CN102936310B - Perfluorinated ion exchange resin and preparation method thereof - Google Patents
Perfluorinated ion exchange resin and preparation method thereof Download PDFInfo
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- CN102936310B CN102936310B CN201210488827.2A CN201210488827A CN102936310B CN 102936310 B CN102936310 B CN 102936310B CN 201210488827 A CN201210488827 A CN 201210488827A CN 102936310 B CN102936310 B CN 102936310B
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Abstract
The invention provides a perfluorinated ion exchange resin and a preparation method thereof. The perfluorinated ion exchange resin has a structure shown in a formula (I). The preparation method of the perfluorinated ion exchange resin comprises the following step: performing complete or partial grafting reaction on a precursor resin and a functional monomer under certain conditions. The perfluorinated ion exchange resin synthesized by the invention can simultaneously meet the requirements for high ion exchange capacity and large mechanical strength, and has wide applicability; and by regulating the ratio of the functional monomer in the raw materials, perfluorinated ion exchange resins which have different ion exchange capacities and mechanical properties to meet various requirements can be prepared.
Description
Technical field
The invention belongs to fluoro-containing macromolecule material technical field, relate to a kind of perfluorinated ion exchange resin with high-exchange-capacity and preparation method thereof, relate in particular to a kind of side chain with perfluorinated ion exchange resin of perfluor sulfonyl imine group and preparation method thereof.
Background technology
After E.I.Du Pont Company was processed into perfluorinated sulfonic resin perfluorinated sulfonic acid type ion-exchange membrane and this film was applied in chlorine industry and Proton Exchange Membrane Fuel Cells the seventies in last century, perfluorinated ion exchange resin has obtained research widely in countries in the world.
Perfluorinated ion-exchange membrane material has stable chemically-resistant degradation property and ionic conductivity and is suitable as electrochemistry barrier film.US3282875 is disclosed first synthetic about sulfonyl fluoride monomer and prepared by the sulfonate resin document of E.I.Du Pont Company, employing be aqueous systems emulsion polymerization, the function monomer structure that wherein contains sulfonic acid fluoride side group is FO
2sCF
2cF
2oCF (CF
3) CF
2oCF=CF
2, this monomer structure is generally adopted at present.US3560568 is one section of preparation and property patent about short side group sulfonyl fluoride monomer and sulfonate resin of E.I.Du Pont Company, and the structure of the sulfonyl fluoride monomer of reporting is FO
2sCF
2cF
2oCF=CF
2, but its route complexity of preparing, yield is low.In US3883885, US3041317, introduced the sulfonate resin of being prepared by novel texture perfluor sulfonyl fluorine monomer, the sulfonyl fluoride monomer structure of employing is R
fcF=CFSO
2f, but the reactive behavior of this monomer is low.US4358545, US4417969 are the disclosed patents of DOW chemical company, this patent relates generally to fluorine-containing vinyl monomer copolymerization such as adopting short side group perfluor sulfonyl fluorine monomer and tetrafluoroethylene and prepares sulfonic fluoropolymer resin, but reports that in research afterwards this sulfonate resin without perfluor structure is less better aspect corrosion-resistant and chemical stability.Patent US7022428, US7041409, US6861489 have reported the preparation process of synthesizing low EW value sulfonate resin by mini-emulsion polymerization, and in polymerization process, have introduced the monomer that contains diene ether structure; EP1091435 discloses a kind of block sulfonate resin structure.Above-mentioned polymkeric substance is all to be prepared by tetrafluoroethylene monomer and the perfluoroalkene ethers copolymerization that contains sulfonic acid fluoride, or further in above-mentioned polymerization system, introduce other and do not have the modified monomer of ion exchanging function, obtain the polymkeric substance that contains sulfonic acid fluoride side group by polymerization technique well known in the art.The ionic resin goods that this base polymer obtains through suitable hydrolysis reaction, can be applicable to fuel cell, electrolyzer, diffusion dialysis, catalysis, the fields such as heavy metal recovery.
An important use of perfluorinated sulfonic resin is exactly to use as the barrier film of electrolytic industry, an important requirement of this class ion-exchange membrane is exactly electroconductibility, in order to improve specific conductivity, known way is to improve the loading capacity of sulfonate resin, but along with the raising of exchange capacity, its mechanical property significantly declines.In order to improve specific conductivity and to reduce mechanicalness loss of energy as far as possible, another way is to adopt composite membrane.There is high conductivity and high-intensity requirement as openly used double layer material composite membrane in the patent such as US5654109, US5246792, reaching simultaneously, but also having certain defect aspect the homogeneity of ionic conduction and the raising of electric conductivity.CN101709101B, CN101709102A discloses the perfluorinated sulfonic resin that contains Br or CN base on side group, this resinoid after treating processes in can form cross-linked network structure with increase product strength.Perfluor sulfonyl imines is a class super acids, and the technology of perfluor sulfonyl imines being introduced to polymer lateral chain is widely studied in solid acid catalysis field.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of polynary perfluorinated ion exchange resin with sulfonic acid and sulfimide side group and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of perfluorinated ion exchange resin, has the structure shown in logical formula I:
The integer that wherein m, n, p are 1-20, the integer that r, t, q are 1-4, x, x ', y, y ' are 0,1,2,3,4 or 5, and x, y are 0,0 < (x+x ')/(x+x '+y+y ') < 1 when different;
In formula, A is (CF
2)
hor (CF
2)
io(CF
2)
j, the wherein integer of h, i, j=2-6;
In formula, B is-SO
3m or
the wherein integer of a=1-4, M is H, NH
4or metal ion.
