CN101709102B - Perfluorinated resin with high exchange capacity as well as preparation method and application thereof - Google Patents
Perfluorinated resin with high exchange capacity as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high exchange capacity perfluorinated resin of two types of short side-radical sulfonyl fluoride with different structures and cyan side-radical. The resin is a polyprotonic copolymer comprising the following components in total molar fraction: 50-85 percent of tetrafluoroethylene polymerization unit, 5-49 percent of the polymerization unit of the two types of short side-radical sulfonyl fluoride vinyl ether with two different structures, and1-10 percent of cyan side-radical vinyl ether polymerization unit. A perfluorinated ion exchange membrane prepared by the resin not only has resistance to various chemical reagents, but also has high ion exchange capacity, electric conductivity, mechanical strength and dimensional stability, low membrane resistance and long service life, and is suitable for usage in fuel cells or high-temperature fuel cells. The invention also provides a preparation method and applications of the resin.
Description
Technical field
The invention belongs to the fluoro-containing macromolecule material field, relate to a kind of high-exchange-capacity perfluorinated resin and preparation method thereof that has, relate in particular to multi-component copolymer perfluorinated ion exchange resin that has short side group sulfonic acid fluoride of two kinds of different structures and cyanic acid side 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 and in chlorine industry and Proton Exchange Membrane Fuel Cells, used the seventies in last century, perfluorinated ion exchange resin had obtained extensive studies in countries in the world.
Contain ion-exchange group, the exchange membrane containing fluorine that especially contains sulfonic group and carboxylic acid group is owing to its chemically-resistant degradation property is more suitable for the ion-exchange membrane as fuel cell and chlor-alkali electrolytic cells.US3282875 is disclosed first document synthetic about sulfonyl fluoride monomer and the sulfonate resin preparation of E.I.Du Pont Company, employing be emulsion polymerization in the aqueous systems, the functional monomer structure that 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 be E.I.Du Pont Company disclosed one piece about short side group sulfonyl fluoride monomer and the preparation of sulfonate resin and the patent of performance, the sulfonyl fluoride monomer structure of being reported is FO
2SCF
2CF
2OCF=CF
2, preparation route complicacy and yield are lower.Introduced the sulfonate resin by the preparation of novel texture perfluor sulfonyl fluorine monomer among US3884885, the US3041317, the structure of the sulfonyl fluoride monomer of employing is R
fCF=CFSO
2F, this monomeric reactive behavior is lower.US4358545, US4417969 are the disclosed patents of U.S. Dow chemical company, and this patent relates generally to and adopts short side group monomer (CF
2=CFOCF
2CF
2SO
2The character and the application of the multipolymer that F) forms with fluorine-containing vinyl monomer copolymerization such as tetrafluoroethylene; The sulfonate resin of preparation is owing to be to adopt solution film-forming by this method; Be difficult to prepare film, and the mechanical strength of film is not high enough, described in patent US4661411, US5718947.US4940525 discloses a kind of preparation method who uses the sulfonyl fluoride monomer copolymer resins of vinylidene fluoride monomers and short side group, and this resin has not possessed the perfluor structure, and is less better aspect erosion resistance.Announced the preparation of low EW value sulfonate resin among the EP0289869, the sulfonyl fluoride monomer of employing is the present general monomer structure that adopts, and its EW value is between 575-800.EP1451233 has reported the method through the low EW value resin of miniemulsion preparation.Patent US7022428, US7041409, US6861489 have reported the preparation of the sulfonate resin of low EW value, adopt the mini-emulsion polymerization reaction, and in polymerization process, have added the monomer that contains diene ether, and diene ether monomer structure is CF
2=CF-O-CF
2CF
2CF
2-OCF=CF
2, the EW value is between 625-850.GB1034197 discloses and has contained sulfonic perfluorinated sulfonic acid polymer, and EP1091435 discloses a kind of structure of block sulfonate resin.Above-mentioned polymkeric substance all is to use tetrafluoroethylene monomer and sulfonic acid fluoride side group alkene ether (such as CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2F) copolymerization is perhaps further introduced monomer component such as the US4940525 that other side groups that do not have ion exchanging function contain two keys in above-mentioned polymerization system; Polymerization method can adopt this area technique known, like solution polymerization (US2393967, US3041317 etc.), letex polymerization (US4789717, US4864006 etc.), micro-emulsion polymerization (like US6639011, EP1172382, US5608022 etc.), dispersion polymerization, suspension polymerization, mini-emulsion polymerization (EP1451233) or the like.The suitable hydrolysis reaction that these polymkeric substance with sulfonic acid fluoride side group can pass through sulfonic acid fluoride obtains the free sulfonic group, is used for fields such as fuel cell, electrolyzer, diffusion dialysis, catalysis, precious metal recovery as ion-exchange membrane.
A most important purposes of perfluorinated sulfonic resin is exactly that it is as the application of mould material in fuel cell; A very important requirement to this type ion-exchange membrane is its ionic conductivity, and in order to improve specific conductivity, known a kind of way is to improve the loading capacity of sulfonate resin; But increase along with loading capacity; Its mechanical property descends, under the extreme case, and the ion exchange resin of high-exchange-capacity even can be dissolved in the water.Mention among the patent EP0031724: the loading capacity total amount for the film that in electric groove, uses will be between 0.5-1.6mmol/g (dried resin), preferred 0.8-1.2mmol/g.If the loading capacity total amount is less than 0.5mmol/g, then the resistivity of film is too high, and bath voltage and energy consumption all can be than higher; Can not satisfy industrial applications; If the loading capacity total amount is greater than 1.6mmol/g, then the mechanical property of mould material is bad, and life-span and use aspect are restricted.In order to improve exchange capacity and to reduce the mechanicalness loss of energy as far as possible; The other way is to adopt composite package; The way that adopts like US5654109, US5246792 is that bilayer or trilamellar membrane material are compound, and inner film has high EW value, bears the physical strength effect; Outside film plays the ionic conduction effect for low EW value; US5981097 adopts multilayer different ions exchange capacity film to carry out compound; And US5082472 has adopted the resin compounded of polytetrafluoroethylporous porous membrane and the low EW value of two-way stretch to obtain composite package to use.Though these ways have kept the physical strength of film to a certain extent, in the raising of the homogeneity of ionic conduction and specific conductivity, certain shortcoming is arranged still.
