaining liquid column chromatography are removed with rotary evaporation
Separating-purifying (n-hexane) is carried out, obtains 2.13g colourless transparent liquids (intermediate compound 2), yield 71%.
Intermediate compound 2：1H NMR(400MHz,CDCl3):δ6.71(s,3H),3.79(s,3H).13C NMR
(100MHz,CDCl3):δ153.4,150.2,136.6,118.9,115.4,110.2,108.1,104.0,56.2.19F NMR
(376MHz,CDCl3):δ -134.1 (dd, 1F), -128.0 (dd, 1F), -120.8 (dd, 1F) .MS (EI):m/z300,
301.Anal.Calcd for C11H6F6O3:C, 44.02%；H, 2.01%.Found:C, 44.03%；H, 2.03%.
3) polymer P FCB-OMe preparation
Compound 2 (3g, 0.01mol) is added in dry 50mL three neck round bottom, is put into liquid nitrogen frozen, is evacuated
10min, inflated with nitrogen thaw；After circulation three times, 180 DEG C of oil bath heating 12h are put into, then heat to 190 DEG C of heating 24h；Room temperature
After cooling, gained solid chloroform (30mL) dissolves, and then adds n-hexane (30mL), filtering, filter cake is in 60 DEG C of vacuum drying
12h, obtain 2.85g solid white polymer PFCB-OMe, yield 95%.
PFCB-OMe：GPC:Mn=26,420g/mol, Mw/Mn=1.21.1H NMR(400MHz,CDCl3):δ6.68(s,
3H),3.76(s,3H).19F NMR(376MHz,CDC13):δ -131.69~128.20 (m, 6F)
4) polymer P FCB-OH-50 preparation
The neck round bottoms of 250mL tri- that compound PFCB-OMe (3.20g, 1mmol) is put into the drying equipped with dropping funel burn
In bottle, the dissolving of 100mL dichloromethane is added, the dichloromethane of Boron tribromide (0.13mL, 0.5mmol) is added in dropping funel
(50mL) solution；Reaction bulb is put into ice-water bath, Boron tribromide solution is slowly added dropwise, is stirred after being added dropwise in ice-water bath
After 0.5h, 6h is stirred at room temperature；Add ethanol (1mL) and reaction, gained mixture room temperature cooling and standings 1h is quenched；Filtering, uses dichloro
Methane is washed (10mL × 3)；Filter cake is dried in vacuo 12h at 60 DEG C, obtains solid white polymer PFCB-OH-50.
PFCB-OH-50：GPC:Mn=22,780g/mol, Mw/Mn=1.37.1H NMR(400MHz,CDCl3):δ6.71,
3.76,5.85.19F NMR(376MHz,CDC13):δ -131.69~128.20 (m, 6F)
5) preparation of sulfonation 4- fluorine benzophenone
After 4- fluorine benzophenone (10g, 0.05mol) and 30% oleum (16mL) are well mixed, add at 110 DEG C
Hot 20h；Gained mixture is cooled to room temperature, is subsequently poured into frozen water (120mL), adds NaCl (56g) and obtains white precipitate；
Filtering, solid is re-dissolved in 120mL water, resulting solution pH value is adjusted into 6~7 with 2NNaOH；Excessive NaCl is added,
White precipitate is obtained, is filtered, filter cake is dried in vacuo 24h at 100 DEG C, obtains white solid；With first alcohol and water (v/v, 7:3) tie again
Crystalline substance, filtering, filter cake are dried in vacuo 24h at 100 DEG C, obtain 16g white powder sulfonation 4- fluorine benzophenone, yield 80%.
Sulfonation 4- fluorine benzophenone：1H NMR(400MHz,CDCl3):δ8.06(s,1H),7.94(s,1H),7.89(t,
1H),7.73(m,1H),7.62(d,1H),7.53(t,1H),7.35(t,1H).
