CN102936310A - Perfluorinated ion exchange resin and preparation method thereof - Google Patents
Perfluorinated ion exchange resin and preparation method thereof Download PDFInfo
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- CN102936310A CN102936310A CN2012104888272A CN201210488827A CN102936310A CN 102936310 A CN102936310 A CN 102936310A CN 2012104888272 A CN2012104888272 A CN 2012104888272A CN 201210488827 A CN201210488827 A CN 201210488827A CN 102936310 A CN102936310 A CN 102936310A
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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 the 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 used in chlorine industry and Proton Exchange Membrane Fuel Cells the seventies in last century, perfluorinated ion exchange resin had obtained widely research in countries in the world.
The perfluorinated ion-exchange membrane material has stable chemically-resistant degradation property and ionic conductivity and is suitable as the electrochemistry barrier film.US3282875 is disclosed first document synthetic about sulfonyl fluoride monomer and the sulfonate resin preparation of E.I.Du Pont Company, employing be the aqueous systems emulsion polymerization, the function monomer structure that wherein contains the 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 piece 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 the route of its preparation is complicated, and yield is low.Introduced the sulfonate resin by the preparation of novel texture perfluor sulfonyl fluorine monomer among US3883885, the US3041317, 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 the sulfonic fluoropolymer resin, but reports thisly do not have the sulfonate resin of perfluor structure less better aspect corrosion-resistant and the chemical stability in research afterwards.Patent US7022428, US7041409, US6861489 have reported the preparation process by the synthetic low EW value sulfonate resin of mini-emulsion polymerization, and have introduced the monomer that contains the diene ether structure in polymerization process; EP1091435 discloses a kind of block sulfonate resin structure.Above-mentioned polymkeric substance all is 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 containing the polymkeric substance of sulfonic acid fluoride side group by polymerization technique well known in the art.This base polymer can be applicable to fuel cell, electrolyzer, diffusion dialysis, catalysis, the fields such as heavy metal recovery through the ionic resin goods that suitable hydrolysis reaction obtains.
An important use of perfluorinated sulfonic resin is exactly the barrier film use as 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 descends.In order to improve specific conductivity and to reduce the mechanicalness loss of energy as far as possible, another way is to adopt composite membrane.As openly using the double layer material composite membrane in the patents such as US5654109, US5246792, reach and have simultaneously high conductivity and high-intensity requirement, but also having certain defective aspect the raising of the homogeneity of ionic conduction and electric conductivity.CN101709101B, CN101709102A disclose the perfluorinated sulfonic resin that contains Br or CN base on the side group, this resinoid after treating processes in can form cross-linked network structure to increase product strength.The perfluor sulfonyl imines is a class super acids, and the technology of the perfluor sulfonyl imines being introduced polymer lateral chain is widely studied in the 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 the logical formula I:
Wherein m, n, p are the integer of 1-20, and r, t, q are the integer of 1-4, and x, x ', y, y ' are 0,1,2,3,4 or 5, and x, y are not 0,0＜(x+x ')/(x+x '+y+y ')＜1 simultaneously;
A is (CF in the formula
2)
hOr (CF
2)
iO(CF
2)
j, the integer of h, i, j=2-6 wherein;
B is-SO in the formula
3M or
The integer of a=1-4 wherein, M is H, NH
4Or metal ion.
According to the present invention, preferred A is-CF in the formula I
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, preferred B is in the formula I
A=1 wherein, 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 shown in (II) formula:
Described function monomer is
Or
A is (CF
2)
hOr (CF
2)
iO(CF
2)
jIn a kind of, the integer of h, i, j=2-6 wherein; B is-SO
3M or
The integer of a=1-4 wherein, 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 the organic solvent, contain functional group-SO in function monomer and the precursor resin
2The amount of F is than being (1 ~ 10): (10 ~ 1), the mass volume ratio of described precursor resin and organic solvent are 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 ℃, and constant temperature stirred 1-60 hour; Filter, wash, in 70-85 ℃ 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, also add the reaction promoter triethylamine in the reaction system, the volume ratio of triethylamine and organic solvent is 1.5 ~ 5:50.