According to the present invention, in formula I, preferred A is-CF
2cF
2-,-CF
2cF
2oCF
2cF
2-,-CF
2cF
2cF
2cF
2-,-CF
2cF
2cF
2cF
2oCF
2cF
2-or-CF
2cF
2cF
2cF
2cF
2cF
2-; Particularly preferred A is CF
2cF
2oCF
2cF
2-or-CF
2cF
2cF
2cF
2-.
According to the present invention, in formula I, preferred B is
wherein a=1, M is H, Na, K or Li ion.
According to the present invention, the number-average molecular weight of formula I perfluorinated ion exchange resin is 10-60 ten thousand, is preferably 15-30 ten thousand, is particularly preferably 18-25 ten thousand.
Perfluorinated ion exchange resin preparation method of the present invention, carries out all or part of graft reaction under certain condition by precursor resin and function monomer and obtains perfluorinated ion exchange resin; Described precursor resin general structure is as shown in (II) formula:
Described function monomer is
or
a is (CF
2)
hor (CF
2)
io(CF
2)
jin one, the wherein integer of h, i, j=2-6; B is-SO
3m or
the wherein integer of a=1-4, M is H, NH
4or metal ion;
Step is as follows:
Precursor resin and the function monomer of getting above-mentioned general formula (II) join in organic solvent, in function monomer and precursor resin, contain functional group-SO
2the amount of F is than being (1 ~ 10): (10 ~ 1), and the mass volume ratio of described precursor resin and organic solvent is 1:10 ~ 15, the g/ml of unit; Described organic solvent is ethyl acetate, butyl propionate, acetonitrile, ethylene dichloride, DMF or dimethyl sulfoxide (DMSO); Under argon gas or nitrogen atmosphere, be heated to 30-100 DEG C, and constant temperature stirs 1-60 hour; Filter, wash, in 70-85 DEG C of vacuum-drying 2-30 hour, obtain perfluorinated ion exchange resin.
Preparation in accordance with the present invention, preferred, described function monomer is: H
2nSO
2cF
2cF
2cF
2cF
2sO
2nHSO
2cF
3, (CH
3)
3siHNSO
2cF
2cF
2oCF
2cF
2sO
3h, H
2nSO
2cF
2cF
2cF
2cF
2sO
3h, (CH
3)
3siHNSO
2cF
2cF
2cF
2cF
2sO
3h with and corresponding salt in one or more.
Preparation in accordance with the present invention, preferred, in reaction system, also add reaction promoter triethylamine, the volume ratio of triethylamine and organic solvent is 1.5 ~ 5:50.
Preparation in accordance with the present invention is preferred, chloroform or acetone, dilute hydrochloric acid, water washing for the throw out after filtration.
The ratio of different structure function monomer can be regulated according to the size of design loading capacity, the height of mechanical property; The functional group ratio being obtained by the graft modification of different structure function monomer is not done arbitrarily requirement, and (x+y)/(x+y+x '+y ') ratio is percentage of grafting, requires adjustable according to product performance.
The number-average molecular weight of perfluorinated ion exchange resin prepared by aforesaid method is 10-60 ten thousand, is preferably 15-30 ten thousand, is particularly preferably 18-25 ten thousand.
The precursor resin of described general formula (II) can adopt the known technology of this area to carry out polyreaction and obtain, and preferably adopts emulsion polymerization way to synthesize.The invention provides following synthetic method as an example:
Reactor is cleaned and added successively deionized water, emulsifying agent, reaction promoter, starts whipping appts, replaces three times, after the interior oxygen level of detection reaction still is qualified, in reactor, adds a certain amount of alkene ether monomer, and described alkene ether monomer is to have structural formula:
(monomer 1, the integer of q=1-4) or
(monomer 2, r, the integer of t=1-4) one of or the mixing of two kinds, in reactor, be filled with tetrafluoroethylene monomer, and keep reaction pressure, be warming up to temperature of reaction, in reactor, add initiator solution with volume pump, initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reacting kettle inner pressure constant, maintain speed of response to adding initiator in reactor during this time, after reaction finishes, be cooled to room temperature, reclaim unreacted tetrafluoroethylene monomer simultaneously, material in still is emitted, by high speed shear breakdown of emulsion, separation obtains white polymer powder, with after pure water washing 3-5 time, in 120 DEG C of baking ovens, dry, obtain the functional resin with sulfonic acid fluoride side group.
Above-described emulsifying agent, reaction promoter, initiator are routine techniques in emulsion polymerisation process.For example emulsifying agent ammonium perfluorocaprylate or sodium laurylsulfonate, reaction promoter dobell's solution or SODIUM PHOSPHATE, MONOBASIC-Sodium phosphate dibasic, initiator ammonium persulfate, Potassium Persulphate or azo dibutyl amidine hydrochloride.
The present invention has following beneficial effect:
1, the present invention adopts the precursor resin of formula II with sulfonic acid fluoride side group, with meeting generating portion sulfimide side group after function monomer grafting, synthetic perfluorinated ion exchange resin can meet the requirement that loading capacity is high, physical strength is large simultaneously, more than its loading capacity can reach 2.3mmol/g dried resin, physical strength still exceedes 20MPa, and because the sulfimide group of introducing by graft modification is a kind of super acids, it introduces the exchange capacity that increases resin on side group, has strengthened its characteristic as solid super-strong acid simultaneously; The resin of preparation has kept the strongly-acid of perfluorinated sulfonic resin, high temperature resistant, resistance to oxidation, the common characteristic of the perfluorinated material such as chemical-resistant reagent.