For improving the physical strength and the dimensional stability of exchange membrane; Resin structure is being carried out in the way of modification; Known way have in resin structure introduce can be crosslinked group such as US20020014405, US6767977 in resin structure, introduced diene monomers; One Chinese patent application numbers 200480033602.1 discloses a kind of way of in polymerization system, introducing itrile group, and is crosslinked through after handling itrile group being carried out, and increases the physical strength of film.One Chinese patent application numbers 200480033631.8 discloses a kind of cyanic acid, chlorine, iodo in polymerization system, introduced, and carries out crosslinked through electron beam.Existing other a kind of way is to shorten the side group of comonomer sulfonic acid fluoride at present; When increasing loading capacity, promote the physical strength of mould material; But US6680346 mentions in patent: by lacking side group sulfonyl fluoride monomer synthetic polymkeric substance because the difference of polymerizing condition can produce cyclization; Caused the chain transfer of polyreaction, thereby molecular weight reduces, the mechanical strength of material reduces; And, the lifting of loading capacity and the stability of material have been limited along with short side group sulphonyl monomer and tetrafluoroethylene monomer molar ratio increase the generation that can further promote this type side reaction.
A most important purposes of perfluorinated sulfonic resin be exactly its as the application of mould material in fuel cell, be its chemicalstability and intensifier electrode catalyzer anti-carbon monoxide (CO) toxic ability to this type by an important requirement of ion-exchange membrane and the formed membrane electrode of catalyst layer.The working temperature of the fuel cell membrane electrode of current broad research and demonstration is between 25-80 ℃; The poisoning behavior promptly can take place in the catalyst layer that reaches membrane electrode in the 10ppm environment at CO content; In order to overcome the many insoluble difficulties of present low-temperature fuel cell membrane electrode, as improving catalyst activity and utilization ratio, intensifier electrode catalyzer anti-carbon monoxide poisoning performance etc.; Effective solution is to improve the use temperature of fuel cell; When surpassing 100 ℃, catalyzer can bring up to 1 to the tolerance of CO in the membrane electrode, about 000ppm.The exploitation high temperature proton exchange film can improve the electrical efficiency of fuel cell better, reduces the cost of battery system, adapts to the business-like requirement of fuel cell more.The major country of fuel cell studies begins to drop into lot of manpower and material resources research in the world at present.The known sulfonate resin with long side group sulfonic acid fluoride of fuel cell field can not satisfy the high temperature request for utilization at present.
Summary of the invention
One object of the present invention is, a kind of high-exchange-capacity perfluorinated resin is provided, and this high-exchange-capacity perfluorinated resin has the short side group sulfonic acid fluoride and the cyanic acid side group of two kinds of different structures, has high loading capacity and favorable mechanical performance.Another object of the present invention is, a kind of preparation method of above-mentioned high-exchange-capacity perfluorinated resin is provided.Another purpose of the present invention is, a kind of ion-exchange membrane that is prepared from above-mentioned high-exchange-capacity perfluorinated resin is provided.A purpose more of the present invention is, a kind of fuel cell or electrolyzer that comprises above-mentioned ion-exchange membrane is provided.A further object of the present invention is, a kind of purposes of above-mentioned high-exchange-capacity perfluorinated resin is provided.
Above-mentioned purpose of the present invention adopts following technical scheme to realize:
On the one hand; The present invention provides a kind of high-exchange-capacity perfluorinated resin; Its short side group sulfonic acid fluoride alkene ether monomer by tetrafluoroethylene, two kinds of different structures, a kind of cyanic acid side group alkene ether monomer multi-component copolymer close and form, and this resin mainly contains with the repeating unit shown in the following formula (I):
The wherein integer of n=0-3, preferably n=0; The integer of m=2-4; The integer of a, b, c=3-15, the integer of a ', b ', c '=1-3; X/ (x+y+z)=0.2-0.7, y/ (x+y+z)=0.2-0.79, z/ (x+y+z)=0.01-0.1.
Preferably, the structural formula of the short side group sulfonic acid fluoride alkene ether monomer of said two kinds of different structures is respectively:
The structural formula of said cyanic acid side group alkene ether monomer is:
The wherein integer of n=0-3, preferably n=0; The integer of m=2-4.
Preferably; The shared molar content percentage ratio of each polymerized unit is in the said resin: the overall x in tetrafluoroethylene polymerization unit is 50～85%; The overall x of short side group sulphonyl fluroxene polymerized unit of two kinds of different structures is 5～49%, and the overall x of cyanic acid side group alkene ether polymerized unit is 1～10%.
Preferably; The shared molar content percentage ratio of each polymerized unit is in the said resin: the overall x in tetrafluoroethylene polymerization unit is 70～80%; The overall x of short side group sulphonyl fluroxene polymerized unit of two kinds of different structures is 15～29%, and the overall x of cyanic acid side group alkene ether polymerized unit is 1～5%.
Preferably, the mol ratio of the short side group sulphonyl fluroxene polymerized unit (1) of two kinds of different structures and (2) is 0.2-0.8: 0.8-0.2 in the said resin; Be preferably 0.4-0.6: 0.6-0.4.
On the other hand; The present invention provides the preparation method of above-mentioned high-exchange-capacity perfluorinated resin; This preparation method comprises that the short side group sulfonic acid fluoride alkene ether monomer that makes tetrafluoroethylene, two kinds of different structures, a kind of cyanic acid side group alkene ether monomer carry out polyreaction under the initiator effect, and preferably, the reaction times of said polyreaction is 1～8 hour; Temperature of reaction is 10～80 ℃, and reaction pressure is 2～10MPa.
Preferably, said initiator is selected from N
2F
2, in perfluoroalkyl superoxide and the persulphate one or more.
Preferably, said perfluoroalkyl superoxide is to be selected from peroxo-perfluoroalkyl acyl compound, peroxo-perfluoro alkoxy acyl compounds, the fluorine-containing alkyl acyl compound of peroxo-part and the peroxo-part fluoroalkoxy acyl compounds one or more; Said persulphate is to be selected from persulfuric acid ammonium salt, basic metal persulfide and the earth alkali metal persulfide one or more.
More preferably, said perfluoroalkyl superoxide for be selected from perfluoro propionyl superoxide, 3-chlorine fluorine propionyl superoxide, perfluor methoxyl group acetyl pexoxide,
-H-perfluor butyryl superoxide,
-SO
2F-perfluor-2,5,8-trimethylammonium-3,6,9-trioxa-undecyl superoxide, CF
3CF
2CF
2CO-OO-COCF
2CF
2CF
3,
CF
3CF
2CF
2OCFCF
3CO-OO-COCFCF
3OCF
2CF
2CF、
CF
3CF
2CH
2CO-OO-COCH
2CF
2CF
3And CF
3OCF
2CF
2CO-OO-COCF
2CF
2OCF
3In one or more; Said persulphate is to be selected from ammonium persulphate and the Potassium Persulphate one or more.
Preferably, said preparation method also is included in the step that aqueous phase carries out emulsion polymerization.
Preferably, in the emulsion polymerization step, emulsifying agent is selected from anionic emulsifier, for example sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate and sodium alkylarysulfonate; And nonionic emulsifier, alkyl phenol polyether alcohols for example is like in polyoxyethylene nonylphenol, polyoxyethylene fatty acid and the polyoxyethylene fatty acid ether one or more.