Preparation in accordance with the present invention is preferred, and the throw out after the filtration is with chloroform or acetone, dilute hydrochloric acid, water washing.
The ratio of different structure function monomer can be regulated according to the size of design loading capacity, the height of mechanical property; Do not do arbitrarily requirement by the functional group ratio that the graft modification of different structure function monomer obtains, (x+y)/(x+y+x '+y ') ratio is percentage of grafting, requires adjustable according to product performance.
The number-average molecular weight of the perfluorinated ion exchange resin of aforesaid method preparation 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 cleaned and added successively deionized water, emulsifying agent, reaction promoter starts whipping appts, replace three times, in the detection reaction still oxygen level qualified after, a certain amount of alkene ether monomer of adding in the reactor, described alkene ether monomer is to have structural formula:
(monomer 1, the integer of q=1-4) or
(monomer 2, r, one of the integer of t=1-4) or two kinds mixing, in reactor, be filled with tetrafluoroethylene monomer, and keep reaction pressure, be warming up to temperature of reaction, add initiator solution with volume pump in reactor, initiated polymerization continues to pass into tetrafluoroethylene monomer and keeps reacting kettle inner pressure constant, add initiator in the reactor during this time and keep speed of response, reaction is cooled to room temperature after finishing, and reclaims simultaneously unreacted tetrafluoroethylene monomer, material in the still is emitted, by the high speed shear breakdown of emulsion, separate obtaining the white polymer powder, after pure water washing 3-5 time, in 120 ℃ of baking ovens, dry, obtain the functional resin with the sulfonic acid fluoride side group.
Above-described emulsifying agent, reaction promoter, initiator are routine techniques in the 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 formula II with the precursor resin of sulfonic acid fluoride side group, with meeting generating portion sulfimide side group after the function monomer grafting, synthetic perfluorinated ion exchange resin can satisfy loading capacity height, requirement that physical strength is large simultaneously, its loading capacity can reach more than the 2.3mmol/g dried resin, physical strength still surpasses 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 at side group, has strengthened simultaneously its characteristic as solid super-strong acid; The resin of preparation has kept the strongly-acid of perfluorinated sulfonic resin, and is 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 the 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 anti-various chemical mediator, also have high electroconductibility and high mechanical strength, low membrane resistance is highly suitable in fuel cell or the chlor-alkali electrolysis cell and uses.
4, preparation method's step of perfluorinated ion exchange resin of the present invention is simple, and the usage ratio of function monomer can arbitrarily be regulated flexible operation according to the size of loading capacity, the height of mechanical property in the raw material.
Description of drawings:
Fig. 1 is the IR spectrogram of the perfluorinated ion exchange resin of embodiment 1 preparation.
Fig. 2 is the IR spectrogram of the perfluorinated ion exchange resin of embodiment 2 preparations.
Fig. 3 is the IR spectrogram of the perfluorinated ion exchange resin of embodiment 3 preparations.
Embodiment
Also the present invention will be further described by reference to the accompanying drawings below by specific embodiment.The dilute hydrochloric acid concentration of washing usefulness is 5 ~ 10wt% among the embodiment.