2, perfluorinated ion exchange resin applicability of the present invention is wide, can be for the manufacture of the ion-exchange membrane in fuel cell or electrolyzer, also can be used as a kind of super acids and be applied to chemical catalysis, can also be applied to electrodialysis, sea water desaltination, gas delivery, gas drying, the aspects such as sewage disposal.
3, can adopt solution casting technique to make the perfluorinated sulfonic acid ion exchange membrane of suitable thickness, the perfluorinated ion-exchange membrane of making not only has resistance to various chemical mediator, also have high electroconductibility and high mechanical strength, low membrane resistance, is highly suitable in fuel cell or chlor-alkali electrolysis cell and uses.
4, preparation method's step of perfluorinated ion exchange resin of the present invention is simple, and in raw material, the usage ratio of function monomer can arbitrarily regulate according to the height of the size of loading capacity, mechanical property, flexible operation.
Brief description of the drawings:
Fig. 1 is the IR spectrogram of the perfluorinated ion exchange resin prepared of embodiment 1.
Fig. 2 is the IR spectrogram of the perfluorinated ion exchange resin prepared of embodiment 2.
Fig. 3 is the IR spectrogram of the perfluorinated ion exchange resin prepared of embodiment 3.
Embodiment
Below by specific embodiment, also the present invention will be further described by reference to the accompanying drawings.The dilute hydrochloric acid concentration of washing use in embodiment is 5 ~ 10wt%.
Embodiment 1: a kind of preparation method of perfluorinated ion exchange resin, step is as follows:
Preparation precursor resin:
The aqueous solution, the 100ml mass concentration that 6L deionized water, 100ml contain 8g ammonium perfluorocaprylate cleaned and added to 10L reactor is 3% dobell's solution, start whipping appts, replace three times, after tested after the interior oxygen level qualified (lower than 5ppm) of reactor, vacuumize, to adding 500g sulfonic acid fluoride side group alkene ether monomer 1 in reactor, (structural formula is: CF
2=CF-O-CF
2-CF
2-SO
2f) and 500g sulfonic acid fluoride side group alkene ether monomer 2 (structural formula is: CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2sO
2f) after, in reactor, be filled with tetrafluoroethylene monomer and keep pressure to 2.3MPa, be warming up to 65 DEG C, adding 100g mass concentration with volume pump is 3% ammonium persulfate aqueous solution (initiator solution), initiated polymerization, continue to pass into tetrafluoroethylene monomer and keep reaction pressure at 2.3MPa, in system, adding 25g initiator solution (being that mass concentration is 3% ammonium persulfate aqueous solution) every 30min, stopped reaction after reaction 2h; Temperature of reaction kettle is down to room temperature, reclaim unreacted tetrafluoroethylene monomer simultaneously, oyster white slurry in still is put into after-treatment system by lower dispensing valve, by high speed shear breakdown of emulsion, separation obtains white polymer powder, with after pure water washing 3-5 time, in 120 DEG C of baking ovens, dry, obtain the precursor resin with sulfonic acid fluoride side group.The data of gained precursor resin:
Through F
19nMR, IR analyze and turn out to be ter-polymers, the molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by fluorine nuclear-magnetism is 63.02%, containing sulfonic acid fluoride side group alkene ether monomer 1 molecular fraction is 21.3%, containing sulfonic acid fluoride side group alkene ether monomer 2 molecular fractions is 15.5%, in overall resin-and SO
2f content is 1.86mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 356 DEG C.
The preparation of perfluorinated ion exchange resin:
Get the H of 50g precursor resin and 26g
2nSO
2cF
2cF
2sO
3h adds in 500ml ethylene dichloride, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 60 DEG C, and constant temperature stirs 48 hours; After filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, obtain perfluorinated ion exchange resin 68.3g.
The test of perfluorinated ion exchange resin:
According to GB GB 8144-87 Zeo-karb exchange capacity measuring method, the exchange capacity of the gained perfluorinated ion exchange resin of survey is 2.47mmol/g dried resin; Calculate according to titration measuring result, with-SO
2f is benchmark, and the knot branch rate of resin is 81%.To obtain after perfluorinated ion exchange resin transfers H type to carrying out TGA test, under nitrogen atmosphere, the initial decomposition temperature of perfluorinated ion exchange resin is 290 DEG C;
IR spectrogram: 1056cm
-1there is SO
3the stretching vibration peak of H, 1468cm
-1place-SO
2the peak intensity of F obviously weakens, and 1200 and 1148cm
-1two absorb the most by force by CF vibration and cause, 984cm
-1for CF
3vibration causes; 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 2: a kind of preparation method of perfluorinated ion exchange resin, comprises the following steps:
Precursor resin according to the method preparation of embodiment 1 with sulfonic acid fluoride side group, difference is: add 600g sulfonyl fluoride monomer 1(CF
2=CF-O-CF
2cF
2-SO
2and 300g sulfonyl fluoride monomer 2(CF F)
2=CF-O-CF
2cF(CF
3)-O-CF
2cF
2sO
2f), and keep carrying out polyreaction under the reaction pressure of 1.8MPa, obtain precursor resin.
The data of precursor resin:
Through F
19nMR, IR analyze and turn out to be ter-polymers, and the molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by fluorine nuclear-magnetism is 58.1%, contains sulfonic acid fluoride group alkene ether monomer (CF
2=CF-O-CF
2-CF
2-SO
2f) molecular fraction is 33.4%, contains sulfonic acid fluoride group alkene ether monomer (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2sO
2f) molecular fraction is 8.5%, in overall resin-and SO
2f content is 2.18mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 343 DEG C.