6) S-PFCB-50 preparation
One equipped with Dean-Stark water knockout drums three neck round bottom in add PFCB-OH-50 (3.12g,
0.1mmol), sulfonation 4- fluorine benzophenone (0.081g, 0.2mmol), Anhydrous potassium carbonate (0.021g, 0.15mmol), DMAc
(20mL) and toluene (10mL), with nitrogen bubble, remove the oxygen in mixture；Gained mixture 145 DEG C flow back 24h, so
After steam toluene；Gained residue is heated to 170 DEG C, reacts 20h；Under vigorous stirring, gained mixture was slowly poured into
In the hydrochloric acid (5wt%) of amount, filtering, it is washed with water, gained solid dries 24h in 100 DEG C of vacuum drying ovens, obtains S-PFCB-
50, yield 81%.
S-PFCB-50：1H NMR(400MHz,DMSO-d6):δ6.5-8.5(m,10H).7.8919F NMR(376MHz,
CDC13):δ -133.3~125.7 (m, 6F)
7) preparation of sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM
S-PFCB-50 is dissolved in dimethyl acetamide (DMAc), is made into 7wt% solution, 0.45 μ of resulting solution
M PTFE filtering heads are filtered, and in culture dish casting film-forming, in 80 DEG C of dry 24h, 18h is then dried in vacuo at 100 DEG C, are cooled down
To room temperature, it is stripped in deionized water, film is placed in progress proton exchange 24h in 2M sulfuric acid, then with deionized water repeatedly
Washing obtains sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM until pH=6~7.By testing, above-mentioned acquisition
The thickness of sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM is 70~80 μm, sulfonation degree 50%.
Above-mentioned steps 6) obtain S-PFCB-50 hydrogen nuclear magnetic resonance spectrum as shown in figure 1, the S-PFCB-50 of above-mentioned acquisition
Fluorine nmr spectrum as shown in Fig. 2 thermal gravimetric analysis curves of the S-PFCB-50 (sour form) in air atmosphere of above-mentioned acquisition
As shown in figure 3, the S-PFCB-50 films of above-mentioned acquisition and Nafion115 water absorption rate curve are as shown in figure 4, the S- of above-mentioned acquisition
PFCB-50 films and Nafion115 swelling ratio curve is as shown in figure 5, the S-PFCB-50 films and Nafion115 of above-mentioned acquisition
Proton conductivity curve is as shown in Figure 6.
As depicted in figs. 1 and 2, S-PFCB-x prepared by present invention structure obtains through hydrogen nuclear magnetic resonance and fluorine nmr
Confirm；Thermogravimetric analysis such as Fig. 3 shows that the weightless temperature of such polymer (sour form) 5% can be to more than 217 DEG C；Such as Fig. 4 and
Shown in Fig. 5, compared with commercialized Nafion115 films, there is low suction using the films prepared of the S-PFCB-x obtained by the present invention
Water rate, swelling ratio；Proton conductivity test as described in Figure 6 shows that such membrane material its proton conductivity at 85 DEG C is reachable
0.143S/cm.S-PFCB-x prepared by these as shown by data present invention can be as the proton exchange membrane material of fuel cell.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of preparation method of sulfonated perfluorocarbon cyclobutyl polyarylether polymer, it is characterised in that including following preparation process：
（1）With different methoxyl group fragrance dihydric phenol and 1,2- dibromotetrafluoroethane for raw material, the trifluoro second containing methoxyl group is prepared
Alkenyl aryl ether monomer；
（2）(π of 2 π+2) thermal cyclization polymerization of Trifluorovinyl Aryl Ethers monomer described in (1) is utilized, is obtained containing methoxyl group
Perfluorocyclobutanearyl polyarylether polymer；
（3）Perfluorocyclobutanearyl polyarylether polymer containing methoxyl group acts on Boron tribromide, removes protection ylmethyl, and preparation has
The perfluorocyclobutanearyl polyarylether polymer of different hydroxy radical contents；
