CN1853302A

CN1853302A - Membrane-electrode assembly for solid polymer fuel cell

Info

Publication number: CN1853302A
Application number: CNA2004800267445A
Authority: CN
Inventors: 星信人; 植松信之; 斋藤秀夫; 服部真贵子; 青柳岳司; 池田正纪
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2003-09-17
Filing date: 2004-09-17
Publication date: 2006-10-25
Anticipated expiration: 2024-09-17
Also published as: CN100530792C

Abstract

A membrane/electrode assembly for solid polymer fuel cells is disclosed wherein a fluorinated sulfonic acid polymer having a monomer unit represented by the following general formula (3): (3) (wherein, Rf<1> represents a divalent perfluorohydrocarbon group having 4-10 carbon atoms) is used for at least one of the membrane and the catalyst binder. The fluorinated sulfonic acid polymer has a melt flow rate (MFR) of not more than 100 g/10min at 270 1/2 C when the -SO3H group in the polymer is changed into -SO2F.

Description

The membrane electrode assembly that is used for solid polymer fuel cell

Technical field

The present invention is based on following discovery: the fluorinated sulfonic polymer with particular side chain structure and molecular weight ranges provides a kind of excellent chemical stability (non-oxidizability and thermal stability) that has, high-fire resistance, the material of change in size between high proton conductance and high mechanical properties and little dry and wet state, and relate to and have excellent durability and be particularly suitable at the used membrane electrode assembly of the polymer electrolyte fuel cells of high-temperature area work, it is characterized in that using at least a as film and catalyst binder of described fluorinated sulfonic polymer, also relate to its relevant component materials.

Prior art

Recently, proposed use solid polymer barrier film, compressed (compact) size and weight because it can reduce as electrolytical fuel cell, even and relatively also providing high output density under the low temperature, therefore, quickening its development.

The solid polymeric material that is used for these purposes need have excellent proton conductivity, suitable moisture holding capacity, to the barrier properties for gases of hydrogen, oxygen etc.After deliberation various contain the polymer of sulfonic acid group, phosphonyl group and similar group and proposed many materials (referring to, for example, O.Savadogo, Journal of New Materials for Electrochemical Systems I, 47-66 (1998).)

Under the actual operating conditions of fuel cell, produced active oxygen species on the electrode with hyperoxia voltinism.Therefore, especially need be in the durability under the oxidizing atmosphere of this harshness so that fuel cell move long-term and stably.Many hydrocarbon base material material packages of Ti Chuing are drawn together those materials with excellent fuel cell initialization characteristic up to now, yet they still have endurance issues.

Therefore, the main now research direction that adopts the perfluorinated sulfonic acid polymer shown in the following general formula (1) to use as reality:

(wherein, k/l=3 to 10, m=2, and n=0 or 1).

This polymer can be by the film forming of copolymer between perfluorovinyl sulfide ether monomer shown in the following general formula (2) and the tetrafluoroethene (TFE), the reaction that is hydrolyzed then obtains:

(wherein, m with n with identical in general formula (1)).

Yet, recently, confirmed under the harsh service conditions of fuel cell, even the film of this perfluorinated sulfonic acid polymer also can decompose gradually, and in running, can in water, discharge fluoride ion, therefore need the method for head it off.Yet, about having the structure of the fluorinated sulfonic polymer of excellent chemical stability for solving the resolution problem of perfluorinated sulfonic acid compound under the fuel cell service condition, also without any argumentation, have excellent machinery, the high-durability film and a this use of dimensional stability about what fuel cell was used, then still less touch upon with polymer of high chemical stability.

JP-A-57-25331 has proposed a kind of film, it has the ion exchange capacity (with equivalent (EW) expression) of 800 to 1500 gram/equivalents and is lower than 22,000 hydration (hereinafter will make an explanation), and as comparing the film with low swelling ratio with the dielectric film corresponding to the general formula (1) of n=1 and m=2.As its example, enumerated the structure of general formula (1), and the preferable range of m is 2 and 3 corresponding to n=0 and m=1 to 6.Yet, m is not less than the object lesson of 4 polymer and characteristic thereof without any explanation.In addition, do not mention the different of this polymer chemistry stability that the difference because of the m value causes and non-oxidizability.Similarly, JP-A-63-297406 proposed a kind of EW less than 800 gram/equivalents and hydration less than 29,000 film, and, exemplified the structure of general formula (1) corresponding to n=0 and m=1 to 4 as its example.Yet the polymer of the structure of correspondence is without any explanation, and not about the suggestion of its chemical stability and non-oxidizability when having m=4.

JP-A-2000-268834 discloses the polymer shown in the general formula (1) of m=3 and n=0 as the purposes that is used for the film of fuel cell, and JP-A-6-333574 discloses its purposes as catalyst binder.Yet, about this polymer, to the dimensional stability between its chemical stability, non-oxidizability, the dry and wet state, performances such as decomposition under the fuel cell operation condition without any argumentation.In addition, as the raw material monomer methods of making this polymer, known method is very complicated and many steps are arranged.

JP-A-58-93728 disclose shown in the general formula (1) of m=4 and n=0, ion exchange capacity (with equivalent (EW) expression) is the polymer of 990 gram/equivalents, it is used as the ion exchange membrane material that saline electrolysis is used.JP-A-2001-194798 disclose shown in the general formula (1) of m=4 and n=1, EW is the membrane material that the polymer of 1,044 gram/equivalent is used as antireflection.Yet, in these specifications, for the application of these polymer in fuel cell material without any argumentation.In addition, these two specifications all do not have explanation, and low EW polymer can be used as fuel cell material especially because of the high proton conductance.JP-A-2002-533877 also discloses the polymer shown in the general formula (1) of m=5 and n=1, but for the characteristic of non-oxidizability and so on without any explanation.

International open WO2004/062019 discloses the film that is used for fuel cell of polymer shown in the general formula (1) of a kind of m=4 of use and n=0, and described the film that can use described polymer to obtain to have high EW (small ion cation exchange groups density) and the long-pending value of hyperhydrated, and this film is suitable as the film that fuel cell is used.Particularly, to disclose a kind of EW be that 800 to 1,200 gram/equivalents and hydration are not less than 22,000 preferred film to the document.In the document, " hydration " is the parameter as giving a definition---the equivalent of the water that per 1 equivalent sulfonic acid group film absorbs and the product of EW.Water absorption is by placing boiling water to measure film.Described specification claims, this film is owing to high EW has excellent mechanical property, and because the long-pending proton conductivity with excellence of hyperhydrated.

The fact is, as WO 2004/062019 open described in, big hydration is necessary for obtaining for the high ionic conductivity by the film with high EW, this have the long-pending film of hyperhydrated and make that the film change in size between the dry and wet state is very big.Therefore, when using this film when being used for the film of fuel cell, following point can appear and be difficult to make can long-term work the very durable film used of utility fuel battery:

1. because the change in size that causes because of humidity is very big, thereby be difficult to the stack assemblies and the fuel cell of membrane electrode assembly are carried out process control, therefore also be difficult to control the quality of products obtained therefrom.

2. because in the on-off cycling process of fuel cell, the film change in size that produces because of humidity is very big, thereby having the membrane electrode assembly that is used for fuel cell of this film, the structure of membrane electrode assembly can not keep stable and break at short notice easily.

3. when having the long-pending film suction of hyperhydrated, film-strength greatly reduces.Therefore, because film-strength reduces and the influence of above-mentioned film change in size, membrane electrode assembly is as easy as rolling off a log impaired in the fuel cell operation process.

4. can not obtain extra high proton conductivity in having the film of high EW, amass even it has hyperhydrated, therefore, what film thickness should design is thin to obtain practical proton conductivity.In this case, because the reduction of film-strength under wet condition as mentioned above, this film can not provide practical intensity.

The specification of WO 2004/062019 does not disclose chemical stability, thermal endurance, non-oxidizability and the decomposing property of described polymer under the fuel cell operation condition.

Brief summary of the invention

The problem that the present invention is to be solved

An object of the present invention is to have at least a as film and catalyst binder of excellent proton conductivity, chemical stability, non-oxidizability and stable on heating fluorinated sulfonic polymer by use, a kind of membrane electrode assembly that is used for polymer electrolyte fuel cells is provided, it has excellent durability, is particularly suitable for operating at high-temperature area.More specifically, the present invention is by using film and/or the catalyst binder of described fluorinated sulfonic polymer as polymer electrolyte fuel cells, a kind of membrane electrode assembly that is used for polymer electrolyte fuel cells is provided, even it does not almost have polymer unwinds yet and can use long-term and stably under the high-temperature operation condition, keep macroion conductance and high mechanical properties and good dimensional stability simultaneously.

The means of dealing with problems

The present inventor broad research the relation between polymer architecture and molecular weight and polymer property or the membrane property, finding out the suitable fluorinated sulfonic polymer of using for the solid electrolyte film or the catalyst binder of fuel cell of polymer, and can solve the problems referred to above of material known in the state of the art.The result, the present inventor finds, has the particular side chain structure and is not less than the molecular weight melt mobility of particular value (or be not higher than) of particular value and preferably further has the EW that is not higher than particular value and the fluorinated sulfonic polymer of hydration or both products can be used as fuel cell material.

After inventing out the present invention, the open WO 2004/062019 in the above-mentioned world is disclosed.The polymer architecture that constitutes film in the document has comprised polymer architecture of the present invention.Yet the document discloses the film that can use wherein said polymer manufacturing to have high EW and the long-pending value of hyperhydrated, and this film is suitable as the film that fuel cell is used.That is to say, the membrane material of describing in the document be based on the material of the antipodal notion of material of the invention described above, and nature can not satisfy as the requirement of fuel cell of the present invention with material.