Get (the CH of 50g precursor resin and 60g
3)
3siHNSO
2cF
2cF
2oCF
2cF
2sO
3h adds in 500ml ethylene dichloride, under argon gas atmosphere, is heated to 60 DEG C, and constant temperature stirs 48 hours, after filtering with acetone, dilute hydrochloric acid, water washing, obtain sample in vacuum drying oven 80 DEG C dry 24 hours, obtain perfluorinated ion exchange resin 81.3g.
The test of perfluorinated ion exchange resin:
According to GB GB 8144-87 Zeo-karb exchange capacity measuring method, the exchange capacity of the perfluorinated ion exchange resin of survey is 2.31mmol/g dried resin, according to volumetry test result calculations, with-SO
2f is benchmark, and the knot branch rate of resin is 70.5%, carries out TGA test after transferring perfluorinated ion exchange resin to H type, and under nitrogen atmosphere, resin initial decomposition temperature is 287 DEG C.
IR spectrogram, as shown in Figure 2: 1058cm
-1there is SO
3the stretching vibration peak of H, 1468cm
-1place-SO
2the peak intensity of F obviously weakens, and 1200 and 1148cm
-1two absorb the most by force by CF vibration and cause, 984cm
-1for CF
3vibration causes; 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 3: a kind of preparation method of perfluorinated ion exchange resin, comprises the following steps:
Reactor is cleaned and added 6L deionized water, the aqueous solution that 100ml contains 10g sodium laurylsulfonate, start whipping appts, vacuumize, fill high pure nitrogen displacement three times, after tested in reactor oxygen level below 10ppm after, vacuumize, in reactor, add 1000g sulfonic acid fluoride side group alkene ether monomer 1 (CF by liquid feeding valve
2=CF-O-CF
2-CF
2-SO
2f) after, in reactor, fill tetrafluoroethylene monomer pressure to 2.0MPa, be warming up to 55 DEG C, adding 100g mass concentration with volume pump is 4.5% the azo dibutyl amidine hydrochloride aqueous solution (initiator solution), initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reaction pressure at 2.0MPa, in system, add 30g initiator solution every 30min, after reaction 2h, stop adding initiator, allow reaction proceed after 30min, stop adding tetrafluoroethylene monomer.Be cooled to room temperature by cooling recirculation system to reactor, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in still is put into after-treatment system after by lower dispensing valve, adding 1L concentration is 10% ammonium carbonate solution, separation obtains white polymer powder, with pure water washing 3-5 time, in 100 DEG C of baking ovens, dry, obtain the precursor resin with sulfonic acid fluoride side group.
The data analysis of precursor resin:
Analyze and turn out to be binary polymer through IR, the molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by diffuse reflectance infrared spectroscopy peak is 81.1%, contains sulfonic acid fluoride side group alkene ether monomer (CF
2=CF-O-CF
2-CF
2-SO
2f) molecular fraction is 18.9%, in overall resin-and SO
2f content is 1.4mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 392 DEG C.
Get the H of the above-mentioned resin of 50g and 40g
2nSO
2cF
2cF
2cF
2cF
2sO
3h adds in 500ml acetonitrile, under argon gas atmosphere, splashes into triethylamine 15ml, is heated to 80 DEG C, and constant temperature stirs 20 hours; After filtering, use acetone, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, obtain perfluorinated ion exchange resin 73g.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom by volumetry is 1.9mmol/g dried resin, according to volumetry test result calculations, with-SO
2f is benchmark, and the knot branch rate of resin is 95%.Transfer perfluorinated ion exchange resin to H type and carry out TGA test, under nitrogen atmosphere, resin initial decomposition temperature is 276 DEG C.
IR spectrogram, as shown in Figure 3: 1056cm
-1there is SO
3the stretching vibration peak of H, 1468cm
-1place-SO
2the peak intensity of F obviously weakens, and 1200 and 1148cm
-1two absorb the most by force by CF vibration and cause, 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 4: a kind of preparation method of perfluorinated ion exchange resin, comprises the following steps:
Reactor being cleaned and added 6L deionized water, the aqueous solution that 100ml contains 10g sodium laurylsulfonate, 100ml concentration is 3% Sodium Tetraborate, 1.2kg sulfonic acid fluoride side group alkene ether monomer 2 (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2sO
2f), start whipping appts, vacuumize, fill high pure nitrogen displacement three times, after tested in reactor oxygen level below 10ppm after, in reactor, fill tetrafluoroethylene monomer pressure to 1.1MPa, be warming up to 70 DEG C, adding 100g mass concentration with volume pump is 3% persulfate aqueous solution (initiator solution), initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reaction pressure at 2.0MPa, in system, add 20g initiator solution every 15min, after reaction 2h, stop adding initiator, allow reaction proceed after 15min, stop adding tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in still is put into after-treatment system after by lower dispensing valve, high-speed stirring makes its breakdown of emulsion, separation obtains white polymer powder, with pure water washing 3-5 time, in 100 DEG C of baking ovens, dry, obtain the precursor resin with sulfonic acid fluoride side group.
The data of precursor resin:
The molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by diffuse reflectance infrared spectroscopy peak is 82.1%, contains sulfonic acid fluoride side group alkene ether monomer (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2sO
2f) molecular fraction is 17.9%, in overall resin-and SO
2f content is 1.1mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 345 DEG C.