（4）Using the method for grafting, sulfonation side base is introduced, obtains sulfonated perfluorocarbon cyclobutyl polyarylether polymer, is obtained for preparing
Obtain PEM；
The structural formula of the sulfonated perfluorocarbon cyclobutyl polyarylether polymer is：
；
Wherein：M is more than 0, less than 1；N is more than 0, less than 1；And m+n=1；Ar includes following chemicals：
。
2. the preparation method of sulfonated perfluorocarbon cyclobutyl polyarylether polymer according to claim 1, it is characterised in that specific
Including following preparation process：
1）The preparation of intermediate compound 1：
7.0 g 5- methoxyl group resorcinols are taken to be added in 200 mL dimethyl sulfoxides, stirring makes 5- methoxyl group resorcinols molten
Solution；After depressurizing 30 min with oil pump, with nitrogen into solution the min of bubbling 30 to remove the oxygen in solution；Protected in nitrogen
Under, add 48.9 g cesium carbonates；With nitrogen after the min of bubbling 30,38.9 g 1,2- dibromotetrafluoroethanes are added into solution；
50 DEG C are warming up to, is stirred 2 days；Stop heating, reactant mixture is transferred in 1 L beaker, after system is cooled to room temperature,
Add 200 mL water, stir 10 min, then add 100 mL dichloromethane, separate organic phase, organic phase washes 3 times, every time
With water 50mL；Merge aqueous phase, with n-hexane extraction 3 times, use the mL of n-hexane 50 every time；Merge organic phase, done with anhydrous magnesium sulfate
It is dry；Filter, solvent is removed with Rotary Evaporators；Remaining liquid carries out separating-purifying with column chromatography, and it is colourless to obtain 15.1 g
The intermediate compound 1 of prescribed liquid；
2）The preparation of intermediate compound 2：
Reflux condensing tube is filled in 250 mL three neck round bottom, adds 1.56 g zinc granules, 4.98 g steps 1）In obtaining
Between the acetonitriles that newly steam of the mL of compound 1 and 100, the h of heating reflux reaction 24；Stop heating, the h of room temperature cooling and standings 1；Generation
Salt is deposited in three-necked bottle bottom, pours out supernatant liquor；Remaining mixture adds washing, with n-hexane extraction 3 times, every time with just
The mL of hexane 30, organic phase are dried with anhydrous magnesium sulfate；Merge organic phase, solvent, remaining liquid post are removed with rotary evaporation
Chromatography carries out separating-purifying, obtains 2.13 g colourless transparent liquids intermediate compounds 2；
3）The preparation of perfluorocyclobutanearyl polyarylether polymer containing methoxyl group：
3 g steps 2 are added in 50 dry mL three neck round bottom）The intermediate compound 2 of acquisition, is put into liquid nitrogen frozen, takes out
The min of gas 10, inflated with nitrogen thaw；After circulation three times, 180 DEG C of h of oil bath heating 12 are put into, then heat to 190 DEG C of 24 h of heating；
After room temperature cooling, gained solid is dissolved with 30 mL chloroforms, then adds 60 mL n-hexanes, and filtering, filter cake is done in 60 DEG C of vacuum
Dry 12 h, obtain perfluorocyclobutanearyl polyarylether polymer of the 2.85 g white solids containing methoxyl group；
4）The preparation of the perfluorocyclobutanearyl polyarylether polymer of hydroxyl：
By 3.20g steps 3）The perfluorocyclobutanearyl polyarylether polymer containing methoxyl group obtained is put into the drying equipped with dropping funel
250mL three neck round bottom in, add 100 mL dichloromethane dissolving, in dropping funel add contain 0.13 mL tribromides
50 mL dichloromethane solutions of boron；Reaction bulb is put into ice-water bath, Boron tribromide solution is slowly added dropwise, after being added dropwise
After 0.5 h is stirred in ice-water bath, 6 h are stirred at room temperature；Add 1 mL ethanol and reaction, gained mixture room temperature cooling and standings 1 are quenched