More preferably; In the emulsion polymerization step; The mass percent concentration of emulsifying agent in water is 0.1-20%; The mass percent concentration of short side group sulfonic acid fluoride alkene ether monomer in water of two kinds of different structures is 5-30%, and the mass percent concentration of cyanic acid side group alkene ether monomer in water is 1～12%.
Another aspect, the present invention provides a kind of ion-exchange membrane that is prepared from above-mentioned high-exchange-capacity perfluorinated resin.
On the one hand, the present invention provides a kind of fuel cell or electrolytic cell device that comprises above-mentioned ion-exchange membrane again; Said fuel cell is preferably proton membrane fuel battery or high-temperature fuel cell, more preferably the high temperature proton membrane fuel battery; Said electrolyzer is preferably chlor-alkali electrolysis cell.
On the one hand, the present invention provides above-mentioned high-exchange-capacity perfluorinated resin to be used to make the purposes of fuel cell or electrolytic cell device intermediate ion exchange membrane again; Said fuel cell is preferably proton membrane fuel battery or high-temperature fuel cell, more preferably the high temperature proton membrane fuel battery; Said electrolyzer is preferably chlor-alkali electrolysis cell; Preferably, before the use, earlier that the cyanic acid side group is crosslinked through the chemical process cyclisation.
Compared with prior art, the present invention has the following advantages at least:
1, perfluorinated resin of the present invention has the short side group sulfonic acid fluoride and the cyanic acid side group of two kinds of different structures; Solved the opposed contradiction of prior art intermediate ion exchange capacity and physical strength, the perfluorinated resin that has high loading capacity and favorable mechanical performance simultaneously is provided.
2, perfluorinated resin of the present invention has the short side group sulfonic acid fluoride and the cyanic acid side group of two kinds of different structures; Solved short side group sulfonic acid fluoride alkene ether monomer chain transfer reaction has taken place in polymerization process; The not high enough problem of molecular resin amount that obtains; Concrete reaction mechanism can be following: one of which, adopted two kinds of short side group sulfonic acid fluoride alkene ether monomers in the polymerization process with different structure, and these two kinds of monomers act synergistically each other; Its two, have cyanic acid alkene ether in the polymerization system, interact with other two kinds of alkene ether monomers when participating in polyreaction, the existence of these different sorts alkene ethers makes polyreaction work in coordination with to carry out to the HMW direction, eliminated the chain transfer cyclization.
3, the present invention adopts tetrafluoroethylene (TFE) and two kinds of short side group sulfonic acid fluoride alkene ether monomer and cyanic acid side group alkene ether monomers that have different structure to carry out multi-component copolymer; Obtain HMW high-exchange-capacity perfluorinated resin, this multiple copolymer has high chemicalstability, high loading capacity and good high-temperature mechanical stability.
The perfluorinated resin of high-exchange-capacity of the present invention can be used for preparing the ion-exchange membrane of devices such as fuel cell (for example high-temperature fuel cell) and chlor-alkali electrolytic cells.The mould material of using this resins has high current efficiency, low membrane resistance, high dimensional stability and higher physical strength.
Below be detailed description of the present invention:
The present invention provides a kind of short side group sulfonic acid fluoride of two kinds of different structures and high-exchange-capacity perfluorinated resin of cyanic acid side group of having; This perfluorinated resin is closed and is formed by the short side group sulfonic acid fluoride alkene ether monomer of tetrafluoroethylene, two kinds of different structures, a kind of cyanic acid side group alkene ether monomer multi-component copolymer, and the molecular formula of polymer chain is:
The wherein integer of n=0-3, preferably n=0; The integer of m=2-4; The integer of a, b, c=3-15, the integer of a ', b ', c '=1-3; X/ (x+y+z)=0.2-0.7, y/ (x+y+z)=0.2-0.79, z/ (x+y+z)=0.01-0.1.
The shared molar content percentage ratio of various polymerized units in the polymkeric substance: the overall x in tetrafluoroethylene polymerization unit is 50～85%; The overall x of short side group sulphonyl fluroxene polymerized unit of two kinds of different structures is 5～49%, and the overall x of cyanic acid side group alkene ether polymerized unit is 1～10%.
Preferably; The shared molar content percentage ratio of various polymerized units in the polymkeric substance: the overall x in tetrafluoroethylene polymerization unit is 70～80%; The overall x of sulfonic acid fluoride side group alkene ether polymerized unit of two kinds of different structures is 15～29%, and the overall x of cyanic acid side group alkene ether polymerized unit is 1～5%.
The structural formula of the short side group sulfonic acid fluoride alkene ether monomer of described two kinds of different structures is respectively:
The structural formula of described cyanic acid side group alkene ether monomer is:
N=0-3 in the formula, preferably n=0; The integer of m=2-4.
The number-average molecular weight of above-mentioned high-exchange-capacity perfluorinated resin is 10～600,000, is preferably 15～300,000, most preferably is 18-25 ten thousand.The MWD numerical value of above-mentioned high-exchange-capacity perfluorinated resin (being meant that weight-average molecular weight is than number-average molecular weight) is 1.5-2.0.
The present invention provides the preparation method of the perfluorinated ion exchange resin of above-mentioned short side group sulfonic acid fluoride that has two kinds of different structures and cyanic acid side group; This preparation method be the short side group sulfonic acid fluoride alkene ether monomer through tetrafluoroethylene, two kinds of different structures, a kind of cyanic acid side group alkene ether monomer 10～80 ℃, under action of evocating, carry out copolyreaction (polyreaction) and prepare; The reaction times of this copolyreaction is 1～8 hour, and reaction pressure is 2～10MPa.
Among the above-mentioned preparation method, initiator can use initiator well known in the art, also can use homemade initiator.
Said initiator is selected from: N
2F
2, perfluoroalkyl superoxide or persulphate.
Preferably, said perfluoroalkyl superoxide comprises: peroxo-perfluoroalkyl acyl compound, peroxo-perfluoro alkoxy acyl compounds, the fluorine-containing alkyl acyl compound of peroxo-part and peroxo-part fluoroalkoxy acyl compounds.More preferably, said perfluoroalkyl superoxide be perfluoro propionyl superoxide, 3-chlorine fluorine propionyl superoxide, perfluor methoxyl group acetyl pexoxide,
-H-perfluor butyryl superoxide,
-SO
2F-perfluor-2,5,8-trimethylammonium-3,6,9-trioxa-undecyl superoxide, CF
3CF
2CF
2CO-OO-COCF
2CF
2CF
3, CF
3CF
2CF
2OCFCF
3CO-OO-COCFCF
3OCF
2CF
2CF
3, CF
3CF
2CH
2CO-OO-COCH
2CF
2CF
3Or CF
3OCF
2CF
2CO-OO-COCF
2CF
2OCF
3
Preferably, said persulphate comprises persulfuric acid ammonium salt, basic metal persulfide or earth alkali metal persulfide; More preferably, said persulphate is ammonium persulphate or Potassium Persulphate etc.