Get the H of the above-mentioned resin of 50g and 35g
2nSO
2cF
2cF
2cF
2cF
2sO
3h adds in 500ml acetonitrile, is added dropwise to wherein the triethylamine of 30ml, under argon gas atmosphere, be heated to 80 DEG C, and constant temperature stirs 20 hours, after filtering with chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, obtain perfluorinated ion exchange resin 69g.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom by volumetry is 1.6mmol/g dried resin; According to infrared measurement ,-SO
2f group is converted into sulfimide group completely.The initial decomposition temperature that TGA test obtains resin nitrogen atmosphere is 271 DEG C.
IR spectrogram: 1056cm
-1there is SO
3the stretching vibration peak of H, 1468cm
-1place-SO
2the peak of F disappears, and 1200 and 1148cm-
1two absorb the most by force by CF vibration and cause, 984cm
-1for CF
3vibration causes; 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 5:
Get the precursor resin 50g that obtains in embodiment 4 and the H of 30g
2nSO
2cF
2cF
2cF
2cF
2sO
2nHSO
2cF
3add the triethylamine that is added dropwise to wherein 50ml in 500ml ethyl acetate, under argon gas atmosphere, be heated to 77 DEG C, and constant temperature stirs 20 hours, after filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, obtain perfluorinated ion exchange resin 69g.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom by volumetry is 1.29mmol/g dried resin.Calculate according to titrate the analysis result, in precursor resin-SO
2the percentage of grafting of F is 61%.To obtain after perfluorinated ion exchange resin transfers H type to carrying out TGA test, under nitrogen atmosphere, resin initial decomposition temperature is 271 DEG C.
IR spectrogram: 1632cm
-1there is the vibration absorption peak of N-H, 1367cm in place
-1appearance-the SO of place
2-absorption, 1468cm
-1place-SO
2the peak of F obviously weakens, 984cm
-1place is CF
3vibration absorption peak, 1468cm
-1place-SO
2the peak of F obviously weakens.
Embodiment 6:
Reactor being cleaned and added 6L deionized water, the aqueous solution that 100ml contains 10g ammonium perfluorocaprylate, 100ml concentration is 3% dobell's solution, 240g sulfonic acid fluoride side group alkene ether monomer 1 (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2sO
2f), start whipping appts, vacuumize, fill high pure nitrogen displacement three times, after tested in reactor oxygen level below 10ppm after, in reactor, add 960g sulfonic acid fluoride side group alkene ether monomer (CF by liquid phase feeding valve
2=CF-O-CF
2cF
2cF
2cF
2sO
2f), be warming up to 70 DEG C, in reactor, fill tetrafluoroethylene monomer pressure to 1.3MPa, adding 100g mass concentration with volume pump is 3% persulfate aqueous solution (initiator solution), initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reaction pressure at 1.3MPa, in system, add 20g initiator solution every 15min, after reaction 2h, stop adding initiator, allow reaction proceed after 15min, stop adding tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in still is put into after-treatment system after by lower dispensing valve, high-speed stirring makes its breakdown of emulsion, separation obtains white polymer powder, with pure water washing 3-5 time, in 100 DEG C of baking ovens, dry, obtain the precursor resin with sulfonic acid fluoride side group.The data analysis of precursor resin is as follows:
Through F
19nMR, IR analyze and turn out to be ter-polymers, and the molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by fluorine nuclear-magnetism is 73.52%, contains sulfonic acid fluoride side group alkene ether monomer (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2sO
2f) molecular fraction is 4.3%, contains sulfonic acid fluoride side group alkene ether monomer (CF
2=CF-O-CF
2cF
2cF
2cF
2sO
2f) molecular fraction is 22.18%, in overall resin-and SO
2f content is 1.5mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 377 DEG C.
Get above-mentioned precursor resin 50g resin, by (the CH of resin and 26g
3)
3siNNaSO
2cF
2cF
2sO
3na adds in the DMF of 500ml, under nitrogen atmosphere, is heated to 75 DEG C, and constant temperature stirs 8 hours, leaches toner, uses washing with acetone 2-3 time, in the vacuum drying oven of 80 DEG C, dries, and obtains perfluorinated ion exchange resin 61.2g.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom by volumetry is 1.85mmol/g dried resin, and according to exchange capacity titration test result calculations, obtaining precursor resin percentage of grafting is 51%.To obtain after perfluorinated ion exchange resin transfers H type to carrying out TGA test, resin initial decomposition temperature under nitrogen atmosphere is 263 DEG C.