Embodiment 1: a kind of preparation method of perfluorinated ion exchange resin, and step is as follows:
The preparation precursor resin:
The 10L reactor being cleaned and add the aqueous solution, the 100ml mass concentration that 6L deionized water, 100ml contain the 8g ammonium perfluorocaprylate is 3% dobell's solution, start whipping appts, replace three times, after tested after the interior oxygen level qualified (being lower than 5ppm) of reactor, vacuumize, (structural formula is: CF to add 500g sulfonic acid fluoride side group alkene ether monomer 1 in the reactor
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 ℃, adding the 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, add 25g initiator solution (being that mass concentration is 3% ammonium persulfate aqueous solution) every 30min, stopped reaction behind the reaction 2h; Temperature of reaction kettle is down to room temperature, reclaim simultaneously unreacted tetrafluoroethylene monomer, oyster white slurry in the still is put into after-treatment system by lower dispensing valve, by the high speed shear breakdown of emulsion, separate and obtain the white polymer powder, after pure water washing 3-5 time, in 120 ℃ of baking ovens, dry, obtain the precursor resin with the 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 integrated value by the fluorine nuclear-magnetism contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 1.86mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 356 ℃.
The preparation of perfluorinated ion exchange resin:
Get the H of 50g precursor resin and 26g
2NSO
2CF
2CF
2SO
3H adds in the 500ml ethylene dichloride, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 60 ℃, and constant temperature stirred 48 hours; With chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, obtain perfluorinated ion exchange resin 68.3g after filtering.
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 the 2.47mmol/g dried resin; Calculate according to the titration measuring result, with-SO
2F is benchmark, and the knot branch rate of resin is 81%.To obtain carrying out the TGA test after perfluorinated ion exchange resin transfers the H type to, the initial decomposition temperature of perfluorinated ion exchange resin is 290 ℃ under the nitrogen atmosphere;
IR spectrogram: 1056cm
-1SO appears
3The stretching vibration peak of H, 1468cm
-1Place-SO
2The peak intensity of F obviously weakens, and 1200 and 1148cm
-1Two absorptions the strongest cause 984cm by the CF vibration
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 2: a kind of preparation method of perfluorinated ion exchange resin may further comprise the steps:
According to the precursor resin of the method for embodiment 1 preparation with the sulfonic acid fluoride side group, difference is: add 600g sulfonyl fluoride monomer 1(CF
2=CF-O-CF
2CF
2-SO
2F) and 300g sulfonyl fluoride monomer 2(CF
2=CF-O-CF
2CF(CF
3)-O-CF
2CF
2SO
2F), and carry out polyreaction under the reaction pressure of maintenance 1.8MPa, obtain precursor resin.
The data of precursor resin:
Through F
19NMR, IR analyze and to turn out to be ter-polymers, and the molecular fraction that the integrated value by the fluorine nuclear-magnetism contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 2.18mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 343 ℃.
Get (the CH of 50g precursor resin and 60g
3)
3SiHNSO
2CF
2CF
2OCF
2CF
2SO
3H adds in the 500ml ethylene dichloride, under argon gas atmosphere, is heated to 60 ℃, and constant temperature stirred 48 hours, with acetone, dilute hydrochloric acid, water washing, obtains sample 80 ℃ of dryings 24 hours in vacuum drying oven after filtering, and obtains 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 the 2.31mmol/g dried resin, according to the volumetry test result calculations, with-SO
2F is benchmark, and the knot branch rate of resin is 70.5%, perfluorinated ion exchange resin is transferred to carry out the TGA test behind the H type, and the resin initial decomposition temperature is 287 ℃ under the nitrogen atmosphere.
The IR spectrogram, as shown in Figure 2: 1058cm
-1SO appears
3The stretching vibration peak of H, 1468cm
-1Place-SO
2The peak intensity of F obviously weakens, and 1200 and 1148cm
-1Two absorptions the strongest cause 984cm by the CF vibration
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 3: a kind of preparation method of perfluorinated ion exchange resin may further comprise the steps:
Reactor is cleaned and adding 6L deionized water, 100ml contains the aqueous solution of 10g sodium laurylsulfonate, start whipping appts, vacuumize, fill high pure nitrogen displacement three times, oxygen level vacuumizes after below the 10ppm in the reactor after tested, adds 1000g sulfonic acid fluoride side group alkene ether monomer 1 (CF by the liquid feeding valve in reactor
2=CF-O-CF
2-CF
2-SO
2F) after, in reactor, fill tetrafluoroethylene monomer pressure to 2.0MPa, be warming up to 55 ℃, adding the 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 the 30g initiator solution every 30min, behind the reaction 2h, stop to add initiator, after allowing reaction proceed 30min, stop to add 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 the still is put into after-treatment system after by lower dispensing valve, adding 1L concentration is 10% ammonium carbonate solution, separate and obtain the white polymer powder, with pure water washing 3-5 time, in 100 ℃ of baking ovens, dry, obtain the precursor resin with the sulfonic acid fluoride side group.