Preferably, the mol ratio of the short side group sulphonyl fluroxene polymerized unit of tetrafluoroethylene polymerization unit, two kinds of different structures and cyanic acid side group alkene ether polymerized unit is in the resin: 50～85: 5～49: 1～10.
Preferably, the short side group sulphonyl fluroxene polymerized unit (1) of two kinds of different structures and (2) the mol ratio 0.2-0.8 in resin: 0.8-0.2; More preferably, the short side group sulphonyl fluroxene polymerized unit (1) of two kinds of different structures and (2) mol ratio in resin are 0.4-0.6: 0.6-0.4.
Preferably, above-mentioned copolyreaction is carried out letex polymerization at aqueous phase, and concrete emulsion polymerization is following:
1) reaction kettle is cleaned after; Two kinds short side group sulfonic acid fluoride alkene ether monomers, cyanic acid side group alkene ether monomer and emulsifying agents adding pure water, different ratios; The oeverall quality percentage concentration of emulsifying agent in water is 0.1-20%; The mass percent concentration of two kinds short side group sulphonyl fluroxenes in water is 5-30%, and the mass percent concentration of cyanic acid side group alkene ether monomer in water is 1～12%;
Wherein, said emulsifying agent comprises anionic emulsifier and nonionic emulsifier.Said anionic emulsifier comprises sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate, sodium alkylarysulfonate etc.; Said nonionic emulsifier comprises the alkyl phenol polyether alcohols, like polyoxyethylene nonylphenol, polyoxyethylene fatty acid, polyoxyethylene fatty acid ether.Mentioned emulsifier can use separately also can multiple composite use.
2) in reaction kettle, filling tetrafluoroethylene monomer to pressure through the aerometer measuring tank is 2-10MPa;
3) reaction kettle is warming up to 10～80 ℃, in reaction system, adds the initiator initiation reaction through volume pump and carries out, and continues to add tetrafluoroethylene monomer and initiator to reaction kettle, keeps reaction kettle reaction pressure 2-10MPa, and the reaction times is 1～8 hour;
When 4) reaction finishes, stop in reaction kettle, to add initiator and tetrafluoroethylene monomer, reclaim unreacted tetrafluoroethylene monomer through reaction kettle blowdown piping and accumulator tank emptying; Obtain milky polymer paste; Liquid slurry is got in the finishing apparatus through material drain system; High speed shear; Filtering separation obtains the white polymer powder, in 100 ℃ of baking ovens, dries, and obtains having the short side group sulfonic acid fluoride of two kinds of different structures and the high-exchange-capacity perfluorinated resin of cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the filtered liq and cyanic acid side group alkene ether monomer are recycled through recovery system.
In the above-mentioned polyreaction, said initiator is selected from: N
2F
2, perfluoroalkyl superoxide or persulphate; Those skilled in the art can select initiator concentration according to the common practise of this area.
Said perfluoroalkyl superoxide comprises: peroxo-perfluoroalkyl acyl compound, peroxo-perfluoro alkoxy acyl compounds, the fluorine-containing alkyl acyl compound of peroxo-part or peroxo-part fluoroalkoxy acyl compounds.
Said persulphate comprises ammonium persulphate, alkali metal persulphate or earth alkali metal persulphate; Initiator system of ammonium persulfate or Potassium Persulphate.
Of the present inventionly have the short side group sulfonic acid fluoride of two kinds of different structures and the high-exchange-capacity perfluorinated resin of cyanic acid side group can be used for making fuel cell, for example the ion-exchange membrane of high-temperature fuel cell.
The high-exchange-capacity perfluorinated resin of short side group sulfonic acid fluoride that has two kinds of different structures of the present invention and cyanic acid side group can be used in the devices such as proton membrane fuel battery (for example high temperature proton membrane fuel battery) or chlor-alkali electrolytic cells as ion-exchange membrane.This type ion-exchange membrane has high chemicalstability, high current efficiency, low membrane resistance, high dimensional stability and higher physical strength etc.
The high-exchange-capacity perfluorinated resin of short side group sulfonic acid fluoride that has two kinds of different structures of the present invention and cyanic acid side group can adopt solution casting technology to process the perfluorinated sulfonic acid ion exchange membrane of suitable thickness or adopt to melt extrude equipment and extrude the mould material of preparing suitable thickness through high-temperature fusion.Then that mould material is crosslinked through known way such as radiation crosslinking, thermal treatment, add light trigger and cause crosslinked or cause through radical initiator that crosslinked that the cyanic acid side group is carried out cyclisation is crosslinked; Sulfonic acid fluoride side group made the transition and be sulfonic acid lateral group thereafter; The perfluorinated ion-exchange membrane of processing not only has anti-various chemical mediator property; Also have high electroconductibility, high mechanical strength and high dimensional stability; Low membrane resistance is highly suitable in fuel cell, high-temperature fuel cell or the chlor-alkali electrolysis cell and uses.
When the high-exchange-capacity perfluorinated resin of short side group sulfonic acid fluoride that has two kinds of different structures of the present invention and cyanic acid side group is used in fuel cell; Based on crosslinked water retention capacity, dimensional stability and the physical strength that can further improve ion-exchange membrane of cyanic acid side group cyclisation; Effectively improve the usability of mould material, further increase the time limit of service of mould material.
The invention has the beneficial effects as follows:
The loading capacity of institute of the present invention synthetic perfluorinated ion exchange resin is between 0.5-2.6mmol/g (dried resin); Loading capacity is more little; Its physical strength is big more, and wherein loading capacity surpasses 20MPa between the physical strength of the uncrosslinked resin of 1.28-1.95mmol/g, and the mould material of preparation has extraordinary thermal stability; Mould material is through after the crosslinking Treatment, and its physical strength surpasses 30MPa.The specific conductivity of room temperature measuring mould material is greater than 0.2S/cm, and the specific conductivity of under 100 ℃, 45% humidity situation, measuring still is higher than 0.05S/cm, can satisfy the demand of fuel cell proton film and chloric alkali electrolysis mould material fully.
Description of drawings
Figure 1A and Figure 1B represent the F of the perfluorinated resin of an embodiment of the invention respectively
19NMR collection of illustrative plates and infared spectrum;
Fig. 2 representes the F of the perfluorinated resin of an embodiment of the invention
19The NMR collection of illustrative plates;
Fig. 3 representes the infared spectrum of the perfluorinated resin of an embodiment of the invention;
Fig. 4 representes the F of the perfluorinated resin of an embodiment of the invention
19The NMR collection of illustrative plates.
Embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.If no special instructions; Used reaction kettle is 10L stainless steel autoclave among each embodiment, and is furnished with TP, pressure transmitter, heating circulation system, cooling recirculation system, agitator motor, inner water-cooled tube, microprocessor pump drive, gas feed valve, liquid feeding valve and material in reactor discharging valve.
Do not have outside the special instruction in following examples, loading capacity all is that sulfonic acid fluoride is hydrolyzed to the result who measures behind the sulfonic acid.