Therefore, by inventor's broad research, obtained for the first time that having described in the present invention is used for the polymer of the required various characteristics of the solid polymerization electrolyte of fuel cell and by its product of making.

The present invention is as follows:

1. the membrane electrode assembly that is used for polymer electrolyte fuel cells is characterized in that using the fluorinated sulfonic polymer contain the monomeric unit shown in the following general formula (3) as solid polymerization electrolyte at least a in film and the catalyst binder:

Rf wherein ¹Be that carbon number is 4 to 10 divalence perfluoro-hydrocarbon group, wherein said fluorinated sulfonic polymer-SO ₃H group quilt-SO ₂The polymer that the F group replaces has at 270 ℃ and is not higher than/10 minutes melt flow rate (MFR) (MFR) of 100 grams.

2. according to the membrane electrode assembly of clauses and subclauses 1, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has the ion exchange capacity of 600 to 1,300 gram/equivalents.

3. according to the membrane electrode assembly of clauses and subclauses 1 and 2, it is characterized in that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) has the glass transition temperature that is not less than 130 ℃.

4. according to each membrane electrode assembly of clauses and subclauses 1 to 3, it is characterized in that passing through TGA, when temperature in air rose with 10 ℃/minute, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) had the thermal decomposition initial temperature that is not less than 330 ℃ and is not higher than 450 ℃.

5. according to each membrane electrode assembly of clauses and subclauses 1 to 4, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when the polymer of film shape continuously with 80 ℃ of water saturated air when contacting 8 hours for 200 ℃, the amount of the fluorine ion of generation is no more than 0.3 weight % of fluorine total amount in the original fluorinated sulfonic polymer.

6. according to each membrane electrode assembly of clauses and subclauses 1 to 5, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), based on sulfonic acid group, the activation energy that uses the density function method to calculate reaction rate-determining step in the thermal oxidation decomposable process that obtains is not less than 40 kilocalories/equivalent and is not higher than 80 kilocalories/equivalent.

7. according to each membrane electrode assembly of clauses and subclauses 1 to 6, it is characterized in that described fluorinated sulfonic polymer contains monomeric unit and the tetrafluoroethylene units shown in the general formula (3) at least.

8. according to each membrane electrode assembly of clauses and subclauses 1 to 7, the monomeric unit shown in its formula of (3) is the monomeric unit shown in the following general formula (4):

Wherein p is 4 to 8 integer.

9. according to the membrane electrode assembly of clauses and subclauses 8, wherein in general formula (4), p is 4 or 6.

10. according to each membrane electrode assembly of clauses and subclauses 1 to 9, wherein use ionic conductivity in 23 ℃ water to be not less than the fluorinated sulfonic polymer of 0.06S/cm.

11., wherein use ionic conductivity in 23 ℃ water to be not less than the fluorinated sulfonic polymer of 0.01S/cm according to each membrane electrode assembly of clauses and subclauses 1 to 9.

12., it is characterized in that it is that the monomeric unit of 4 general formula (4) and having is not higher than 100 scattering strength than (I that the fluorinated sulfonic polymer that uses contains p according to each membrane electrode assembly of clauses and subclauses 1 to 11 ²/ I ¹), I wherein ¹Be the scattering strength under 3 ° 2 θ when measuring polymer under water with small angle x-ray scattering (SAXS), and I ²It is the scattering strength under 0.3 ° 2 θ

13. contain the film that is used for polymer electrolyte fuel cells of following fluorinated sulfonic polymer, this fluorinated sulfonic polymer contains the monomeric unit shown in the following general formula (3):

14. be used for the film of polymer electrolyte fuel cells, it contains the fluorinated sulfonic polymer according to clauses and subclauses 13 that is not less than 60 weight %.

15. be used for the film of polymer electrolyte fuel cells, it is characterized in that containing the fluorinated sulfonic polymer that is not less than 60 weight %, and further contain be not less than 0.1 weight % and be lower than 40 weight % at least a and be selected from the polymer that contains aryl, contain the polymer of basic group and the material of reinforcement material according to clauses and subclauses 13.

16. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 15, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has 2 * 10 ⁶To 23 * 10 ⁶Ion exchange capacity and the product of hydration.

17. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 16, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has and is not less than 2,000 and be lower than 22,000 hydration.

18. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 17, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has the ion exchange capacity of 600 to 1,300 gram/equivalents.

19., it is characterized in that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) has the glass transition temperature that is not less than 130 ℃ according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 18.

20. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 19, it is characterized in that measuring by TGA, when temperature in air rose with 10 ℃/minute, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) had the thermal decomposition initial temperature that is not less than 330 ℃ and is not higher than 450 ℃.

21. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 20, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when the polymer of film shape continuously with 80 ℃ of water saturated air when contacting 8 hours for 200 ℃, the amount of the fluorine ion of generation is no more than 0.3 weight % of fluorine total amount in the original fluorinated sulfonic polymer.

22. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 21, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), based on sulfonic acid group, react the rapid activation energy of rate determining step in the thermal oxidation decomposable process that uses the calculating of density function method to obtain and be not less than 40 kilocalories/equivalent and be not higher than 80 kilocalories/equivalent.

23., it is characterized in that the fluorinated sulfonic polymer contains monomeric unit and the tetrafluoroethylene units shown in the general formula (3) at least according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 22.

24. according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 23, the monomeric unit shown in its formula of (3) is the monomeric unit shown in the following general formula (4):

Wherein p is 4 to 8 integer.

25. according to the film that is used for polymer electrolyte fuel cells of clauses and subclauses 24, wherein in general formula (4), p is 4 or 6.

26., it is characterized in that the ionic conductivity in 23 ℃ water is not less than 0.06S/cm according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 25.

27., it is characterized in that the ionic conductivity in 23 ℃ water is not less than 0.1S/cm according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 25.

28., it is characterized in that it is that the monomeric unit of 4 general formula (4) and having is not higher than 100 scattering strength than (I that the fluorinated sulfonic polymer that uses contains p according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 27 ²/ I ¹), I wherein ¹Be the scattering strength under 3 ° 2 θ when measuring polymer under water with small angle x-ray scattering (SAXS), and I ²It is the scattering strength under 0.3 ° 2 θ.

29. be used for the membrane electrode assembly of polymer electrolyte fuel cells, it is characterized in that using according to each the film that is used for polymer electrolyte fuel cells of clauses and subclauses 13 to 28.

30. a fluorinated sulfonic polymer contains p and is the monomeric unit of 6 general formula (4).

31. the solution of a fluorinated sulfonic polymer or dispersion liquid is characterized in that containing the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) of 0.1 to 50 weight %:

32. according to the fluorinated sulfonic polymer solution or the dispersion liquid of clauses and subclauses 31, wherein in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), ion exchange capacity is 600 to 1,300 gram/equivalents.

33., it is characterized in that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) has the glass transition temperature that is not less than 130 ℃ according to the fluorinated sulfonic polymer solution or the dispersion liquid of clauses and subclauses 31 or 32.

34. according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 33, it is characterized in that passing through TGA, when temperature rose with 10 ℃/minute in air, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) had the thermal decomposition initial temperature that is not less than 330 ℃ and is not higher than 450 ℃.

35. according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 34, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when the polymer of film shape continuously with by 80 ℃ of water saturated air when contacting 8 hours for 200 ℃, the fluoride ion amount of generation is no more than 0.3 weight % of fluorine total amount in the original fluorinated sulfonic polymer.

36. according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 35, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), based on sulfonic acid group, react the rapid activation energy of rate determining step in the thermal oxidation decomposable process that uses the calculating of density function method to obtain and be not less than 40 kilocalories/equivalent and be not higher than 80 kilocalories/equivalent.

37., it is characterized in that the fluorinated sulfonic polymer contains monomeric unit and the tetrafluoroethylene units shown in the general formula (3) at least according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 36.

38. according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 37, the monomeric unit shown in its formula of (3) is the monomeric unit shown in the following general formula (4):

Wherein p is 4 to 8 integer.

39. according to the fluorinated sulfonic polymer solution or the dispersion liquid of clauses and subclauses 38, wherein in general formula (4), p is 4 or 6.

40., it is characterized in that the ionic conductivity of fluorinated sulfonic polymer in 23 ℃ water is not less than 0.06S/cm according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 39.

41., it is characterized in that the ionic conductivity of fluorinated sulfonic polymer in 23 ℃ water is not less than 0.1S/cm according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 40.

42. a method of making the fluorinated sulfonic polymer film is characterized in that using according to each fluorinated sulfonic polymer solution or dispersion liquid cast of clauses and subclauses 31 to 41 forming film.

43. according to the method for the manufacturing fluorinated sulfonic polymer film of clauses and subclauses 42, it is characterized in that after cast forms film, carry out annealing in process under the temperature of glass transition temperature being not less than.

44. make the method contain the electrolytical gas-diffusion electrode of solid polymerization, it is characterized in that according to each fluorinated sulfonic polymer solution or dispersion liquid and catalyst mix of clauses and subclauses 31 to 41, coating and dry in substrate then.

45. make the method contain the electrolytical gas-diffusion electrode of solid polymerization, it is characterized in that immersing and not containing the electrolytical gas-diffusion electrode of solid polymerization by making according to each fluorinated sulfonic polymer solution or dispersion liquid of clauses and subclauses 31 to 41, dry then.

46. the method for an operation of fuel cells is characterized in that using each the fuel cell of membrane electrode assembly of clauses and subclauses 1 to 12 and clauses and subclauses 29 being not less than 80 ℃ of operations down.