The data analysis of precursor resin:
Analyze through IR and to turn out to be binary polymer, the molecular fraction that the integrated value by the diffuse reflectance infrared spectroscopy peak contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 1.4mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 392 ℃.
Get the H of the above-mentioned resin of 50g and 40g
2NSO
2CF
2CF
2CF
2CF
2SO
3H adds in the 500ml acetonitrile, under argon gas atmosphere, splashes into triethylamine 15ml, is heated to 80 ℃, and constant temperature stirred 20 hours; With acetone, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, obtain perfluorinated ion exchange resin 73g after filtering.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom with volumetry is the 1.9mmol/g dried resin, according to the volumetry test result calculations, with-SO
2F is benchmark, and the knot branch rate of resin is 95%.Transfer perfluorinated ion exchange resin to the H type and carry out the TGA test, the resin initial decomposition temperature is 276 ℃ under the nitrogen atmosphere.
The IR spectrogram, as shown in Figure 3: 1056cm
-1SO appears
3The stretching vibration peak of H, 1468cm
-1Place-SO
2The peak intensity of F obviously weakens, and 1200 and 1148cm
-1Two absorptions the strongest cause 720cm by the CF vibration
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 4: a kind of preparation method of perfluorinated ion exchange resin may further comprise the steps:
Reactor is cleaned and adding 6L deionized water, and 100ml contains the aqueous solution of 10g sodium laurylsulfonate, and 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 the reactor oxygen level after below the 10ppm, in reactor, fill tetrafluoroethylene monomer pressure to 1.1MPa, be warming up to 70 ℃, adding the 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 the 20g initiator solution every 15min, behind the reaction 2h, stop to add initiator, after allowing reaction proceed 15min, stop to add tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in the still is put into after-treatment system after by lower dispensing valve, high-speed stirring makes its breakdown of emulsion, separate and obtain the white polymer powder, with pure water washing 3-5 time, in 100 ℃ of baking ovens, dry, obtain the precursor resin with the sulfonic acid fluoride side group.
The data of precursor resin:
The molecular fraction that integrated value by the diffuse reflectance infrared spectroscopy peak contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 1.1mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 345 ℃.
Get the H of the above-mentioned resin of 50g and 35g
2NSO
2CF
2CF
2CF
2CF
2SO
3H adds in the 500ml acetonitrile, to the triethylamine that wherein is added dropwise to 30ml, under argon gas atmosphere, be heated to 80 ℃, and constant temperature stirred 20 hours, after filtering with chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, obtain perfluorinated ion exchange resin 69g.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom with volumetry is the 1.6mmol/g dried resin; According to infrared measurement ,-SO
2The F group is converted into the sulfimide group fully.The initial decomposition temperature that the TGA test obtains the resin nitrogen atmosphere is 271 ℃.
IR spectrogram: 1056cm
-1SO appears
3The stretching vibration peak of H, 1468cm
-1Place-SO
2The peak of F disappears, and 1200 and 1148cm-
1Two absorptions the strongest cause 984cm by the CF vibration
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 5:
Get the precursor resin 50g that obtains among the embodiment 4 and the H of 30g
2NSO
2CF
2CF
2CF
2CF
2SO
2NHSO
2CF
3To the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, be heated to 77 ℃ in the adding 500ml ethyl acetate, and constant temperature stirred 20 hours, with chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, obtain perfluorinated ion exchange resin 69g after filtering.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom with volumetry is the 1.29mmol/g dried resin.Calculate according to titrate the analysis result, in the precursor resin-SO
2The percentage of grafting of F is 61%.To obtain carrying out the TGA test after perfluorinated ion exchange resin transfers the H type to, the resin initial decomposition temperature is 271 ℃ under the nitrogen atmosphere.