The perfluoroalkyl initiator that the present invention is adopted in building-up process can prepare according to techniques well known, and the preparation method that the present invention recommends is referring to J.Org.Chem., and 1982,47 (11): 2009-2013.
The Potassium Persulphate that the present invention is adopted in building-up process, ammonium persulphate, N
2F
2Gas all can be bought and obtain.Wherein, Potassium Persulphate, ammonium persulphate can pass through the traditional Chinese medicines institutional purchase.N
2F
2Gas can obtain in Eastern Mountain in the purchase of chemical industry ltd.
The comonomer tetrafluoroethylene that the present invention is adopted in building-up process, short side group sulfonic acid fluoride alkene ether monomer, cyanic acid side group alkene ether monomer can be bought and obtain, and also can prepare by approach well known.Wherein, tetrafluoroethylene monomer of the present invention is available from Shandong Dongyue Polymer Material Co., Ltd.; Short side group sulfonyl fluoride monomer can obtain with reference to the preparation method described in US3560568 and the US6624328, and short side group sulfonyl fluoride monomer employing one Chinese patent application of the present invention number is: the method described in CN200910229444.1, CN200910229446.0, the CN 200910230218.5 prepares; Cyanic acid side group alkene ether monomer can obtain with reference to the preparation method described in US3641104 and the US3852326, and cyanic acid side group alkene ether monomer of the present invention adopts one Chinese patent application number to be: the method described in the CN 200910230075.8 prepares.
Embodiment 1
Reaction kettle is cleaned and adding 5.0L deionized water, 100g X 2073 and 125g polyoxyethylene nonylphenol NP-10 emulsifying agent; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 500g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 650g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2-CF
2-CF
2CF
2-SO
2F) and 405g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF
2-CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 2.9MPa, is warming up to 20 ℃, adds 2.6g peroxo-perfluor butyryl radicals compound (CF with volume pump
3CF
2CF
2CO-OO-CCF
2CF
2CF
3) initiated polymerization, continue to feed tetrafluoroethylene (CF
2=CF
2) monomer keeps reaction pressure at 2.9MPa, whenever in system, adds initiator 0.75g at a distance from 15min, behind the reaction 2h, stops to add initiator, let react proceed 15min after, stop to add tetrafluoroethylene monomer.Lower the temperature to reaction kettle through cooling recirculation system; Reclaim unreacted tetrafluoroethylene monomer through recovery system simultaneously; Oyster white slurry in the still is put into after-treatment system through following dispensing valve, and after high speed shear, filtering separation obtains the white polymer powder; In 100 ℃ of baking ovens, dry, obtain having the perfluorinated ion exchange resin of short side group sulfonic acid fluoride and cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the filtered liq and cyanic acid side group alkene ether monomer reclaim the back recycling through recovery system.
Polymer data: through F
19NMR, IR analyze and turn out to be multiple copolymer; Can know that through fluorine nuclear-magnetism integrated value the molecular fraction that contains tetrafluoroethylene monomer in the polymer architecture is 62.71%; Containing sulfonic acid fluoride side group alkene ether monomer (1) molecular fraction is 16.5%; Containing sulfonic acid fluoride side group alkene ether monomer (2) molecular fraction is 16.3%, and containing cyanic acid side group alkene ether monomer molecular fraction is 4.49%, and overall loading capacity is: the 1.77mmol/g dried resin.Decomposition temperature (T under the TGA test resin nitrogen atmosphere
d) be 403 ℃; IR spectrogram: 1468cm
-1Be S=O vibration absorption peak in the sulfonic acid fluoride; 2272cm
-1The place is-the CN vibration absorption peak; 1200 absorb the most by force to be vibrated by CF with two of 1148cm-1 and cause; 720cm
-1, 641cm
-1Cause by the TFE vibration.
Embodiment 2
Reaction kettle is cleaned and added 5.0L deionized water, 220g X 2073; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 500g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 405g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2CF
2CF
2CF
2-SO
2F) and 225g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF
2CF
2CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 2.9MPa, is warming up to 35 ℃, adds 8.0g peroxo-perfluor propoxy-propylated compound (CF with volume pump
3CF
2CF
2OCF (CF
3) CO-OO-CCF (CF
3) OCF
2CF
2CF
3) initiated polymerization, continue to feed tetrafluoroethylene (CF
2=CF
2) monomer keeps reaction pressure at 2.9MPa, whenever in system, adds initiator 2.3g at a distance from 25min, behind the reaction 2.5h, stops to add initiator, let react proceed 25min after, stop to add tetrafluoroethylene monomer.Lower the temperature to reaction kettle through cooling recirculation system; Reclaim unreacted tetrafluoroethylene monomer through recovery system simultaneously; Oyster white slurry in the still is put into after-treatment system through following dispensing valve, and after high speed shear, filtering separation obtains the white polymer powder; In 100 ℃ of baking ovens, dry, obtain having the perfluorinated ion exchange resin of short side group sulfonic acid fluoride and cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the filtered liq and cyanic acid side group alkene ether monomer reclaim the back recycling through recovery system.
Polymer data: through F
19NMR (shown in Figure 1A), IR (shown in Figure 1B) analyze and turn out to be multiple copolymer; Can know that through fluorine nuclear-magnetism integrated value the molecular fraction that contains tetrafluoroethylene monomer in the polymer architecture is 73.8%; Containing sulfonic acid fluoride side group alkene ether monomer (1) molecular fraction is 15%; Containing sulfonic acid fluoride side group alkene ether monomer (2) molecular fraction is 9%, and containing cyanic acid side group alkene ether monomer molecular fraction is 2.2%, and overall loading capacity is: the 1.53mmol/g dried resin.Decomposition temperature (T under the TGA test resin nitrogen atmosphere
d) be 402 ℃; IR spectrogram: 1468cm
-1Be S=O vibration absorption peak in the sulfonic acid fluoride; 2272cm
-1The place is-the CN vibration absorption peak; 1200 and 1148cm
-1Two absorb the most by force by the CF vibration and cause; 720cm
-1, 641cm
-1Cause by the TFE vibration.
Embodiment 3
Reaction kettle is cleaned and adding 5.0L deionized water, 120g X 2073 and 95g polyoxyethylene nonylphenol NP-10 emulsifying agent; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 300g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 610g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2-CF
2CF
2CF
2-SO
2F) and 250g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF
2CF
2CF
2CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 3.2MPa, is warming up to 80 ℃, adds 10% ammonium persulfate aqueous solution 320g initiated polymerization with volume pump, continues to feed tetrafluoroethylene (CF
2=CF
2) monomer keeps reaction pressure at 3.2MPa, behind the reaction 3h, stops to add tetrafluoroethylene monomer.Lower the temperature to reaction kettle through cooling recirculation system; Reclaim unreacted tetrafluoroethylene monomer through recovery system simultaneously; Oyster white slurry in the still is put into after-treatment system through following dispensing valve, and after high speed shear, filtering separation obtains the white polymer powder; In 100 ℃ of baking ovens, dry, obtain having the perfluorinated ion exchange resin of short side group sulfonic acid fluoride, cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the filtered liq and cyanic acid side group alkene ether monomer reclaim the back recycling through recovery system.