IR spectrogram: SO appears in 1058cm-1 place
3the absorption of Na, 984cm
-1the vibration absorption peak of place's perfluoro-methyl, 1468cm
-1place-SO
2the peak of F disappears, and 1200 and 1148cm
-1two absorb the most by force by CF vibration and cause, 984cm
-1for CF
3vibration causes; 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 7: a kind of preparation method of perfluorinated ion exchange resin, step is as follows:
Reactor is cleaned and added 6L deionized water, the aqueous solution that 100ml contains 15g ammonium perfluorocaprylate, the aqueous solution that 200ml contains 0.9g SODIUM PHOSPHATE, MONOBASIC and 1.3g Sodium phosphate dibasic, start whipping appts, vacuumize, fill high pure nitrogen displacement three times, after tested in reactor oxygen level below 10ppm after, vacuumize, in reactor, add 1100g sulfonic acid fluoride side group alkene ether monomer 1 (CF by liquid feeding valve
2=CF-O-CF
2-CF
2-CF
2cF
2-SO
2f) after, in reactor, fill tetrafluoroethylene monomer pressure to 1.8MPa, be warming up to 70 DEG C, adding 100g mass concentration with volume pump is 3.5% ammonium persulfate aqueous solution (initiator solution), initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reaction pressure at 1.8MPa, in system, add 30g initiator solution every 30min, after reaction 2h, stop adding initiator, allow reaction proceed after 30min, stop adding tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in still is put into after-treatment system after by lower dispensing valve, high-speed stirring breakdown of emulsion, separation obtains white polymer powder, with pure water washing 3-5 time, in 100 DEG C of baking ovens, dry, obtain the precursor resin with sulfonic acid fluoride side group.The data analysis of precursor resin:
The molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by diffuse reflectance infrared spectroscopy peak is 80.9%, contains sulfonic acid fluoride side group alkene ether monomer ((CF
2=CF-O-CF
2-CF
2-CF
2cF
2-SO
2f) molecular fraction is 19.1%, in overall resin-and SO
2f content is 1.24mmol/g dried resin, and TGA test resin is under nitrogen atmosphere, and initial decomposition temperature is 353 DEG C; Show according to infrared result, percentage of grafting is 100%.
Get above-mentioned resin 50g, by (the CH of resin and 20g
3)
3siNNaSO
2cF
2cF
2sO
3na, (the CH of 20g
3)
3siNNaSO
2cF
2cF
2sO
2nNaSO
2cF
3, add in the DMF of 500ml, under nitrogen atmosphere, be heated to 75 DEG C, constant temperature stirs 8 hours, leaches toner, uses washing with acetone 2-3 time, in the vacuum drying oven of 80 DEG C, dries, and obtains perfluorinated ion exchange resin 71.6g.
The test of perfluorinated ion exchange resin:
With the exchange capacity of product that volumetry is surveyed be 1.73mmol/g dried resin, carry out TGA test after perfluorinated ion exchange resin is changed into H type, the initial decomposition temperature of resin under nitrogen atmosphere is 281 DEG C.
IR spectrogram: 1468cm
-1place-SO
2the peak completely dissolve of F, 1058cm
-1appearance-the SO of place
3the absorption peak of Na, 1200 and 1148cm
-1two absorb the most by force by CF vibration and cause, 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 8: a kind of preparation method of perfluorinated ion exchange resin, comprises the following steps:
Reactor being cleaned and added 6L deionized water, the aqueous solution that 100ml contains 10g Sodium perfluorooctanoate, 100ml concentration is 3% dobell's solution, 800g sulfonic acid fluoride side group alkene ether monomer 1 (CF
2=CF-O-CF
2-CF
2-CF
2-CF
2-SO
2and 400g sulfonic acid fluoride side group alkene ether monomer 2 (CF F)
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2cF
2sO
2f), start whipping appts, vacuumize, fill high pure nitrogen displacement three times, after tested in reactor oxygen level below 10ppm after, improve stirring velocity to 500rpm, pre-emulsification 20min, in reactor, fill tetrafluoroethylene monomer pressure to 1.5MPa, be warming up to 60 DEG C, adding 100g mass concentration with volume pump is 3% ammonium persulfate aqueous solution (initiator solution), initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reaction pressure at 1.5MPa, in system, add 25g initiator solution every 30min, after reaction 2h, stop adding initiator, allow reaction proceed after 30min, stop adding tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in still is put into after-treatment system after by lower dispensing valve, after high speed shear, separation obtains white polymer powder, with after pure water washing 3-5 time, in 100 DEG C of baking ovens, dry, obtain the precursor resin with sulfonic acid fluoride side group.The data analysis of precursor resin:
Through F
19nMR, IR analyze and turn out to be ter-polymers, and the molecular fraction that contains tetrafluoroethylene in the known polymer architecture of integrated value by fluorine nuclear-magnetism is 73.1%, contains sulfonic acid fluoride side group alkene ether monomer (CF
2=CF-O-CF
2-CF
2-CF
2-CF
2-SO
2f) molecular fraction is 23.4%, contains sulfonic acid fluoride side group alkene ether monomer (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2cF
2cF
2sO
2f) molecular fraction is 3.5%, in overall resin-and SO
2f content is 1.5mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 358 DEG C.
Get above-mentioned precursor resin 50g, by resin and 10g H
2nSO
2cF
2cF
2cF
2cF
2sO
2nHSO
2cF
3, 20gH
2nSO
2cF
2cF
2cF
2cF
2sO
3h, adds in the ethyl acetate of 500ml, under nitrogen atmosphere condition, be heated to 70 DEG C, slowly drip wherein 30g triethylamine, after being added dropwise to complete, continue constant temperature and stir 8 hours, leach toner, with ether washing 2-3 time, in the vacuum drying oven of 80 DEG C, dry and obtain modified resin, being used concentration is, after 5% KOH aqueous solution transition, with deionized water wash, after drying, to obtain perfluorinated ion exchange resin 80.5 in the vacuum drying oven of 80 DEG C, through infrared test ,-SO
2f completely dissolve, proves that resin grafting is complete.
The test of perfluorinated ion exchange resin:
Surveying products therefrom exchange capacity by volumetry is 1.87mmol/g dried resin, will obtain after perfluorinated ion exchange resin changes into H type carrying out TGA test, and the initial decomposition temperature of resin under nitrogen atmosphere is 277 DEG C.
IR spectrogram: 1468cm
-1place-SO
2the peak completely dissolve of F, the appearance-SO of 1058cm-1 place
3the absorption vibration peak of K, 1200 and 1148cm
-1two absorb the most by force by CF vibration and cause, 984cm
-1the CF of place
3absorption of vibrations grow, 720cm
-1, 641cm
-1caused by TFE vibration.