IR spectrogram: 1632cm
-1The vibration absorption peak of N-H, 1367cm appear in the place
-1Appearance-the SO of place
2-absorption, 1468cm
-1Place-SO
2The peak of F obviously weakens, 984cm
-1The place is CF
3Vibration absorption peak, 1468cm
-1Place-SO
2The peak of F obviously weakens.
Embodiment 6:
Reactor is cleaned and adding 6L deionized water, and 100ml contains the aqueous solution of 10g ammonium perfluorocaprylate, and 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, oxygen level adds 960g sulfonic acid fluoride side group alkene ether monomer (CF by the liquid phase feeding valve after below the 10ppm in the reactor in reactor after tested
2=CF-O-CF
2CF
2CF
2CF
2SO
2F), be warming up to 70 ℃, fill tetrafluoroethylene monomer pressure to 1.3MPa in reactor, adding the 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 the 20g initiator solution every 15min, behind the reaction 2h, stop to add initiator, after allowing reaction proceed 15min, stop to add tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in the still is put into after-treatment system after by lower dispensing valve, high-speed stirring makes its breakdown of emulsion, separate and obtain the white polymer powder, with pure water washing 3-5 time, in 100 ℃ of baking ovens, dry, obtain the precursor resin with the sulfonic acid fluoride side group.The data analysis of precursor resin is as follows:
Through F
19NMR, IR analyze and to turn out to be ter-polymers, and the molecular fraction that the integrated value by the fluorine nuclear-magnetism contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 1.5mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 377 ℃.
Get above-mentioned precursor resin 50g resin, with (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 ℃, and constant temperature stirred 8 hours, leached toner, uses washing with acetone 2-3 time, dries in 80 ℃ vacuum drying oven, obtains perfluorinated ion exchange resin 61.2g.
The test of perfluorinated ion exchange resin:
The exchange capacity of surveying products therefrom with volumetry is the 1.85mmol/g dried resin, and according to exchange capacity titration test result calculations, getting the precursor resin percentage of grafting is 51%.To obtain carrying out the TGA test after perfluorinated ion exchange resin transfers the H type to, resin initial decomposition temperature under nitrogen atmosphere is 263 ℃.
The IR spectrogram: SO appears in the 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 absorptions the strongest cause 984cm by the CF vibration
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 7: a kind of preparation method of perfluorinated ion exchange resin, and step is as follows:
Reactor is cleaned and adding 6L deionized water, 100ml contains the aqueous solution of 15g ammonium perfluorocaprylate, 200ml contains the aqueous solution of 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 the reactor oxygen level after below the 10ppm, vacuumize, in reactor, add 1100g sulfonic acid fluoride side group alkene ether monomer 1 (CF by the 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 ℃, adding the 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 the 30g initiator solution every 30min, behind the reaction 2h, stop to add initiator, after allowing reaction proceed 30min, stop to add tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in the still is put into after-treatment system after by lower dispensing valve, the high-speed stirring breakdown of emulsion, separate and obtain the white polymer powder, with pure water washing 3-5 time, in 100 ℃ of baking ovens, dry, obtain the precursor resin with the sulfonic acid fluoride side group.The data analysis of precursor resin:
The molecular fraction that integrated value by the diffuse reflectance infrared spectroscopy peak contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 1.24mmol/g dried resin, and TGA test resin is under nitrogen atmosphere, and initial decomposition temperature is 353 ℃; Show that according to infrared result percentage of grafting is 100%.