Polymer data: through F
19NMR (as shown in Figure 2), IR analyze and turn out to be multiple copolymer; Can know that through fluorine nuclear-magnetism integrated value the molecular fraction that contains tetrafluoroethylene monomer in the polymer architecture is 75.7%; Containing sulfonic acid fluoride side group alkene ether monomer (1) molecular fraction is 8.9%; Containing sulfonic acid fluoride side group alkene ether monomer (2) molecular fraction is 12.28%, and containing cyanic acid side group alkene ether monomer molecular fraction is 3.12%, and overall loading capacity is: the 1.34mmol/g dried resin.Decomposition temperature (T under the TGA test resin nitrogen atmosphere
d) be 397 ℃; IR spectrogram: 1468cm
-1Be S=O vibration absorption peak in the sulfonic acid fluoride; 2272cm
-1The place is-the CN vibration absorption peak; 984cm
-1For-CF
3Vibration causes; 1200 and 1148cm
-1Two absorb the most by force by the CF vibration and cause; 720cm
-1, 641cm
-1Cause by the TFE vibration.
Embodiment 4
Reaction kettle is cleaned and adding 5.0L deionized water, 180g X 2073 and 45g polyoxyethylene nonylphenol NP-10 emulsifying agent; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 300g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 400g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2-CF
2CF
2CF
2-SO
2F) and 250g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF (CF
3) OCF
2CF
2CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 2.7MPa, is warming up to 20 ℃, introduces by N in reaction kettle with the gas meter dominant discharge
2F
2Initiated polymerization continues to feed tetrafluoroethylene (CF
2=CF
2) monomer, keep reaction pressure slowly to rise from 2.7MPa, continue in system, to add initiator N
2F
2, the reaction 2h after, reaction kettle pressure is 3.0MPa, stops to add initiator, let the reaction proceed 1min after, stop to add tetrafluoroethylene monomer.Lower the temperature to reaction kettle through cooling recirculation system; Reclaim unreacted tetrafluoroethylene monomer through recovery system simultaneously; Oyster white slurry in the still is put into after-treatment system through following dispensing valve, and after high speed shear, filtering separation obtains the white polymer powder; In 100 ℃ of baking ovens, dry, obtain having the perfluorinated ion exchange resin of short side group sulfonic acid fluoride and cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the filtered liq and cyanic acid side group alkene ether monomer reclaim the back recycling through recovery system.
Polymer data: through F
19NMR, IR (as shown in Figure 3) analyze and turn out to be multiple copolymer; Can know that through fluorine nuclear-magnetism integrated value the molecular fraction that contains tetrafluoroethylene monomer in the polymer architecture is 74.5%; Containing sulfonic acid fluoride side group alkene ether monomer (1) molecular fraction is 10.5%; Containing sulfonic acid fluoride side group alkene ether monomer (2) molecular fraction is 13.79%, and containing cyanic acid side group alkene ether monomer molecular fraction is 1.21%, and overall loading capacity is: the 1.54mmol/g dried resin.Decomposition temperature (T under the TGA test resin nitrogen atmosphere
d) be 388 ℃; IR spectrogram: 1468cm
-1Be S=O vibration absorption peak in the sulfonic acid fluoride; 2272cm
-1The place is-the CN vibration absorption peak; 1200 and 1148cm
-1Two absorb the most by force by the CF vibration and cause; 720cm
-1, 641cm
-1Cause by the TFE vibration.
Embodiment 5
Reaction kettle is cleaned and added 5.0L deionized water, 215g X 2073 emulsifying agent; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 780g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 720g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2-CF
2CF
2CF
2-SO
2F) and 650g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF
2CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 2.8MPa, is warming up to 25 ℃, introduces by N in reaction kettle with the gas meter dominant discharge
2F
2Initiated polymerization continues to feed tetrafluoroethylene (CF
2=CF
2) monomer, keep reaction pressure slowly to rise from 2.8MPa, continue in system, to add initiator N
2F
2, the reaction 2h after, reaction pressure is 3.2MPa, stops to add initiator, let the reaction proceed 1min after, stop to add tetrafluoroethylene monomer.Lower the temperature to reaction kettle through cooling recirculation system; Reclaim unreacted tetrafluoroethylene monomer through recovery system simultaneously; Oyster white slurry in the still is put into after-treatment system through following dispensing valve, and after high speed shear, filtering separation obtains the white polymer powder; In 100 ℃ of baking ovens, dry, obtain having the perfluorinated ion exchange resin of short side group sulfonic acid fluoride and cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the reaction liquid and cyanic acid side group alkene ether monomer reclaim the back recycling through recovery system.
Polymer data: through F
19NMR (as shown in Figure 4), IR analyze and turn out to be multiple copolymer; Can know that through fluorine nuclear-magnetism integrated value the molecular fraction that contains tetrafluoroethylene monomer in the polymer architecture is 67.1%; Containing sulfonic acid fluoride side group alkene ether monomer (1) molecular fraction is 14.2%; Containing sulfonic acid fluoride side group alkene ether monomer (2) molecular fraction is 11.46%, and containing cyanic acid side group alkene ether monomer molecular fraction is 7.24%, and overall loading capacity is: the 1.44mmol/g dried resin.Decomposition temperature (T under the TGA test resin nitrogen atmosphere
d) be 385 ℃; IR spectrogram: 1468cm
-1Be S=O vibration absorption peak in the sulfonic acid fluoride; 2272cm
-1The place is-the CN vibration absorption peak; 984cm
-1For-CF
3Vibration causes; 1200 and 1148cm
-1Two absorb the most by force by the CF vibration and cause; 720cm
-1, 641cm
-1Cause by the TFE vibration.
Embodiment 6
Reaction kettle is cleaned and added 5.0L deionized water, 225g X 2073 emulsifying agent; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 420g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 265g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2-CF
2CF
2CF
2-SO
2F) and 350g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF
2CF
2CF
2CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 5.2MPa, is warming up to 45 ℃, adds 20.2g with volume pump
-SO2F-perfluor-2,5,8-trimethylammonium-3,6,9-trioxa-undecyl peroxide polymerization initiator reaction continues to feed tetrafluoroethylene (CF
2=CF
2) monomer keeps reaction pressure at 5.2MPa, whenever in system, adds initiator 6g at a distance from 45min, behind the reaction 2h, stops to add initiator, let react proceed 45min after, stop to add tetrafluoroethylene monomer.Lower the temperature to reaction kettle through cooling recirculation system; Reclaim unreacted tetrafluoroethylene monomer through recovery system simultaneously; Oyster white slurry in the still is put into after-treatment system through following dispensing valve, and after high speed shear, filtering separation obtains the white polymer powder; In 100 ℃ of baking ovens, dry, obtain having the perfluorinated ion exchange resin of short side group sulfonic acid fluoride and cyanic acid side group.Sulfonic acid fluoride alkene ether monomer in the filtered liq and cyanic acid side group alkene ether monomer reclaim the back recycling through recovery system.