Embodiment 9:
Get precursor resin 50g resin in embodiment 1 and the H of 30g
2nSO
2(CF
2)
3sO
3k adds in 500ml butyl propionate, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 60 DEG C, and constant temperature stirs 48 hours; After filtering, with chloroform, dilute hydrochloric acid, water washing, in vacuum drying oven, 80 DEG C are dried 24 hours, make perfluorinated ion exchange resin.
Embodiment 10:
Get precursor resin 50g synthetic in embodiment 1 and the H of 30g
2nSO
2(CF
2)
5sO
3nH
4add in 500ml butyl propionate, be added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, be heated to 50 DEG C, and constant temperature stirs 10 hours; After filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, make perfluorinated ion exchange resin.
Embodiment 11:
Get precursor resin 50g in embodiment 1 and the H of 40g
2nSO
2(CF
2)
6sO
3k adds in 500ml dimethyl sulfoxide (DMSO), is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 35 DEG C, and constant temperature stirs 38 hours; After filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, make perfluorinated ion exchange resin.
Embodiment 12:
Get precursor resin 50g in embodiment 1 and the (CH of 40g
3)
3siHNSO
2(CF
2)
2oCF
2cF
2sO
3h adds in 500ml dimethyl sulfoxide (DMSO), under argon gas atmosphere, is heated to 40 DEG C, and constant temperature stirs 58 hours; After filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly; In vacuum drying oven, 80 DEG C are dried 24 hours, make perfluorinated ion exchange resin.
Embodiment 13:
Get precursor resin 50g in embodiment 1 and the H of 26g
2nSO
2(CF
2)
2o(CF
2)
4sO
2nHSO
2cF
3add in 500ml dimethyl sulfoxide (DMSO), be added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, be heated to 45 DEG C, and constant temperature stirs 50 hours; After filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, make perfluorinated ion exchange resin.
Embodiment 14:
Get precursor resin 50g synthetic in embodiment 1 and the H of 26g
2nSO
2(CF
2)
2o(CF
2)
5sO
2nNH
4sO
2(CF
2)
2f adds in 500ml ethylene dichloride, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 50 DEG C, and constant temperature stirs 60 hours; After filtering, use chloroform, dilute hydrochloric acid, water washing repeatedly, in vacuum drying oven, 80 DEG C are dried 24 hours, make perfluorinated ion exchange resin.
Embodiment 15:
Get precursor resin 50g that embodiment 1 is neutralized into and the H of 30g
2nSO
2(CF
2)
2o(CF
2)
6sO
2nKSO
2(CF
2)
2f adds in 500ml ethylene dichloride, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 60 DEG C, and constant temperature stirs 60 hours; Subsequent disposal makes perfluorinated ion exchange resin with embodiment 1.
Embodiment 16:
Get precursor resin 50g in embodiment 1 and the H of 30g
2nSO
2(CF
2)
2o(CF
2)
5sO
2nNH
4sO
2(CF
2)
2f adds in 500ml acetonitrile, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 75 DEG C, and constant temperature stirs 50 hours; Subsequent disposal makes perfluorinated ion exchange resin with embodiment 1.
Embodiment 17:
Get precursor resin 50g that embodiment 1 is neutralized into and the H of 40g
2nSO
2(CF
2)
5sO
2nHSO
2(CF
2)
4f adds in 500ml acetonitrile, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 60 DEG C, and constant temperature stirs 48 hours; Subsequent disposal makes perfluorinated ion exchange resin with embodiment 1.
Embodiment 19:
Get precursor resin 50g that embodiment 1 is neutralized into and the H of 26g
2nSO
2(CF
2)
2sO
2nKSO
2(CF
2)
2f adds in 500ml ethyl acetate, is added dropwise to wherein the triethylamine of 50ml, under argon gas atmosphere, is heated to 70 DEG C, and constant temperature stirs 48 hours; Subsequent disposal makes perfluorinated ion exchange resin with embodiment 1.
Claims (10)
1. a perfluorinated ion exchange resin, is characterized in that this perfluorinated ion exchange resin has the structure shown in logical formula I:
（Ⅰ）
The integer that wherein m, n, p are 1-20, the integer that r, t, q are 1-4, x, x ', y, y ' are 0,1,2,3,4 or 5, and x, y are 0,0 < (x+x ')/(x+x '+y+y ') < 1 when different;
In formula, A is (CF
2)
hor (CF
2)
io(CF
2)
j, the wherein integer of h, i, j=2-6;
In formula, B is-SO
3m or
, the wherein integer of a=1-4, M is H, NH
4or metal ion.
2. perfluorinated ion exchange resin according to claim 1, is characterized in that: in formula I, A is-CF
2cF
2-,-CF
2cF
2oCF
2cF
2-,-CF
2cF
2cF
2cF
2-,-CF
2cF
2cF
2cF
2oCF
2cF
2-or-CF
2cF
2cF
2cF
2cF
2cF
2-.
3. perfluorinated ion exchange resin according to claim 1, is characterized in that: in formula I, B is
, wherein a=1, M is H, Na, K or Li ion.
4. perfluorinated ion exchange resin according to claim 1, is characterized in that: the number-average molecular weight of perfluorinated ion exchange resin is 10-60 ten thousand.
5. perfluorinated ion exchange resin according to claim 1, is characterized in that: the number-average molecular weight of perfluorinated ion exchange resin is 15-30 ten thousand.