The invention effect

Owing to contain following general formula (3)

(Rf wherein ¹Be divalence perfluoro-hydrocarbon group with 4 to 10 carbon atoms) shown in the fluorinated sulfonic polymer of monomeric unit be in operation and decompose hardly, therefore use it as the film of the membrane electrode assembly that is used for polymer electrolyte fuel cells and/or catalyst binder one of at least the time, this membrane electrode assembly that is used for polymer electrolyte fuel cells can use long-term and stably.

Preferred forms of the present invention

To explain the present invention in detail below.

The present invention relates to be used for the high-durability membrane electrode assembly of polymer electrolyte fuel cells, it is characterized in that using at least a as film and catalyst binder of the fluorinated sulfonic polymer that has the particular side chain structure and have excellent chemical stability, thermal endurance and a non-oxidizability.The invention still further relates to following invention---by using the film that is used for copolymer solid electrolyte that forms by the polymer that is selected from described high stability fluorinated sulfonic polymer, for fuel cell provides the high-durability film with special properties with ad hoc structure.Therefore, when using the membrane electrode assembly that is used for polymer electrolyte fuel cells of the present invention to carry out various fuel cell accelerated tests (for example OCV (open circuit voltage) accelerated test), realized excellent durability.

The present inventor broad research the structure of fluorinated sulfonic polymer can under the fuel cell operation condition, stablize the high stability copolymer solid electrolyte material that uses for a long time to find out.As a result, the present inventor finds, the fluorinated sulfonic polymer that contains monomeric unit shown in the following general formula (3) shows suitable high chemical stability, thermal endurance and the non-oxidizability of copolymer solid electrolyte material to being used for fuel cell:

(Rf wherein ¹Be that carbon number is 4 to 10 divalence perfluoro-hydrocarbon group).

The fluorinated sulfonic polymer that below argumentation is contained monomeric unit shown in the general formula (3).

＜polymer architecture 〉

In general formula (3), Rf ¹Can comprise that carbon number is 4 to 10 divalence perfluoro-hydrocarbon group, it can have circulus, and preferably has 4 to 10 carbon chain lengths between ether group and sulfonic acid group.Especially, in general formula (3), the structure shown in the preferred following general formula (5):

(each integer of 1 to 10 naturally of a, b and c wherein, condition is that a+b+c is 4 to 10;

Rf ², Rf ²And Rf ⁴Be the perfluoroalkyl that contains 1 to 4 carbon atom, condition is (CF ₂) _a(CFRf ²) _b(CRf ³Rf ⁴) _cThe total number of carbon atoms of group is 4 to 10).In general formula (5), (CF ₂), (CFRf ²) and (CRf ³Rf ⁴) can be linked in sequence with any, and Rf ², Rf ²And Rf ⁴Keyed jointing forms circulus mutually.In general formula (5), a+b+c is preferably 4 to 8, and more preferably 4 to 6.

In addition, in general formula (3), the structure shown in the further preferred following general formula (4):

(wherein p is 4 to 10 integer).In general formula (4), p is 4 to 10 integer, more preferably 4 to 8, most preferably 4 to 6.Wherein p is that the polymer of 2 general formula (4) is not suitable as the copolymer solid electrolyte material that is used for fuel cell owing to non-oxidizability is not enough.The polymer of the general formula of p=3 (4) is not less than 4 polymer phase ratio with p, and deficiency is said in the effect of generation on the whole, although its with the polymer phase of p=2 than having slightly high non-oxidizability.

In addition, in the manufacture process of vinyl monomer (it is the raw material of the polymer of p=3), because appreciable side reaction (cyclization) in final vinylation reaction process obtains low yield (not being higher than 50%), so it is not practical manufacture method.If the p in the general formula (4) is not less than 11, because other difficulty in the reduction of glass transition temperature and monomer manufacturing and the operation, this polymer is not suitable for commercial Application.

In the general formula (3)-Rf ¹-SO ₃In group shown in the H and the general formula (4)-(CF ₂) _p-SO ₃The example of group shown in the H is as follows:

-CF ₂CF ₂CF ₂CF ₂SO ₃H

-CF ₂CF ₂CF ₂CF ₂CF ₂SO ₃H

-CF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₃H

-CF ₂CF ₂CF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₃H

Wherein, contain-CF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₃The fluorinated sulfonic polymer of H group is synthetic first in the present invention new compound, and comprises in the present invention.

The fluorinated sulfonic polymer that contains monomeric unit shown in general formula (3) or the general formula (4) is preferably with a kind of or be no less than the copolymer of two kinds of other vinyl monomers.Because its excellent chemical stability, the fluorinated vinyl monomer is preferably as this monomer, and perfluorovinyl sulfide monomer more preferably.Example comprises tetrafluoroethene (TFE), a chlorotrifluoroethylene (CTFE), vinylidene fluoride, hexafluoroethylene etc.TFE or CTFE are preferred, and TFE more preferably.Except two components, can also consider that three components or more multi-component copolymer are with adjusting function by adding perfluoro monomer (for example perfluoroolefine, perfluoroethylene alkyl ether, perfluor-1,3-dioxole and similar monomer) with TFE etc.The similar group that polymer ends has hydroxy-acid group or carbon-hydrogen link usually and generated by chain transfer reaction or cessation reaction, yet, fluorination treatment that can be by polymer ends is these group stabilisations, thereby further improves the thermal stability or the non-oxidizability of polymer.

The example that contains the fluorinated sulfonic polymer of monomeric unit shown in general formula (3) or the general formula (4) is as follows:

(k/l is 2.2 to 9.2)

(k/l is 1.2 to 8.2)

Disclosed general formula (1) among open WO2004/062019 in the above-mentioned world and the JP-A-58-93728 (wherein m be 4 and n be 0) shown in polymer comprise the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) that uses among the present invention, yet, in these specifications, there is not explanation about this polymer chemistry stability (non-oxidizability, thermal stability) or thermal endurance (high glass-transition temperature).That is to say that above-mentioned high chemical stability (non-oxidizability, thermal stability) and the thermal endurance (high glass-transition temperature) that contains the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) is the characteristic that confirms first among the present invention.

In addition, the present inventor has studied the characteristic of described fluorinated sulfonic polymer in great detail, developing the above-mentioned high-durability fuel cell material that contains the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) of a kind of use, this polymer is verified to have high chemical stability (non-oxidizability, thermal stability) and thermal endurance (high glass-transition temperature).

The result, the present inventor finds, when the molecular weight of fluorinated sulfonic polymer is not less than particular value when (just the melt mobility is not higher than particular value), it provides a kind of and has had that change in size has kept above-mentioned chemical stability and stable on heating material simultaneously between high mechanical properties and little dry and wet state, and obtains to be used for the film or the catalyst binder of the membrane electrode assembly of high-durability polymer electrolyte fuel cells thus.As the measurement standard of fluorinated sulfonic polymer molecular weight, evaluate and test polymer usually and contain-SO ₂The F group but not-SO ₃During the H group 270 ℃ melt flow rate (MFR) (MFR).Polymer contains-SO ₂The F group but not-SO ₃During the H group, must be able to not be higher than 100 grams/10 minutes in 270 ℃ melt flow rate (MFR)s (MFR), preferred 80 grams/10 minutes, further preferred 60 grams/10 minutes, further preferred 40 grams/10 minutes, further preferred 20 grams/10 minutes, and preferred especially 10 grams/10 minutes are to show the fluorinated sulfonic polymer property that is fit to above-mentioned fuel cell material.MFR is the value of measuring under the condition in 2.16 kilograms of load and 2.09 millimeters apertures herein.As mentioned above, unique necessity is that the fluorinated sulfonic polymer suitable to the present invention contains at polymer-SO ₂The F group but not-SO ₃Should have the MFR that is not higher than particular value during the H group, so also comprise polymer in this polymer with cross-linked polymer structures.

MFR is too low, just is difficult to obtain the melt film forming, and is difficult to prepare solution or the dispersion liquid that is used to form casting film, therefore, the lower limit of MFR is preferably 0.00001 gram/10 minutes, and more preferably 0.0001 gram is/10 minutes, further preferred 0.001 gram/10 minutes, preferred especially 0.01 gram/10 minutes.

As implied above, in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), owing to be used for the desired characteristic of solid electrolyte polymer of fuel cell (for example dimensional stability between the dry and wet state, heat resistanceheat resistant water-soluble, various mechanical strength, or the like), MFR is not less than the characteristic deficiency of/10 minutes fluorinated sulfonic polymer of 100 grams.Yet described MFR is not less than that the polymer of particular value (for example be not less than 100 gram/10 minutes) is verified to have satisfied above-mentioned characteristic.That is to say, contain the monomeric unit shown in the general formula (3) and its MFR and be not less than that the fluorinated sulfonic polymer of particular value is verified to have high chemical stability (non-oxidizability, thermal stability) and thermal endurance (high glass-transition temperature) and a good physical property (change in size, heat resistanceheat resistant water-soluble, various mechanical strength and similarity between low dry and wet state), as the solid electrolyte polymer that is used for fuel cell, it is verified to be quite excellent material thus.

To explain the MFR value that contains the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) and the relation between the various characteristics below in more detail.

A-1) moisture percentage, hydration

When MFR restrained/10 minutes above 100, the moisture percentage that contains the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) sharply raise, and it also is accompanied by the rapid rising of hydration.Polymer with high-moisture is not suitable as the solid electrolyte polymer that fuel cell is used owing to big change in size, the high solubility in hot water, the decline of swelling film mechanical strength and similar state as described below between the dry and wet state.As an example, containing the MFR of the fluorinated sulfonic polymer of monomeric unit shown in the general formula (6) and the relation between the hydration is presented among Fig. 2.