Polymer data: through F
19NMR, IR analyze and turn out to be multiple copolymer; Can know that through fluorine nuclear-magnetism integrated value the molecular fraction that contains tetrafluoroethylene monomer in the polymer architecture is 80%; Containing sulfonic acid fluoride side group alkene ether monomer (1) molecular fraction is 8.2%; Containing sulfonic acid fluoride side group alkene ether monomer (2) molecular fraction is 9.92%, and containing cyanic acid side group alkene ether monomer molecular fraction is 1.88%, and overall loading capacity is: the 1.27mmol/g dried resin.Decomposition temperature (T under the TGA test resin nitrogen atmosphere
d) be 389 ℃; IR spectrogram: 1468cm
-1Be S=O vibration absorption peak in the sulfonic acid fluoride; 2272cm
-1The place is-the CN vibration absorption peak; 1200 and 1148cm
-1Two absorb the most by force by the CF vibration and cause; 720cm
-1, 641cm
-1Cause by the TFE vibration.
Embodiment 7
Present embodiment is used to explain that the perfluorinated ion exchange resin that uses embodiment 1-6 prepares the process of ion-exchange membrane, and the mechanical property of prepared film.
The preparation process of ion-exchange membrane:
Pellet preparation: respectively the white powder product that obtains among the embodiment 1-6 is melt extruded machine and extrudes the preparation pellet through small-sized; The extrusion temperature that melt extrudes machine is set at: 250 ℃ in screw rod one district, 255 ℃ in screw rod two districts, 260 ℃ in screw rod three districts, 270 ℃ of forcing machine die orifice temperature; Extruding dies diameter 3mm; Through the adjustment shearing rate, the transparent material of the column that will melt extrude is sheared the transparent resin pellet of preparing length 2-4mm, with pellet with the airtight preservation of double-deck PE plastics bag.
Melt extrude crowded film: will melt extrude machine mouth mould and be replaced by the film extrusion die; Screw rod zone design temperature is the same; Adopt the mode that melt extrudes to be prepared into film the transparent pellet of preparation; Film thickness can be regulated through the width of adjustment die orifice, and the film thickness of preparation is 20-100 μ m usually.
Melt extruding mould makes the transition: with the sulfonic acid fluoride (SO of film
2F) side group transfers azochlorosulfonate acid ion (SO to
3H) form is passed through the sodium hydroxide solution of 80 ℃ of mass percentage concentration 30%, the sulphuric acid soln (H of 30 ℃ of mass percent concentrations 30% successively with the film for preparing
2SO
4), mobile deionized water wash groove.Film in alkali lye residence time 30min, the residence time is 10min in sulphuric acid soln; In the de-ionized tank, use deionized water rinsing 10min; Thereafter with the mould material rolling; Airtight preservation promptly obtains the film product, by the ion-exchange membrane of the perfluorinated ion exchange resin of embodiment 1-6 preparation respectively correspondingly note make film 1-film 6.
The film dynamic performance test: test mode employing method is GB/T1040-92; Measure and use the perfluorinated ion exchange resin of embodiment 1-6 preparation to prepare ion-exchange membrane 1-film 6; And the model of E.I.Du Pont Company is the mechanical property of the sulfonate film of NRE 211, and the result lists in table 1.
Table 1
Data through table 1 can be found out, compare with the ion-exchange membrane that is purchased that this area is commonly used, and the film product of resins of the present invention has better mechanical property.
Embodiment 8
The 1.0L reaction kettle is cleaned and adding 500ml deionized water, 10g X 2073 and 13g polyoxyethylene nonylphenol NP-10 emulsifying agent; Start whipping appts; Vacuumize and fill high pure nitrogen displacement three times; Oxygen level vacuumizes after below the 1ppm in the test reaction still, in reaction kettle, adds 50g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F) and 60g sulfonic acid fluoride side group alkene ether monomer (2) (F
2C=CF-O-CF
2-CF
2-CF
2CF
2-SO
2F) and 40g cyanic acid side group alkene ether monomer (F
2C=CF-O-CF
2CF
2-CN) after, in reaction kettle, filling tetrafluoroethylene monomer to pressure is 3.9MPa, is warming up to 80 ℃; In reaction kettle, add the 5.2g ammonium persulfate initiator; The stopped reaction behind 3.9MPa polymerization 2hr that keep-ups pressure obtains the white polymer powder behind the breakdown of emulsion, after the washing drying; The white polymer powder is dissolved in the solution that is mixed with 10mg/ml concentration in the DMF solvent; Carry out GPC test, the result show number-average molecular weight 22.5 ten thousand, weight-average molecular weight is 360,000, do not detect unusual vibration absorption peak among the infrared test result.
Take above same condition, unique change be in reaction kettle, to add 145g sulfonic acid fluoride side group alkene ether monomer (1) (F through the liquid feeding valve
2C=CF-O-CF
2-CF
2-SO
2F); The concentration of total two keys and above term harmonization in the guarantee system; The powder of resulting polymers be dissolved in measure GPC result demonstrate number-average molecular weight 12.3 ten thousand, weight-average molecular weight is 20.5 ten thousand; And detected among the infrared test result-the single bonded antisymmetric stretching vibration absorption peak of S-O-C-, appeared at 830cm
-1The place.These results show that short side group cyclisation can occur really in polymerization process, because the interaction of other alkene ether monomers, cyclization can weaken or eliminate.
Claims (22)
1. high-exchange-capacity perfluorinated resin, its short side group sulfonic acid fluoride alkene ether monomer by tetrafluoroethylene, two kinds of different structures, a kind of cyanic acid side group alkene ether monomer multi-component copolymer close and form, and this resin mainly contains with the repeating unit shown in the following formula (I):
The structural formula of the short side group sulfonic acid fluoride alkene ether monomer of said two kinds of different structures is respectively:
The structural formula of said cyanic acid side group alkene ether monomer is:
The integer of n=0-3 wherein; The integer of m=2-4; The integer of a, b, c=3-15, the integer of a ', b ', c '=1-3; X/ (x+y+z)=0.2-0.7, y/ (x+y+z)=0.2-0.79, z/ (x+y+z)=0.01-0.1.
2. high-exchange-capacity perfluorinated resin according to claim 1 is characterized in that, wherein n=0.
3. high-exchange-capacity perfluorinated resin according to claim 1 and 2; It is characterized in that; The shared molar content percentage ratio of each polymerized unit is in the said resin: the overall x in tetrafluoroethylene polymerization unit is 50～85%; The overall x of short side group sulphonyl fluroxene polymerized unit of two kinds of different structures is 5～49%, and the overall x of cyanic acid side group alkene ether polymerized unit is 1～10%.