Get above-mentioned resin 50g, with (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 ℃, constant temperature stirred 8 hours, leached toner, used washing with acetone 2-3 time, dried in 80 ℃ vacuum drying oven, obtained perfluorinated ion exchange resin 71.6g.
The test of perfluorinated ion exchange resin:
The exchange capacity of the product of surveying with volumetry is the 1.73mmol/g dried resin, carries out the TGA test after perfluorinated ion exchange resin is changed into the H type, and the initial decomposition temperature of resin under nitrogen atmosphere is 281 ℃.
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 absorptions the strongest cause 720cm by the CF vibration
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 8: a kind of preparation method of perfluorinated ion exchange resin may further comprise the steps:
Reactor is cleaned and adding 6L deionized water, and 100ml contains the aqueous solution of 10g Sodium perfluorooctanoate, and 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
2F) and 400g sulfonic acid fluoride side group alkene ether monomer 2 (CF
2=CF-OCF
2-CF (CF
3)-O-CF
2CF
2CF
2SO
2F), start whipping appts, vacuumize, fill high pure nitrogen displacement three times, oxygen level improves stirring velocity to 500rpm, pre-emulsification 20min after below the 10ppm in the reactor after tested, in reactor, fill tetrafluoroethylene monomer pressure to 1.5MPa, be warming up to 60 ℃, adding the 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 the 25g initiator solution every 30min, behind the reaction 2h, stop to add initiator, after allowing reaction proceed 30min, stop to add tetrafluoroethylene monomer.Lower the temperature to reactor by cooling recirculation system, reclaim unreacted tetrafluoroethylene monomer by recovery system simultaneously, oyster white slurry in the still is put into after-treatment system after by lower dispensing valve, after high speed shear, separate and obtain the white polymer powder, after pure water washing 3-5 time, in 100 ℃ of baking ovens, dry, obtain the precursor resin with the sulfonic acid fluoride side group.The data analysis of precursor resin:
Through F
19NMR, IR analyze and to turn out to be ter-polymers, and the molecular fraction that the integrated value by the fluorine nuclear-magnetism contains tetrafluoroethylene as can be known in the polymer architecture 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 the overall resin-and SO
2F content is the 1.5mmol/g dried resin, and the initial decomposition temperature of TGA test resin nitrogen atmosphere is 358 ℃.
Get above-mentioned precursor resin 50g, with 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 the nitrogen atmosphere condition, be heated to 70 ℃, to wherein slowly dripping the 30g triethylamine, after being added dropwise to complete, continue constant temperature and stirred 8 hours, leach toner, with ether washing 2-3 time, oven dry obtains modified resin in 80 ℃ vacuum drying oven, be 5% the KOH aqueous solution after transition with it with concentration, use deionized water wash, obtain perfluorinated ion exchange resin 80.5 after in 80 ℃ vacuum drying oven, drying, through infrared test ,-SO
2The F completely dissolve proves that the resin grafting is complete.
The test of perfluorinated ion exchange resin:
Surveying the products therefrom exchange capacity with volumetry is the 1.87mmol/g dried resin, will obtain carrying out the TGA test after perfluorinated ion exchange resin changes into the H type, and the initial decomposition temperature of resin under nitrogen atmosphere is 277 ℃.
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 absorptions the strongest cause 984cm by the CF vibration
-1The CF of place
3The absorption of vibrations grow, 720cm
-1, 641cm
-1Caused by the TFE vibration.
Embodiment 9:
Get precursor resin 50g resin among the embodiment 1 and the H of 30g
2NSO
2(CF
2)
3SO
3K adds in the 500ml butyl propionate, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 60 ℃, and constant temperature stirred 48 hours; With chloroform, dilute hydrochloric acid, water washing, 80 ℃ of dryings are 24 hours in vacuum drying oven, make perfluorinated ion exchange resin after filtering.