A-2) low gauge variations between the dry and wet state

Have been found that as MFR to surpass 100 grams in the time of/10 minutes,, contain the rapid rising that the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) shows change in size, water content or hydration between dry and wet state along with the rising of MFR value.For example, at EW is 800 to 900 or about 1, in the fluorinated sulfonic polymer shown in 000 the general formula (6), when MFR surpassed 100 grams in the time of/10 minutes, change in size between the dry and wet state sharply raises, and when MFR is about 700 grams/10 minutes the time, be not higher than 100 grams with MFR and compare in the time of/10 minutes, the change in size value between the dry and wet state has raise about 2 times.Change in size between the dry and wet state is meant the rising of the ratio of the area under area after the processing in 100 ℃ of hot water (value when measuring hydration) and the drying regime at this.If the change in size between the dry and wet state is too high, can in the fuel cell operation process, cause film crooked or further folding, so operational efficiency is very poor.It also can improve by the area of wrapping up the compacting of limit, nearly chamber and the difference of not suppressing the swelling ratio between the area, causes the film fracture thus.

A-3) antilysis in hot water

Have been found that as MFR to surpass 100 grams in the time of/10 minutes,, contain the rapid rising that the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) also shows solubility in hot water along with the rising of MFR value.The solubility that polymer improves in hot water means that polymer can wash-out in the fuel cell operation process.In the actual motion of fuel cell, because a variety of causes (for example the hydrogen of seepage and oxygen react), MEA may stand high temperature in the part, also needs to be dissolved in hardly hot water even therefore be used for the solid electrolyte polymer of fuel cell under this high temperature.

The solubility of polymer described in the present invention in hot water is expressed as in pressure vessel the mass value that reduces with 160 ℃ of hot water treatment dry polymers 3 hours and then when dry.For polymer of the present invention, through described hot water treatment, the quality optimization of reduction is no more than 10%, more preferably no more than 8%, further preferably is no more than 6%, further preferably is no more than 4%, is most preferably not exceeding 2%.

A-4) stream temperature

Have been found that along with the rising of MFR value, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) also shows the rapid rising of polymer stream temperature when MFR restrains/10 minutes above 100.The temperature of stream temperature when this is meant that rising modulus of elasticity along with temperature sharply reduces or when when measuring modulus of elasticity fracture taking place, particularly, the measurement result of the variations in temperature by the dynamic viscoelastic under the 35Hz frequency is measured this temperature.In practice, the MEA preparation comprises assembling film and gas-diffusion electrode.Usually, press is everlasting under the temperature of the glass transition temperature that is not less than film and is used improving assembling with heated condition, so the low stream temperature of polymer can cause damaging in assembling process as the polymer of film or catalyst binder.For example, be about in the polymer shown in 1,000 the general formula (6) at EW, along with the rising of MFR, its stream temperature reduces gradually, and is about 500 grams at MFR and reduces to about 180 ℃/10 minutes the time, and being no more than 100 grams/10 minutes the time when the MFR value, stream temperature is up to about 250 ℃.

A-5) in hot water, pierce through intensity

When MFR surpassed 100 grams in the time of/10 minutes,, contain the film-strength reduction of the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) so, particularly under wet condition if as film.For example, along with the rising of MFR, the pierce through intensity of described polymer in 80 ℃ of hot water obviously reduces.In actual use, film is subjected to the extruding of catalyst layer rough surface always under wet condition under operating temperature, and when piercing through intensity when low, this causes serious film to damage easily.For example, be about in the fluorinated sulfonic polymer shown in 800 to 850 the general formula (6),, be about 10 grams with MFR and compare in the time of/10 minutes, pierce through intensity and reduce to about 1/4 when MFR was about 700 grams in the time of/10 minutes at EW.

As mentioned above, international open WO 2004/062019 discloses, about the polymer shown in the general formula (1) that uses m=4 and n=0 (just, polymer shown in the general formula (6)) the film that is used for fuel cell, have high EW and be not less than the film of 22,000 hyperhydrated long-pending (HP) because macroion conductance and high mechanical properties and film that the battery that preferably acts as a fuel is used.Yet disclosed in the document to have the film change in size that the long-pending film of hyperhydrated is found between dry and wet state very high, under wet condition film-strength very a little less than.In addition, can not obtain to have high EW, the film of high proton conductance.Therefore, disclosed film can not obtain to have the film that is used for fuel cell of good battery behavior and high-durability in the document." hydration " (HP) is meant the parameter that defines in the described specification at this, and is the water equivalent of per 1 equivalent sulfonic acid group tunicle absorption and the product of EW.Water absorption is by placing boiling water to measure film.

To explain disclosed polymer and film thereof among the international open WO 2004/062019 below in more detail.

In the embodiment of the document, shown that two kinds are about film that 40,000 polymer constitutes and 4 kinds by hydration and are about the film that 25,000 polymer constitutes by hydration.These films with hyperhydrated long-pending (HP) are owing to change in size between very high dry and wet state has at the described variety of issue of " prior art " part.

The MFR that in WO 2004/062019 discloses, does not represent the polymer of these embodiment, yet, according to being illustrated in the MFR that describes among the a-2 above and Fig. 2 of hydrated product relation, it is found that, hydration is about 40,000 polymer has and is not less than/10 minutes MFR of 500 grams, and hydration is about 25,000 polymer and has and be not less than/10 minutes MFR of 200 grams.As implied above, every kind of polymer describing in the document all has very high MFR, and can not reach the requirement of polymer of the present invention far away, just " is not higher than/10 minutes MFR of 100 grams ".Therefore, as mentioned above, disclosed any film all is not suitable as the film that fuel cell is used among the embodiment of the document.

In WO 2004/062019 is open, both be not suitable for the film example of the film of fuel cell, not about the MFR that contains the fluorinated sulfonic polymer of monomeric unit shown in general formula (3) or the general formula (4) and the explanation of MFR importance yet.Therefore, the present invention, just " MFR is not higher than the solid electrolyte polymer that/10 minutes the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) of 100 grams is suitable for being used for fuel cell ", this is that the research of passing through the inventor realizes first.

In addition, the present inventor has specifically studied the relation of the characteristic of the characteristic of described fluorinated sulfonic polymer and membrance casting condition and gained film, and the fluorinated sulfonic polymer (comprising the polymer shown in the general formula (1) of m=4 and n=0) that contains monomeric unit shown in the general formula (3) with use is developed a kind of high-durability film that is used for fuel cell.The result, the present inventor has been found that, if condition (1): as implied above, use MFR is not higher than the polymer of the fluorinated sulfonic polymer of particular value (for example not being higher than 100 grams/10 minutes), and optimum condition (2): the product of " EW of raw material polymer " and " hydration of gained film " is 2 * 10 ⁶To 23 * 10 ⁶, just can obtain change in size little between the dry and wet state and in water the high mechanical properties under swollen state, this is that to be used for the film of fuel cell needed.That is to say, the product of EW and hydration be between expression proton conductivity, the dry and wet state change in size and in water the unified parameter of each desirable characteristics of the mechanical strength under swollen state.

Be used for the film of fuel cell, if MFR does not reach the value (molecular weight is not less than particular value) of above-mentioned condition (1), just MFR is not higher than particular value, even the product of EW and hydration reaches above-mentioned condition (2) so, can not realize the above-mentioned required characteristic of film that is used for fuel cell.

As mentioned above, in using international open WO 2004/062019, during disclosed film with the long-pending and high EW of hyperhydrated, can not realize good characteristics of fuel cells and high-durability simultaneously.The product of disclosed EW and hydration is 25 * 10 among the international open WO 2004/062019 ⁶To 39 * 10 ⁶Therefore, these exemplary polymer do not reach above-mentioned condition of the present invention (2) and can not realize the above-mentioned required characteristic of film that is used for fuel cell.Because these exemplary polymer do not reach above-mentioned condition (2), so MFR is regarded as outside the scope of above-mentioned condition (1).

With disclosed among the open WO 2004/062019 in the described world to have hyperhydrated these films that are used for fuel cell long-pending and high EW different, the present invention finds, when using MFR not to be higher than the described fluorinated sulfonic polymer of particular value, the film (the not high film of EW and hydration just) that the product of EW and hydration is not higher than particular value shows the suitable characteristic of the film that is used for fuel cell and can become the high-durability film.Therefore, the present invention is based on the world and disclose the antipodal notion of describing among the WO 2004/062019 of film, obtained to be used for the high functional membrane of fuel cell.

To explain the EW of the film that is used for fuel cell that uses among the present invention and the product between the hydration in detail below.

The product of＜EW and hydration 〉

The extensive comparative study that the present inventor carries out the characteristic of film with various EW and hydration, found that, if the product of EW and hydration is too high, although obtained high proton conductivity, but because change in size is bigger between the dry and wet state, just be difficult to accurately assemble, and can not obtain sufficient durability because wet swelling film mechanical strength is not enough.

Yet, have been found that if the product of EW and hydration is too low, although the mechanical strength of the swelling film that the change in size between the dry and wet state is little and wet improves, but can not obtain sufficient proton conductivity, therefore, there is preferred and suitable value in the product of EW and hydration.That is to say that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) in use is during as film, the product of EW and hydration is preferably 2 * 10 ⁶To 23 * 10 ⁶The product upper limit of EW and hydration is preferably 22 * 10 ⁶, more preferably 21 * 10 ⁶, be preferably 20 * 10 especially ⁶, and the lower limit of product more preferably 3 * 10 between EW and the hydration ⁶, more preferably 4 * 10 ⁶, be preferably 5 * 10 especially ⁶

＜hydration 〉

In addition, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) in use is during as film, and the upper limit of hydration preferably is lower than 22,000, more preferably no higher than 21,000, further preferably be not higher than 20,000, further preferably be not higher than 19,000, and especially preferably be not higher than 18,000.The lower limit of hydration is preferably 2,000, and more preferably 3,500, and be preferably 5,000 especially.When the product of EW and hydration above-mentioned 2 * 10 ⁶To 23 * 10 ⁶Scope in the time, the value of hydration needn't be in these scopes.