4. high-exchange-capacity perfluorinated resin according to claim 3; It is characterized in that; The shared molar content percentage ratio of each polymerized unit is in the said resin: the overall x in tetrafluoroethylene polymerization unit is 70～80%; The overall x of short side group sulphonyl fluroxene polymerized unit of two kinds of different structures is 15～29%, and the overall x of cyanic acid side group alkene ether polymerized unit is 1～5%.
5. high-exchange-capacity perfluorinated resin according to claim 1 and 2 is characterized in that, the mol ratio of the short side group sulphonyl fluroxene polymerized unit (1) of two kinds of different structures and (2) is 0.2-0.8: 0.8-0.2 in the said resin.
6. high-exchange-capacity perfluorinated resin according to claim 5 is characterized in that, the mol ratio of the short side group sulphonyl fluroxene polymerized unit (1) of two kinds of different structures and (2) is 0.4-0.6: 0.6-0.4 in the said resin.
7. the preparation method of each described high-exchange-capacity perfluorinated resin of claim 1 to 6; This preparation method comprises that the short side group sulfonic acid fluoride alkene ether monomer that makes tetrafluoroethylene, two kinds of different structures, a kind of cyanic acid side group alkene ether monomer carry out polyreaction under the initiator effect; Wherein, The reaction times of said polyreaction is 1～8 hour, and temperature of reaction is 10～80 ℃, and reaction pressure is 2～10MPa.
8. preparation method according to claim 7 is characterized in that said initiator is selected from N
2F
2, in perfluoroalkyl superoxide and the persulphate one or more.
9. preparation method according to claim 8 is characterized in that, said perfluoroalkyl superoxide is to be selected from peroxo-perfluoroalkyl acyl compound and the peroxo-perfluoro alkoxy acyl compounds one or more; Said persulphate is to be selected from persulfuric acid ammonium salt, basic metal persulfide and the earth alkali metal persulfide one or more.
10. according to Claim 8 or 9 described preparing methods, it is characterized in that, said perfluoroalkyl superoxide for be selected from perfluoro propionyl superoxide, 3-chlorine fluorine propionyl superoxide, perfluor methoxyl group acetyl pexoxide,
-H-perfluor butyryl superoxide,
-SO
2F-perfluor-2,5,8-trimethylammonium-3,6,9-trioxa-undecyl superoxide, CF
3CF
2CF
2CO-OO-COCF
2CF
2CF
3, CF
3CF
2CF
2OCFCF
3CO-OO-COCFCF
3OCF
2CF
2CF
3, CF
3CF
2CH
2CO-OO-COCH
2CF
2CF
3And CF
3OCF
2CF
2CO-OO-COCF
2CF
2OCF
3In one or more; Said persulphate is to be selected from ammonium persulphate and the Potassium Persulphate one or more.
11. preparation method according to claim 7 is characterized in that, said preparation method also is included in the step that aqueous phase carries out emulsion polymerization, and in the emulsion polymerization step, emulsifying agent is selected from anionic emulsifier; And in the nonionic emulsifier one or more.
12. preparation method according to claim 11 is characterized in that, said anionic emulsifier is sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate or sodium alkylarysulfonate; Said nonionic emulsifier is the alkyl phenol polyether alcohols.
13. preparation method according to claim 12 is characterized in that, said alkyl phenol polyether alcohols is polyoxyethylene nonylphenol, polyoxyethylene fatty acid or polyoxyethylene fatty acid ether.
14. preparation method according to claim 11; It is characterized in that; In the emulsion polymerization step; The mass percent concentration of emulsifying agent in water is 0.1-20%, and the mass percent concentration of short side group sulfonic acid fluoride alkene ether monomer in water of two kinds of different structures is 5-30%, and the mass percent concentration of cyanic acid side group alkene ether monomer in water is 1～12%.
15. ion-exchange membrane that is prepared from each described high-exchange-capacity perfluorinated resin of claim 1 to 6.
A 16. fuel cell or electrolytic cell device that comprises the described ion-exchange membrane of claim 15.
17. fuel cell according to claim 16 or electrolytic cell device is characterized in that, said fuel cell is proton membrane fuel battery or high-temperature fuel cell, and said electrolyzer is a chlor-alkali electrolysis cell.
18., it is characterized in that said fuel cell is the high temperature proton membrane fuel battery according to claim 16 or 17 described fuel cell or electrolytic cell devices.
19. each described high-exchange-capacity perfluorinated resin of claim 1 to 6 is used to make the purposes of fuel cell or electrolytic cell device intermediate ion exchange membrane.
20. purposes according to claim 19 is characterized in that, and is before the use, earlier that the cyanic acid side group is crosslinked through the chemical process cyclisation.
21., it is characterized in that said fuel cell is proton membrane fuel battery or high-temperature fuel cell according to claim 19 or 20 described purposes, said electrolyzer is a chlor-alkali electrolysis cell.
22., it is characterized in that said fuel cell is the high temperature proton membrane fuel battery according to claim 19 or 20 described purposes.
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| WO2011072417A1 (en) * | 2009-12-15 | 2011-06-23 | 山东东岳神舟新材料有限公司 | High exchange capacity perfluorinated resin, preparation method and use thereof |
| CN106977640B (en) * | 2017-04-18 | 2019-06-28 | 浙江汉丞科技有限公司 | The fluorine-containing single side of conducting polymer containing chlorine filled composite film of one kind and preparation method thereof |
| US11136424B2 (en) | 2017-04-18 | 2021-10-05 | Zhejiang Hyproof Technology Co., Ltd. | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
| CN113861327B (en) * | 2021-09-10 | 2023-09-26 | 广州市乐基智能科技有限公司 | Perfluorinated sulfonic acid resin binder with high proton conductivity and mechanical property and preparation method thereof |
| CN115991823B (en) * | 2021-10-18 | 2023-12-29 | 山东东岳未来氢能材料股份有限公司 | Mixed perfluorinated proton exchange membrane and preparation method thereof |
| CN116284538A (en) * | 2023-03-16 | 2023-06-23 | 国家电投集团氢能科技发展有限公司 | Perfluorosulfonic acid resin, its preparation method and application |
| CN117964522B (en) * | 2024-03-29 | 2024-06-07 | 山东东岳未来氢能材料股份有限公司 | Method and device for recovering perfluoro 3, 6-dioxa-4-methyl-7-octenesulfonyl fluoride monomer in polymer |
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| EP1533325A1 (en) * | 2003-11-17 | 2005-05-25 | 3M Innovative Properties Company | Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant |
| CN101220120A (en) * | 2007-01-12 | 2008-07-16 | 山东东岳神舟新材料有限公司 | Fluor resin with sulfuryl fluoride and aether terminal group lateral group, synthesizing method and application thereof |
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