h；Filtering, is washed 3 times with dichloromethane, every time with 10 mL dichloromethane；Filter cake is dried in vacuo 12 h at 60 DEG C, obtains white solid
The perfluorocyclobutanearyl polyarylether polymer PFCB-OH-50 of body hydroxyl；
5）The preparation of sulfonation 4- fluorine benzophenone
After 10g 4- fluorine benzophenone and 16 mL 30% oleum are well mixed, 20 h are heated at 110 DEG C；Gained
Mixture is cooled to room temperature, is subsequently poured into 120 mL frozen water, adds 56 g NaCl and obtains white precipitate；Filtering, by white
Solid is re-dissolved in 120 mL water, and resulting solution pH value is adjusted into 6-7 with 2N NaOH；Excessive NaCl is added, is obtained white
Color precipitates, and filtering, filter cake is dried in vacuo 24 h at 100 DEG C, obtains white solid；It is 7 with volume ratio:3 first alcohol and water recrystallization,
Filtering, filter cake are dried in vacuo 24 h at 100 DEG C, obtain 16 g white powder sulfonation 4- fluorine benzophenone；
6）The preparation of sulfonated perfluorocarbon cyclobutyl polyarylether polymer
3.12 g step 4 is added in a three neck round bottom equipped with Dean-Stark water knockout drums）The PFCB-OH- of acquisition
50,0.081 g step 5）The sulfonation 4- fluorine benzophenone of acquisition, 0.021 g Anhydrous potassium carbonate, 20 mL dimethylacetamides
Amine and 10 mL toluene, with nitrogen bubble, remove the oxygen in mixture；Gained mixture is in 145 DEG C of backflows 24 h, Ran Houzheng
Go out toluene；Gained residue is heated to 170 DEG C, reacts 20 h；Under vigorous stirring, gained mixture is slowly poured into excessive
In 5 wt% hydrochloric acid, filtering, it is washed with water, gained solid dries 24 h in 100 DEG C of vacuum drying ovens, obtains sulfonated perfluorocarbon ring fourth
Base polyarylether polymer.
3. a kind of method that sulfonated perfluorocarbon cyclobutyl polyarylether polymer prepares PEM, it is characterised in that specific steps
For：
The sulfonated perfluorocarbon cyclobutyl polyarylether polymer that claim 1 obtains is dissolved in dimethyl acetamide, is made into 7 wt
% solution, resulting solution are filtered with 0.45 μm of PTFE filtering head, in culture dish casting film-forming, in 80 DEG C of dry 24 h, then
18 h are dried in vacuo at 100 DEG C, after being cooled to room temperature, are stripped in deionized water, film is placed in 2M sulfuric acid and carries out matter
Son exchanges 24 h, then is washed repeatedly to pH=6-7 with deionized water, obtains sulfonated perfluorocarbon cyclobutyl polyarylether polymer proton
Exchange membrane.
4. the sulfonated perfluorocarbon cyclobutyl polyarylether polymer PEM that method according to claim 3 is prepared, it is special
Sign is in applied to fuel cell.
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| CN106905525B (en) * | 2017-03-24 | 2019-04-30 | 福州通尔达电线电缆有限公司 | One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method |
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| CN1760233A (en) * | 2005-09-30 | 2006-04-19 | 中国科学院广州化学研究所 | The sulfonated polyether and preparation method thereof and the intermediate that contain conjugated structure |
| CN102585204A (en) * | 2012-02-26 | 2012-07-18 | 吉林大学 | Side-chain sulfonic acid type polyarylether, preparation method thereof and application of polyarylether in preparation of proton exchange membrane |
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| CN1760233A (en) * | 2005-09-30 | 2006-04-19 | 中国科学院广州化学研究所 | The sulfonated polyether and preparation method thereof and the intermediate that contain conjugated structure |
| CN102585204A (en) * | 2012-02-26 | 2012-07-18 | 吉林大学 | Side-chain sulfonic acid type polyarylether, preparation method thereof and application of polyarylether in preparation of proton exchange membrane |
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