For making EW and the product value of hydration or the membrane material of value in above-mentioned preferable range of hydration, should satisfy certain conditions.One of these conditions are membrance casting conditions, and another condition is the condition of polymer molecular weight.

＜membrance casting condition 〉

At first, explain membrance casting condition.The product of EW and hydration in particular value film or the manufacture method of the film of hydration in particular value comprise method (a): the method for fusion film forming, for example under state of polymer the compacting or extrude, this moment sulfonic acid group change into-SO ₂F group, saponification and carry out acid treatment then; Or method (b):, under sufficiently high temperature, carry out the method for annealing in process then by the solution or the dispersion liquid cast film forming of sulfonic acid polymer.Can also further stretch under various conditions to improve the dimensional stability or the mechanical strength of the film that forms thus.

The annealing temperature of casting film is not less than the Tg of described sulfonic acid polymer, yet, temperature difference between annealing temperature and the Tg is preferably bigger, and when specifically representing, preferably be not less than 150 ℃ by temperature, further preferably be not less than 160 ℃, further preferably be not less than 170 ℃, further preferably be not less than 180 ℃, further preferably be not less than 190 ℃, especially preferably be not less than 200 ℃.If annealing temperature is too high, polymer can decompose, so annealing temperature preferably is not higher than 250 ℃, more preferably no higher than 240 ℃, further preferably is not higher than 230 ℃.Annealing time is had no particular limits, yet optimum condition is not to be shorter than 10 seconds,, uses not to be shorter than 30 seconds, not to be shorter than 1 minute, not to be shorter than 5 minutes, not to be shorter than 10 minutes, not to be shorter than 30 minutes and not to be shorter than 1 hour for effective annealing.The upper limit to annealing time has no particular limits, however optimum condition is in 24 hours, is provided in 5 hours, in 1 hour, in 30 minutes or in 10 minutes to obtain economic processing method.When the annealing temperature of casting film or annealing time were not enough, the hydration of gained film uprised easily, therefore makes this film have the dimensional stability of poor mechanical strength or difference under the state of wet and swelling.

The molecular weight of＜polymer 〉

When the molecular weight of polymer (is just worked as MFR and is higher than particular value inadequately greatly, for example be higher than 100 grams in the time of/10 minutes) time, even used these film build methods, the product of EW and hydration or the value of hydration and can not provide the intensity and the dimensional stability of abundance as the film that is used for fuel cell material not in OK range.Especially, when the EW value lower (for example, be lower than 1,000, be lower than 950, be lower than 900, be lower than 850 and be lower than 800 EW) time, the molecular weight of polymer should be enough high, and the annealing temperature that pours in the membrane process at film should be enough high, obtaining the EW in OK range and the product or the hydration of hydration, and shows being used for the suitable characteristic of solid electrolyte polymer of fuel cell.

That is to say, the present inventor finds, at the film that is used for fuel cell that constitutes by described fluorinated sulfonic polymer, even the EW of film is lower, the film that uses the sufficiently high polymer of molecular weight (MFR is not higher than the polymer of particular value) and use sufficiently high annealing temperature to obtain in the cast film forming shows change in size between high strength and good dry and wet state.In addition, because low EW, this film also has the high proton conductance, and has chemical stability (non-oxidizability, thermal stability) and thermal endurance (high glass-transition temperature) as mentioned above.Therefore, the film of making thus shows good battery behavior, even and be the film that is used for fuel cell that long-play also can show stability in high temperature range.

<EW>

The fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) in use is during as film that is used for polymer electrolyte fuel cells and/or catalyst binder, owing to provide higher proton conductivity, therefore preferred lower sulfonic acid group density (just lower ion exchange capacity).Therefore, when using equivalent value (EW) the expression ion exchange capacity that polymer weight is obtained divided by the molal quantity of sulfonic acid group, EW preferably is not higher than 1,300 gram/equivalents are more preferably no higher than not being higher than 1,200 gram/equivalent, more preferably no higher than 1,100 gram/equivalents are more preferably no higher than 1,000 gram/equivalent, more preferably no higher than 950 gram/equivalents, more preferably no higher than 900 gram/equivalents, more preferably no higher than 890 gram/equivalents, more preferably no higher than 850 gram/equivalents, more preferably no higher than 800 gram/equivalents, more preferably no higher than 790 gram/equivalents,, especially preferably be not higher than 760 gram/equivalents more preferably no higher than 780 gram/equivalents.If the EW value is too low, will cause lower mechanical strength under wet and solvent swelling state, perhaps can be created in deliquescent problem in the water, so EW preferably is not less than 600 gram/equivalents, more preferably be not less than 640 gram/equivalents, most preferably be not less than 680 gram/equivalents.Even EW in above-mentioned scope, for described polymer or the film that constitutes by described polymer, the product of MFR, EW and hydration or hydration preferably in above-mentioned scope to show mechanical strength or dimensional stability excellent under wet and solvent swelling state.

＜glass transition temperature 〉

Operating temperature is preferably high as far as possible, because fuel cell can move under superpotential little activation, and can make the radiator miniaturization in automobile is used.The glass transition temperature of polymeric material (for example film that uses in the fuel cell or catalyst binder use polymer) also preferably can be higher than the operating temperature of fuel cell, to guarantee fuel cell operation with security and stability in high temperature range.Yet the glass transition temperature of the main polymer (corresponding to the general formula (1) of n=1) that uses is 120 ℃ or lower at present, so operating temperature can not be set at high temperature.Yet through studies confirm that of inventor, the glass transition temperature that contains the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) that uses among the present invention remains on higher level, even described polymer has long side-chain structure.That is to say, have been found that described polymer not only shows excellent chemical stability, thermal endurance and non-oxidizability as mentioned above, also provides the mechanical strength of suitable hot operation.The glass transition temperature that contains the fluorinated sulfonic polymer of monomeric unit shown in the general formula (3) that uses among the present invention preferably is not less than 130 ℃, more preferably is not less than 140 ℃.Glass transition temperature among the present invention is expressed as: when with the dynamic viscoelastic of the described polymer of frequency measurement of 35Hz, provide the temperature of maximum loss factor.

＜heat decomposition temperature/non-oxidizability 〉

In the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when in inert gas and under 10 ℃/minute heating rate, passing through TGA (TGA) measurement, the thermal decomposition initial temperature preferably is not less than 340 ℃, more preferably be not less than 350 ℃, more preferably be not less than 360 ℃, more preferably be not less than 370 ℃, more preferably be not less than 380 ℃, most preferably be not less than 385 ℃.Inert gas is argon gas, nitrogen and similar gas herein, and argon gas is preferred.In this case, preferably when not being higher than 1000ppm, oxygen concentration begins to measure.The thermal decomposition initial temperature of measuring by TGA (TGA) in air and under 10 ℃/minute heating rate preferably is not less than 330 ℃, more preferably be not less than 335 ℃, more preferably be not less than 340 ℃, more preferably be not less than 345 ℃, more preferably be not less than 350 ℃, most preferably be not less than 355 ℃.In identical TGA, in inert gas, on the thermal decomposition initial temperature under 10 ℃/minute the heating rate, be limited to 500 ℃, in air, on the thermal decomposition initial temperature under 10 ℃/minute the heating rate, be limited to 450 ℃.Can by obtain temperature-figure-of-merit curve in TGA inert gas or in air with determination of heating rate the present invention of 10 ℃/minute in the initial temperature of thermal decomposition, and be the temperature at the place, tangent line crosspoint of the curve after curve before thermal decomposition begins and thermal decomposition begin.

Usually, the moisture absorption of sulfonic acid polymer height, so can observe quality before in TGA measures, reaching about 200 ℃ and reduce, yet this is by the desorb that absorbs moisture but not is caused by decomposition that the TGA that therefore is enough to consider to be not less than substantially under 200 ℃ shows.

Above-mentioned pyrolysis initial temperature preferably than commercial product Nafion (from Dupont Co., the registered trade mark of the product of U.S.A) 117 films are (corresponding to the fluorinated sulfonic polymer of the general formula (1) of n=1 and m=2, its ion exchange capacity is 1,100 gram/equivalents) or ion exchange capacity be 900 to 1,20 ℃ of fluorinated sulfonic polymerization object heights shown in the n=1 of 000 gram/equivalent and the general formula of m=2 (1), further preferred high 30 ℃, most preferably high 40 ℃.

＜fluoride ion the amount that decompose to produce by high-temperature oxydation 〉

When the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) under the membrane stage continuously with by water saturated 80 ℃ of air when contacting 8 hours for 200 ℃, the fluoride ion amount of generation is no more than 0.2 weight % of fluorine total amount in the original polymer.The film that will have the fluorinated sulfonic polymer of about gross thickness is cut into 3 centimetres of sizes of 3 cm x (about 0.1 grammes per square metre), it is put in the SUS sampling pipe of 5 centimetres of internal diameter 5 millimeters long, and two end is all linked to each other with the PTFE tube road with SUS.Whole sampling pipe is placed in 200 ℃ the baking oven, and in the middle of the SUS pipeline, feeds water, thereby flow into wet air with the speed of 20 ml/min 80 ℃ of heating through bubbler.With 8 milliliters of rare NaOH aqueous solution (6 * 10 ^-3N) add the PTFE tube road to collect decomposed substance 8 hours, to collect the fluoride ion in the liquid by the chromatography of ions quantitative analysis at outlet side.The amount of collecting fluoride ion in the liquid preferably is not higher than 0.2 weight % of fluorine total amount in the original fluorinated sulfonic polymer, further preferably is not higher than 0.1 weight %, especially preferably is not higher than 0.05 weight %.In this case, because the effect of impurity etc. in the polymer, can collect the fluoride ion of relative higher concentration in the starting stage of decomposing, yet, in this case, can after per hour collecting amount is stablized, measure 8 hours collecting amount, perhaps can change into 8 hours value stablizing back collecting amount hourly.