Embodiment 10:
Get precursor resin 50g synthetic among the embodiment 1 and the H of 30g
2NSO
2(CF
2)
5SO
3NH
4Add in the 500ml butyl propionate, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, be heated to 50 ℃, and constant temperature stirred 10 hours; With chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, make perfluorinated ion exchange resin after filtering.
Embodiment 11:
Get precursor resin 50g among the embodiment 1 and the H of 40g
2NSO
2(CF
2)
6SO
3K adds in the 500ml dimethyl sulfoxide (DMSO), to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 35 ℃, and constant temperature stirred 38 hours; With chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, make perfluorinated ion exchange resin after filtering.
Embodiment 12:
Get precursor resin 50g among the embodiment 1 and the (CH of 40g
3)
3SiHNSO
2(CF
2)
2OCF
2CF
2SO
3H adds in the 500ml dimethyl sulfoxide (DMSO), under argon gas atmosphere, is heated to 40 ℃, and constant temperature stirred 58 hours; Use chloroform, dilute hydrochloric acid, water washing repeatedly after filtering; 80 ℃ of dryings are 24 hours in vacuum drying oven, make perfluorinated ion exchange resin.
Embodiment 13:
Get precursor resin 50g among the embodiment 1 and the H of 26g
2NSO
2(CF
2)
2O(CF
2)
4SO
2NHSO
2CF
3Add in the 500ml dimethyl sulfoxide (DMSO), to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, be heated to 45 ℃, and constant temperature stirred 50 hours; With chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, make perfluorinated ion exchange resin after filtering.
Embodiment 14:
Get precursor resin 50g synthetic among the embodiment 1 and the H of 26g
2NSO
2(CF
2)
2O(CF
2)
5SO
2NNH
4SO
2(CF
2)
2F adds in the 500ml ethylene dichloride, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 50 ℃, and constant temperature stirred 60 hours; With chloroform, dilute hydrochloric acid, water washing repeatedly, 80 ℃ of dryings are 24 hours in vacuum drying oven, make perfluorinated ion exchange resin after filtering.
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 the 500ml ethylene dichloride, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 60 ℃, and constant temperature stirred 60 hours; Subsequent disposal makes perfluorinated ion exchange resin with embodiment 1.
Embodiment 16:
Get precursor resin 50g among the embodiment 1 and the H of 30g
2NSO
2(CF
2)
2O(CF
2)
5SO
2NNH
4SO
2(CF
2)
2F adds in the 500ml acetonitrile, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 75 ℃, and constant temperature stirred 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 the 500ml acetonitrile, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 60 ℃, and constant temperature stirred 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 the 500ml ethyl acetate, to the triethylamine that wherein is added dropwise to 50ml, under argon gas atmosphere, is heated to 70 ℃, and constant temperature stirred 48 hours; Subsequent disposal makes perfluorinated ion exchange resin with embodiment 1.
Claims (9)
1. perfluorinated ion exchange resin is characterized in that this perfluorinated ion exchange resin has the structure shown in the logical formula I:
Wherein m, n, p are the integer of 1-20, and r, t, q are the integer of 1-4, and x, x ', y, y ' are 0,1,2,3,4 or 5, and x, y are not 0,0＜(x+x ')/(x+x '+y+y ')＜1 simultaneously;
A is (CF in the formula
2)
hOr (CF
2)
iO(CF
2)
j, the integer of h, i, j=2-6 wherein;
B is-SO in the formula
3M or
The integer of a=1-4 wherein, M is H, NH
4Or metal ion.
2. perfluorinated ion exchange resin according to claim 1 is characterized in that: A is-CF in the formula I
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-; Preferred A is CF
2CF
2OCF
2CF
2-or-CF
2CF
2CF
2CF
2-.
3. perfluorinated ion exchange resin according to claim 1, it is characterized in that: B is in the formula I
A=1 wherein, M is H, Na, K or Li ion.