6. the preparation method of perfluorinated ion exchange resin described in claim 1 ~ 5 any one, carries out all or part of graft reaction under certain condition by precursor resin and function monomer and obtains perfluorinated ion exchange resin; Described precursor resin general structure is as shown in (II) formula:
（Ⅱ）
Described function monomer is
or
, A is (CF
2)
hor (CF
2)
io(CF
2)
jin one, the wherein integer of h, i, j=2-6; B is-SO
3m or
, the wherein integer of a=1-4, M is H, NH
4or metal ion;
Step is as follows:
Precursor resin and the function monomer of getting above-mentioned general formula (II) join in organic solvent, in function monomer and precursor resin, contain functional group-SO
2the amount of F is than being (1 ~ 10): (10 ~ 1), and the mass volume ratio of described precursor resin and organic solvent is 1:10 ~ 15, the g/ml of unit; Described organic solvent is ethyl acetate, butyl propionate, acetonitrile, ethylene dichloride, DMF or dimethyl sulfoxide (DMSO); Under argon gas or nitrogen atmosphere, be heated to 30-100 DEG C, and constant temperature stirs 1-60 hour; Filter, wash, in 70-85 DEG C of vacuum-drying 2-30 hour, obtain perfluorinated ion exchange resin.
7. the preparation method of perfluorinated ion exchange resin according to claim 6, is characterized in that described function monomer is H
2nSO
2cF
2cF
2cF
2cF
2sO
2nHSO
2cF
3, (CH
3)
3siHNSO
2cF
2cF
2oCF
2cF
2sO
3h, H
2nSO
2cF
2cF
2cF
2cF
2sO
3h, (CH
3)
3siHNSO
2cF
2cF
2cF
2cF
2sO
3one or more in H and corresponding salt thereof.
8. the preparation method of perfluorinated ion exchange resin according to claim 6, is characterized in that, in reaction system, also adding reaction promoter triethylamine, the volume ratio of triethylamine and organic solvent is 1.5 ~ 5:50.
9. the preparation method of perfluorinated ion exchange resin according to claim 6, is characterized in that, chloroform or acetone, dilute hydrochloric acid, water washing for the throw out after filtration.
10. the preparation method of perfluorinated ion exchange resin according to claim 6, is characterized in that, the precursor resin of described general formula (II) adopts emulsion polymerization way to synthesize, and step is as follows:
Reactor is cleaned and also added successively deionized water, emulsifying agent, reaction promoter, start whipping appts, replace three times, after the interior oxygen level of detection reaction still is qualified, in reactor, add a certain amount of alkene ether monomer, described alkene ether monomer is the mixing with one of monomer of following structural or two kinds:
In reactor, be filled with tetrafluoroethylene monomer, and keep reaction pressure, be warming up to temperature of reaction, in reactor, add initiator solution with volume pump, initiated polymerization, continuing to pass into tetrafluoroethylene monomer keeps reacting kettle inner pressure constant, maintain speed of response to adding initiator in reactor during this time, after reaction finishes, be cooled to room temperature, reclaim unreacted tetrafluoroethylene monomer simultaneously, material in still is emitted, by high speed shear breakdown of emulsion, separation obtains white polymer powder, with after pure water washing 3-5 time, in 120 DEG C of baking ovens, dry, obtain the functional resin with sulfonic acid fluoride side group.
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| CN114133477B (en) * | 2021-11-26 | 2023-11-14 | 国家电投集团氢能科技发展有限公司 | Ion exchange resin, preparation method thereof, ion exchange membrane and application thereof |
| CN114835842B (en) * | 2022-06-15 | 2024-04-12 | 浙江巨化技术中心有限公司 | Polymerization method of perfluorosulfonyl fluoride resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026783A (en) * | 1973-12-17 | 1977-05-31 | E. I. Du Pont De Nemours And Company | Electrolysis cell using cation exchange membranes of improved permselectivity |
| JPS61118407A (en) * | 1984-08-13 | 1986-06-05 | ザ ダウ ケミカル カンパニ− | Manufacture of acid type partially neutralized strongly acidic cation exchange resin |
| EP1060200B1 (en) * | 1998-03-03 | 2003-01-15 | E.I. Du Pont De Nemours And Company | Substantially fluorinated ionomers |
| CN101768236A (en) * | 2009-12-25 | 2010-07-07 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin as well as preparation method and application thereof |
| CN101798365A (en) * | 2009-12-11 | 2010-08-11 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin and preparation method and application thereof |
-
2012
- 2012-11-26 CN CN201210488827.2A patent/CN102936310B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026783A (en) * | 1973-12-17 | 1977-05-31 | E. I. Du Pont De Nemours And Company | Electrolysis cell using cation exchange membranes of improved permselectivity |
| JPS61118407A (en) * | 1984-08-13 | 1986-06-05 | ザ ダウ ケミカル カンパニ− | Manufacture of acid type partially neutralized strongly acidic cation exchange resin |
| EP1060200B1 (en) * | 1998-03-03 | 2003-01-15 | E.I. Du Pont De Nemours And Company | Substantially fluorinated ionomers |
| CN101798365A (en) * | 2009-12-11 | 2010-08-11 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin and preparation method and application thereof |
| CN101768236A (en) * | 2009-12-25 | 2010-07-07 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin as well as preparation method and application thereof |
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Effective date of registration: 20201207 Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd Address before: 256401 Tangshan Town, Huantai County, Zibo, Shandong Patentee before: SHANDONG HUAXIA SHENZHOU NEW MATERIAL Co.,Ltd. |