Above-mentioned collecting amount preferably is not higher than commercial product Nafion (from Dupont Co., the registered trade mark of the product of U.S.A) 117 films or be 1 corresponding to general formula (1) and the ion exchange capacity of n=1 and m=2, the film of 50 micron thickness of 000 gram/equivalent in similar test collecting amount 1/2, further preferably be not higher than 1/3, especially preferably be not higher than 1/4.

Above-mentioned test is preferably as follows and is containing-SO ₂Carry out on the polymer of F type end functional groups: use press, extruder etc. to carry out the fusion film forming, carry out saponification, acid treatment then so that this end functional groups is changed into-SO ₃H type and water fully wash.

Fluorinated sulfonic polymer for using among the present invention can be used as it is the polymer that polymerisation in solution or emulsion polymerization are made, yet owing to show high stability, the polymer of handling with fluorine gas after polymerization is preferred.

The activation energy of＜decomposition reaction 〉

In the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), react the rapid activation energy of rate determining step in the thermal oxidation decomposable process that uses the calculating of density function method to obtain and preferably be not less than 40 kilocalories/equivalent (as the unit of sulfonic acid group), further preferably be not less than 41 kilocalories/equivalent, most preferably be not less than 42 kilocalories/equivalent.Use density generic function method to calculate reacting the rapid activation energy of rate determining step in the thermal oxidation decomposable process that obtains is 80 kilocalories/equivalent.

To explain " the rapid activation energy of reaction rate determining step in the thermal oxidation decomposable process " below in detail, it can be the parameter of described fluorinated sulfonic polymer stabilizing.

At first, the work of the active oxygen by OH group, singlet oxygen and so on attracts the hydrogen atom of sulfonic acid group in the described fluorinated sulfonic polymer in order to the free radical mode, and form thus-SO ₃Group is attacked side chain or main chain and is calculated activation energy when decomposing.In this case, predictablely be, according to each decomposition step calculating energy, and it is rapid to provide the peaked step of this energy to be chosen as the reaction rate determining step, and its energy value is defined as " the rapid activation energy of reaction rate determining step in the thermal oxidation decomposable process ".The present inventor has been found that " the rapid activation energy of reaction rate determining step in the thermal oxidation decomposable process " the fluorinated sulfonic polymer in above-mentioned scope that calculates thus produces low-down fluoride ion elution amount in the thermal decomposition test.

As the activator class in the present invention's calculating, consider that the OH group calculates just enough.

Yet, be difficult based on the calculating of polymer self, therefore use to have the model compound of simplified structure as substitute in this calculating.For example, have-SO via the interval base band in side chain terminal ₃Under the situation of the perfluor base addition polymers of H, can use (CF ₃) ₂The CF-group is as the main chain model, and can to use structure be (CF ₃) ₂-CF-(base at interval)-SO ₃The compound of H is as the model compound that is used to calculate.

For calculation procedure of the present invention, use from Accelrys Co., the DMo13 of U.S.A, and use respectively DNP as basic function (base function) and use PW91 model gradient calibration potential energy as electron exchange to specific potential energy.

In the thermal oxidation decomposition reaction in this technology, suppose decompose because-SO ₃Group (as mentioned above, it is generated by reaction between sulfonic acid group and the active oxygen) carries out the attack of side chain or main chain, yet compound structure is depended in the position of being attacked.The activation energy of the rapid reaction of rate determining step is that the attack of each position is calculated and got, and will provide the attack position of minimum value to be defined as reflecting point, and this value can be as the activation energy among the present invention.

Reflecting point for example almost depends on the structure of the polymer that is generated by the sulfonic acid group on perfluoroalkyl vinyl ether and the side chain terminal, can calculate in the base position as the ether group sulfonic acid side of reflecting point.In this case, use contains (CF ₂) _qAt interval the examples of compounds of base is as the following elaboration thermal oxidation of model compound decomposition reaction:

Wherein q is not less than 2 integer

＜ionic conductivity 〉

Use contains the fluorinated sulfonic polymer of monomeric unit shown in general formula (3) or the general formula (4) as the film and/or the adhesive that are used for polymer electrolyte fuel cells, so its ionic conductivity is preferably high as far as possible.The ionic conductivity that the fluorinated sulfonic polymer that uses among the present invention is measured in 23 ℃ of water with the film shape preferably is not less than 0.06S/cm, more preferably is not less than 0.08S/cm, further preferably is not less than 0.09S/cm, and especially preferably is not less than 0.1S/cm.

When not specializing, the ionic conductivity of film or polymer is meant in the present invention, in 23 ℃ water, at this film or by the proton conductivity on the polymer film of various film forming method preparations.

＜moisture percentage 〉

Moisture percentage is preferably in particular range, so that macroion conductance and the mechanical strength under wet and solvent swelling state to be provided.Usually, preferably be not less than 10 weight %, more preferably be not less than 12 weight %, further preferably be not less than 15 weight %, and especially preferably be not less than 18 weight % at the lower limit of 80 ℃ of water content.Yet, if 80 ℃ water content is too high, can cause the change in size between the dry and wet state too big, so the upper limit preferably is not higher than 50 weight %, and further preferably is not higher than 40 weight %.80 ℃ moisture percentage is following acquisition: polymer was soaked 30 minutes in 80 ℃ of hot water, dry surface water then, and be expressed as the percent value of calculating and obtaining: compare the weight of the weight of increase divided by dry polymer with dry polymer.

Similarly, in hydration is measured, determine 100 ℃ the absorption water yield also preferably in particular range.Usually, preferably be not less than 15 weight %, more preferably be not less than 20 weight %, especially preferably be not less than 25 weight % at the lower limit of 100 ℃ the absorption water yields.Yet this upper limit preferably is not higher than 70 weight %, and further preferably is not higher than 60 weight %.Described in JP-A-57-25331, soaked 30 minutes in 100 ℃ of hot water at 16 hours polymer of 110 ℃ of dryings, take out then, in room temperature water, placed 5 minutes, take out this film, dry surface water rapidly, this moment is based on the moisture percentage of weight measurement at 100 ℃.This measured value is expressed as dries the percent value that the weight of comparing increase behind the surface water with dry polymer obtains divided by the weight of dry polymer.In specification of the present invention, be expressed as " moisture percentage " 80 ℃ water absorptions and be expressed as " suction content " 100 ℃ water absorption.

＜low-angle X-ray scattering (SAXS) 〉

The present inventor has been found that, in the low-angle X-ray scattering of under Riddled Condition, measuring, as the polymer and the defective polymer phase ratio of these characteristics with excellent specific property (in the mechanical strength of the film of water swelling, the dimensional stability between the dry and wet state etc.) of the solid electrolyte polymer that is used for fuel cell, has very little scattering strength being no more than under 1 ° 2 θ.Its reason and unclear, however according to estimates, the scattering under being no more than 1 ° 2 θ is that the big waters that exists in by polymer produces, and also the amount in this big waters has been considered to influence the performance of above-mentioned intensity and so on.That is to say that if its amount is too high, big waters is regarded as not only directly having shared proton conductivity, also causes intensity to reduce.Therefore, preferably as far as possible little in the scattering that is no more than under 1 ° 2 θ, for example, if the fluorinated sulfonic polymer shown in the general formula (6), the scattering strength (I under 0.3 ° 2 θ ²) and the scattering strength (I under 3 ° 2 θ ¹) ratio, I ²/ I ¹, preferably be not higher than 100, more preferably no higher than 90, further preferably be not higher than 80, further preferably be not higher than 70, especially preferably be not higher than 60.

The scattering strength ratio, I ²/ I ¹, can be by determining in the measurement that contains the low-angle X-ray scattering on the moisture film.Usually, use with the CuK alpha ray make radiation source and have can measure scattering angle 2 θ (its be wider than at least 0.3 °＜2 θ＜3 °) X-ray scattering instrument as measuring equipment.The at present scattering strength that the detector that uses can each scattering angle of detection by quantitative, for example location-sensitive proportional counter tube, image photographic plate etc.At 25 ℃ the film that is immersed in pure water or the ion exchange water is carried out scatterometry.From shining the X-ray with the direction of film Surface Vertical.On from the scattering of blank cell and on slit etc., proofread and correct the gained measurement result, because gained result and measuring condition have nothing to do.Can obtain the scattering strength of 2 θ=0.3 ° and 3 ° from thus obtained scatter intensity distribution, measure scattering strength thus and compare I ²/ I ¹

＜monomer synthetic method 〉

As the monomer shown in the raw-material following general formula (8) of monomeric unit shown in the general formula (4):

CF ₂＝CFO(CF ₂) _pSO ₂F (8)

(wherein p is 4 to 10 integer) can be synthetic by following method.A kind of method is to make the compound shown in the following general formula (9):

X(CF ₂) _pOCF＝CF ₂ (9)

(wherein X=Br and I, and p is with identical in general formula (8)) its pair key adding under the protection attitude of chlorine or under non-protection attitude with the compound reaction that is selected from dithionite or rhodanate, then by X being changed into SO with the chlorine reaction ₂The Cl group is by further changing into SO with fluoride salt compound (for example NaF, KF etc.) reaction ₂The F group, and under the protected situation of two keys, use further dechlorination reactions such as zinc.