4. perfluorinated ion exchange resin according to claim 1, it is characterized in that: the number-average molecular weight of perfluorinated ion exchange resin is 10-60 ten thousand; Be preferably 15-30 ten thousand.
5. the preparation method of each described perfluorinated ion exchange resin of claim 1 ~ 4 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 shown in (II) formula:
Described function monomer is
Or
A is (CF
2)
hOr (CF
2)
iO(CF
2)
jIn a kind of, the integer of h, i, j=2-6 wherein; B is-SO
3M or
The integer of a=1-4 wherein, 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 the organic solvent, contain functional group-SO in function monomer and the precursor resin
2The amount of F is than being (1 ~ 10): (10 ~ 1), the mass volume ratio of described precursor resin and organic solvent are 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 ℃, and constant temperature stirred 1-60 hour; Filter, wash, in 70-85 ℃ of vacuum-drying 2-30 hour, obtain perfluorinated ion exchange resin.
6. the preparation method of perfluorinated ion exchange resin according to claim 5 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
3In H and the corresponding salt thereof one or more.
7. the preparation method of perfluorinated ion exchange resin according to claim 5 is characterized in that, also adds the reaction promoter triethylamine in the reaction system, and the volume ratio of triethylamine and organic solvent is 1.5 ~ 5:50.
8. the preparation method of perfluorinated ion exchange resin according to claim 5 is characterized in that, the throw out after the filtration is with chloroform or acetone, dilute hydrochloric acid, water washing.
9. the preparation method of perfluorinated ion exchange resin according to claim 5 is characterized in that, the precursor resin of described general formula (II) adopts emulsion polymerization way to synthesize, and step is as follows:
Reactor cleaned and added successively deionized water, emulsifying agent, reaction promoter starts whipping appts, replace three times, in the detection reaction still oxygen level qualified after, a certain amount of alkene ether monomer of adding in the reactor, described alkene ether monomer is to have structural formula:
(monomer 1, the integer of q=1-4) or
(monomer 2, r, one of the integer of t=1-4) or two kinds mixing, in reactor, be filled with tetrafluoroethylene monomer, and keep reaction pressure, be warming up to temperature of reaction, add initiator solution with volume pump in reactor, initiated polymerization continues to pass into tetrafluoroethylene monomer and keeps reacting kettle inner pressure constant, add initiator in the reactor during this time and keep speed of response, reaction is cooled to room temperature after finishing, and reclaims simultaneously unreacted tetrafluoroethylene monomer, material in the still is emitted, by the high speed shear breakdown of emulsion, separate obtaining the white polymer powder, after pure water washing 3-5 time, in 120 ℃ of baking ovens, dry, obtain the functional resin with the sulfonic acid fluoride side group.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133477A (en) * | 2021-11-26 | 2022-03-04 | 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 |
| JP2022105588A (en) * | 2018-03-15 | 2022-07-14 | 三菱マテリアル電子化成株式会社 | Fluorine-containing sulfonyl imide |
| CN114835842A (en) * | 2022-06-15 | 2022-08-02 | 浙江巨化技术中心有限公司 | Polymerization method of perfluorosulfonyl fluororesin |
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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022105588A (en) * | 2018-03-15 | 2022-07-14 | 三菱マテリアル電子化成株式会社 | Fluorine-containing sulfonyl imide |
| JP7382445B2 (en) | 2018-03-15 | 2023-11-16 | 三菱マテリアル電子化成株式会社 | A fluorine-containing sulfonylimide, a method for producing a reactive fluorine-containing sulfonylimide, and a method for producing a copolymer. |
| CN114133477A (en) * | 2021-11-26 | 2022-03-04 | 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 |
| 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 |
| CN114835842A (en) * | 2022-06-15 | 2022-08-02 | 浙江巨化技术中心有限公司 | Polymerization method of perfluorosulfonyl fluororesin |
| 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 |
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