According to another kind of method, by D.J.Burton etc., Journal of Fluorine Chemistry, volume 60, the p.93-100 compound shown in (1993) synthetic general formula (10) of method of describing:

I(CF ₂) _pSO ₂F (10)

(wherein p is with identical in general formula (8)),

By the compound oxidation shown in the general formula (10) being obtained the compound shown in the following general formula (11) with oleum etc.:

FCO(CF ₂) _p-1SO ₂F (11)

(wherein p is with identical in general formula (8)),

Obtain the compound shown in the following general formula (12) by the further reaction of using KF etc. to make catalyst and HFPO (HFPO) then:

(wherein p is with identical in general formula (8)).This compound and K ₂CO ₃And so on alkali compounds carry out thermal decarboxylation reaction to obtain the monomer of general formula (8).

The compound of general formula (11) also can be synthetic by the electrofluorination reaction of corresponding cyclic hydrocarbon compound (ring-type sultone compound) precursor according to the method for describing among the JP-A-57-164991.In addition, its can by contain with the ring-type or the non-cyclic hydrocarbon compound precursor of the corresponding skeleton structure of compound of general formula (11) or contain and the partially fluorinated compound precursor of the corresponding skeleton structure of compound of general formula (11) directly fluoridize synthetic.

＜as the method for the used film of fuel cell 〉

At the membrane electrode assembly that is used for polymer electrolyte fuel cells of the present invention, use to contain the monomeric unit shown in the general formula (3) and work as polymer and contain-SO ₂The F group but not-SO ₃MFR during the H group is not higher than at least a as film and catalyst binder of/10 minutes fluorinated sulfonic polymer of 100 grams.

At first, explain the situation of this polymer of using as membrane material.

Contain and comprise the monomeric unit shown in the general formula (3) and contain-SO when polymer ₂The F group but not-SO ₃The film that is not higher than/10 minutes fluorinated sulfonic polymer of 100 grams at 270 ℃ MFR during the H group also within the scope of the invention.

When using described fluorinated sulfonic polymer as film, thickness is preferably 5 to 200 microns, and more preferably 10 to 150 microns, most preferably 20 to 100 microns.The thickness that surpasses 200 microns can reduce fuel cell performance, because can improve resistance when this film is used for fuel cell.The thickness that is lower than 5 microns can reduce fuel cell performance, because can reduce film-strength when this film is used for fuel cell and improve the transit dose of fuel gas.

When using described fluorinated sulfonic polymer as film, general step is the SO that at first obtains to contain monomeric unit shown in the following general formula (13) ₂F type (being total to) polymer:

(Rf wherein ¹With identical in general formula (3)), use various one-tenth embrane methods (for example be pressed into embrane method or be extruded into embrane method) to carry out film forming then, saponification is also carried out acid treatment etc., to change into sulfonic acid group.Can use the sulfonic acid fundamental mode polymer that makes by the whole bag of tricks as solution or dispersion liquid, to form film by casting.In passing through the process of casting film forming, dry annealing in process under suitable temperature afterwards is preferred, because too low baking temperature can make the film-strength deficiency.Preferred annealing conditions is as described in about the explanation of above-mentioned membrance casting condition.

When the membrane material, the fluorinated sulfonic polymer can use separately, yet, can other material of chemical combination to carry out the film reinforcement or to carry out characteristic and regulate.For example, can mix organic filler (fluorocarbon resin etc. for example, for example PTFE etc.) and inorganic filler (for example powder or must shape filler, for example silicon dioxide or aluminium oxide etc.) to reach the purpose of reinforcement.The braid, nonwoven fabrics, fiber etc. that can also use fluorocarbon resin (for example PTFE etc.) or various aromatics or non-aromatics engineering resin are as core.Fluorocarbon resin (for example PTFE etc.) etc. and the perforated membrane based on the resin of hydrocarbon that is soaked with the fluorinated sulfonic polymer can be used as film.On the other hand, other polymer be can mix, polymer (for example polyimides, polyphenylene oxide and polyphenylene sulfide) that contains aryl or the polymer that contains various basic groups (usually for example polybenzimidazoles etc.) comprised, to be used to regulate durability or swelling property.

In these cases, when mixing other material, described fluorinated sulfonic polymer ratio preferably is not less than 60 weight %, more preferably is not less than 70 weight %, further preferably is not less than 80 weight %, to keep the high proton conductance.Other material that is selected from supporting material at chemical combination (comprises above-mentioned the contain polymer of aryl, the polymer that contains basic group or above-mentioned organic filler; The core of inorganic filler, braid, nonwoven fabrics and fiber; Perforated membranes etc.) time, the content of at least a type of selecting from the polymer that contains aryl, the polymer that contains basic group and supporting material is for being not less than 0.1 weight % and not being higher than 40 weight %.When not being higher than 0.1 weight % with the amount of other material of described fluorinated sulfonic polymer chemical combination is not preferred, because the adjection that provides is less, the amount that is not less than 40 weight % is not preferred yet, because can make described composite membrane produce low ionic conductivity.

＜solution 〉

When manufacturing contained the casting film of described fluorinated sulfonic polymer or catalyst binder, the fluorinated sulfonic polymer used with the form of its solution or dispersion liquid.Under the situation of the polymer shown in the general formula (1) of n=1 and m=2, its water white in appearance solution type is sold on market as dispersion liquid, and in fact, known its is not the solution type of polymer but dispersion liquid.Can also prepare similar fluorinated sulfonic polymer solution, therefore in the present invention, its water white in appearance solution type is known as " solution or dispersion liquid ".Under any circumstance, contain 0.1 to 50 weight % contain the monomeric unit shown in the general formula (3) and 270 ℃ melt flow rate (MFR) (MFR) (when polymer contains-SO ₂The F group but not-SO ₃MFR during the H group) " solution or the dispersion liquid " of fluorinated sulfonic polymer that is not higher than/10 minutes fluorinated sulfonic polymer of 100 grams is novel and within the scope of the invention.

About the solution of described fluorinated sulfonic polymer or the solvent of dispersion liquid, make water and alcohol (for example ethanol, propyl alcohol etc.) or fluorinated compound (for example fluorine-containing alcohol or perfluoro-hydrocarbon etc.) separately or use as mixed solvent.Usually obtain solution or dispersion liquid by following manufacture method: described fluorinated sulfonic polymer and mixed solvent (for example, water and alcohol) are added pressure vessel,, stir (hereinafter being called dissolution process) simultaneously then 150 to 250 ℃ of heating.Polymer concentration in the dissolution process is generally 1 to 20 weight %, yet,, the polymer concentration in described solution or the dispersion liquid is adjusted to 0.1 to 50 weight % by the dilution after the dissolution process or concentrated, preferred 1 to 40 weight %, further preferred 5 to 30 weight %.Even can not obtain solution or dispersion liquid, even in the system of simple water or dimethylacetylamide and so on, also can obtain solution or dispersion liquid by once preparing solution or dispersion liquid by solvent exchange by direct dissolution process.

<MEA>

Then, discuss the membrane electrode assembly that is used for polymer electrolyte fuel cells (hereinafter being abbreviated as MEA (Membrane Electrode assembly)) that uses the fluorinated sulfonic polymer.This MEA is by constituting as electrolytical film with the gas-diffusion electrode of this film assembling.

Gas-diffusion electrode is the unified structure between electrode catalyst layer and gas diffusion layers, and is being used under the situation of fuel cell, further comprises the protonically conductive polymer as catalyst binder usually.Electrode catalyst contains the electric conducting material of supported catalyst metal, and can contain water repellent agent if desired.

As catalyst metals, use platinum, palladium, rhodium, ruthenium or their alloy etc., and in many cases, use platinum or its alloy.Catalyst loadings is about 0.01 to 10 milligram/cubic centimetre under electrode formation state.As electric conducting material, use various metals or material with carbon element, and carbon black, graphite etc. are preferred.

Can use the adhesive of fluorinated sulfonic polymer as this catalyst.Can use the gas-diffusion electrode of fluorinated sulfonic polymer by following method manufacturing as catalyst binder.At first, in one approach, the solution or the dispersion liquid of fluorinated sulfonic polymer are mixed with the electric conducting material of supported catalyst, and the method by for example silk screen printing and spraying process and so on is coated on the gained slurry on the suitable substrates (for example PTFE plate etc.) with thin layer form then, and dry.In another approach, the solution or the dispersion liquid of described fluorinated sulfonic polymer is immersed in the gas-diffusion electrode that does not contain protonically conductive polymer, dry then.In described drying process, in film forming, high annealing is effective.The preferable range of annealing conditions (temperature, time) and the annealing conditions in the above-mentioned film forming are similar in this case.

Use the fluorinated sulfonic polymer as film and/or catalyst binder, it can be independent polymer or polymeric blends.

Use provides the equipment of pressurization and heating to carry out assembling between film and the gas-diffusion electrode.Usually use equipment such as hot press, roll squeezer to carry out.In this case, can apply any press temperature,, and be generally 130 to 250 ℃, preferred 170 to 250 ℃ as long as it is not less than the glass transition temperature of film.Press pressure depends on the hardness of gases used diffusion electrode, but is generally 5 to 200 kilograms/square centimeter, and preferred 20 to double centner/square centimeter.

The MEA of the present invention that as above forms is added fuel cell.Use the fuel cell of MEA of the present invention preferably under higher relatively temperature, to move, because this improves catalyst activity and reduces the overvoltage electrode.Film can't play a role under the situation of humidity not having, so it must work under the temperature that can control water content, and this causes fuel cell to move difficulty under very high temperature.Therefore, preferred operating temperature is a room temperature to 150 ℃, preferred room temperature to 120 ℃, more preferably room temperature to 100 ℃.Use the maximum feature of the fuel cell of MEA of the present invention to be, 70 to 80 ℃ common operating temperatures or under 80 to 90 ℃ temperature range, show and the suitable performance of the corresponding conventional film of general formula (1) of n=1 and m=2 (for example Nafion (registered trade mark) film etc.), be not less than 90 ℃ or be not less than the high temperatures operation in 95 ℃ of zones simultaneously.Certainly, use the fuel cell of MEA of the present invention under the mild temperature of about room temperature, to move, and can temporarily under the low temperature that is not higher than room temperature, move, for example the start-up operation of fuel cell.

MEA of the present invention shows excellent durability when adding fuel cell and long-play as mentioned above.Usually proposed many accelerated tests and evaluated and tested this durability at short notice, even and carry out this accelerated test, use the fuel cell of MEA of the present invention also to show excellent durability.As an example, a kind of OCV accelerated test as durability evaluating method under the high temperature low humidity condition is arranged.OCV is meant " open circuit voltage ", and this OCV accelerated test is the accelerated test that is used to quicken chemometamorphism of carrying out under the OCV state by polyelectrolyte membranes is remained on.

Based on the commissioned research of General Development Organization of Japan New Energy andIndustry Technology, at Asahi Kasei Corp., Japan is at " R﹠amp; The the 55th to the 57th page R﹠amp among the D ona polymer electrolyte fuel cell (relating to estabilishment of membraneaccelerated evaluation technology and the like); The details of this OCV accelerated test have been described in D result's report.In the present invention, under 100 ℃ battery temperature, test, hydrogen and air all are under 50 ℃ the humidified condition, and hydrogen permeability reaches 10 times of required times conducts " durable time " before the OCV test, according to this time, confirmed to have excellent durability by the film that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) constitutes.That is to say, regardless of the m value, the film that is made of the polymer shown in the general formula (1) of n=1 only shows low durability owing to hang down Tg, and the film that constitutes by the polymer of n=0, when m=3, show not enough improvement effect, when m=2, show low durability, and when m is not less than 4, reach high-durability first.

Even under the following conditions in the another kind of long-time endurance test of conduct---100 ℃ battery temperature, hydrogen and air are all at 60 ℃ of humidifications, at anode-side 0.3MPa with under the pressurized state of cathode side 0.15MPa, current density with 0.3 peace/square centimeter---in service continuously, compare with the film that is made of the polymer shown in the general formula (1) of n=1 and m=2 or by the film that the polymer of n=0 and m=2 constitutes, the film that is made of the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) is found and shows excellent durability.

Embodiment

Specifically illustrate the present invention based on the following example.

Reference example 1

CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F's (No. 1) is synthetic

With 900 gram ICF ₂CF ₂CF ₂The mixtures of COF, 39 milliliters of tetraethylene glycol dimethyl ethers, 390 milliliters of adiponitriles and 15 gram potassium fluorides add in 2 liters of autoclaves, and add 633 gram HFPOs (HFPO) with 15 hours, and the while is 0 ℃ of stirring.After reaction, discharge excessive HFPO, and from reactant mixture, isolate bottom by fluid separation applications.Then thus obtained liquid distillation is obtained 1,066 gram ICF ₂CF ₂CF ₂CF ₂OCF (CF ₃) COF.

Boiling point: 77 ℃ (14 kPas)

¹⁹F-NMR δ (CFCl ₃Base): 24.7 (1F) ,-62.3 (2F) ,-79.9 (1F) ,-83.7 (3F) ,-87.2 (1F) ,-1 14.8 (2F) ,-125.7 (2F) ,-131.7ppm (1F).

Then, restrain ICF at 120 ℃ with 490 ₂CF ₂CF ₂CF ₂OCF (CF ₃) COF dropwise adds and be furnished with mechanical agitator and reflux cooler and contain in advance in 1 liter of three-neck flask of the dry potash of 276 grams.After dropwise interpolation is finished, stirred lasting 1 hour again.Change reflux cooler into still head, when remaining on 20 kPas, this system is heated to 180 ℃.Continue heating until stopping to produce distillate, then the liquid distillation of collecting is purified to obtain 335 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂I.

Boiling point: 79 ℃ (21 kPas)

¹⁹F-NMR δ (CFCl ₃Base) :-63.4 (2F) ,-85.5 (2F) ,-113.7 (1F) ,-114.0 (2F) ,-122.1 (1F) ,-124.6 (2F) ,-136.4ppm (1F).

Then, at 30 to 60 ℃ chlorine is blown into and is furnished with gas blow pipe and reflux cooler and contains 335 gram CF in advance ₂=CFOCF ₂CF ₂CF ₂CF ₂In 1 liter of flask of I.Air blowing continues to raw material and exhausts to obtain the rough CF of 388 grams ₂ClCFClOCF ₂CF ₂CF ₂CF ₂I.

With the rough CF of 388 grams ₂ClCFClOCF ₂CF ₂CF ₂CF ₂I at room temperature dropwise adds in 3 liters of flasks that contain the 2000 gram sodium dithionites that are dissolved in 1500 ml waters-acetonitrile (volume ratio=1: 1) in advance.After stirring 2 hours, with vinyl acetate extractive reaction product.From vinyl acetate mutually solvent evaporated with obtain 375 the gram rough CF ₂ClCFClOCF ₂CF ₂CF ₂CF ₂SO ₂Na.

Restrain above-mentioned rough CF at 0 ℃ to being dissolved with 375 in advance ₂ClCFClOCF ₂CF ₂CF ₂CF ₂SO ₂Be blown into chlorine in 700 ml waters of Na.After raw material exhaust, extract be separated in the bottom liquid level and distill with obtain 262 the gram CF ₂ClCFClOCF ₂CF ₂CF ₂CF ₂SO ₂Cl.

With thus obtained 262 gram CF ₂ClCFClOCF ₂CF ₂CF ₂CF ₂SO ₂Cl is dissolved in 1 liter of acetonitrile, add 130 gram KF then and when stirring 50 ℃ of heating 4 hours.After reactant mixture added entry, extract the liquid level that is separated in the bottom and like this distillation obtain 152 gram CF ₂ClCFClOCF ₂CF ₂CF ₂CF ₂SO ₂F.

With 152 gram CF ₂ClCFClOCF ₂CF ₂CF ₂CF ₂SO ₂F is dissolved in 300 milliliters of ethanol, adds then in advance to restrain zinc powders with 29 of watery hydrochloric acid washing and drying, and 80 ℃ of reactions 1.5 hours.Reactant mixture is cooled to room temperature in air, filters, wash with water, distillation obtains 110 gram CF then ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F.

Boiling point: 91.8 ℃ (40.4 kPas)

¹⁹F-NMR δ (CFCl ₃Base): 43.8 (1F) ,-86.9 (2F) ,-110.0 (2F) ,-116.8 (1F) ,-122.2 (2F) ,-124.3 (1F) ,-126.9 (2F) ,-138.4ppm (1F).

GC-MS(EI)：m/z?283、169、131、119、100、69、67。

Reference example 2

CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F's (No. 2) is synthetic

With 300 gram I (CF ₂) ₄The mixture of I, 675 milliliters of acetone and 225 ml waters adds to be furnished with in 2 liter of four neck flask of reflux column and blender, is placed in the ice bath then and slowly adds 86.7 gram Na ₂S ₂O ₄Stir 3 hours afterreaction mixtures ¹⁹F-NMR the analysis showed that the I (CF that has generated 35.3 moles of % ₂) ₄SO ₂The NaO of Na and 8.1 moles of % ₂S (CF ₂) ₄SO ₂Na.Use evaporator decompression distillation from above-mentioned reactant mixture to fall acetone and I (CF ₂) ₄Behind the I, reactant mixture is added in 300 ml waters, uses ethyl acetate extraction then 3 times.Decompression concentrates ethyl acetate solution, obtains brown solid, warp ¹⁹F-NMR analyzes and confirms that it is I (CF ₂) ₄SO ₂Na (yield: 35.3%).

To contain I (CF ₂) ₄SO ₂The above-mentioned viscous liquid of Na is transferred in 1 liter of four neck flask being furnished with gas blow pipe and is further added 300 ml waters.This flask is placed ice bath, and in liquid, be blown into chlorine to form the layer of two separation.Isolate lower floor, obtain 99.2 grams and contain I (CF ₂) ₄SO ₂The liquid of Cl (yield: 99.6%, based on described I (CF ₂) ₄SO ₂Na).

With the 99.2 gram I (CF that as above obtain ₂) ₄SO ₂Cl adds in 500 ml flasks of being furnished with reflux column with 40.4 gram KF and 200 milliliters of acetonitriles, stirs 2 hours at 50 ℃ then.After reaction was finished, it was two-layer to be divided into to add entry in reactant mixture.Isolate lower floor, obtain 86.5 grams and contain I (CF ₂) ₄SO ₂The liquid of F (yield: 90.9%).

The 86.5 gram I (CF that as above obtaining ₂) ₄SO ₂Adding 225 grams 60% oleum under atmospheric pressure heated 19 hours at 60 ℃ then among the F, and at room temperature left standstill the layer with two separation that obtain reactant mixture, and conversion ratio is 89%.Isolate the upper strata, with concentrated sulfuric acid washing, distillation is purified then

(boiling point: 70 ℃/75 kPas) is to obtain 36.2 gram liquid.This liquid warp ¹⁹F-NMR analyzes to confirm it is FOC (CF ₂) ₃SO ₂F (yield: 61.3%).

¹⁹F-NMR δ (CFCl ₃Base): 44.3ppm (1F), 22.5ppm (1F) ,-109.8ppm (2F) ,-119.5ppm (2F) ,-122.4ppm (2F).

With 66.4 gram FOC (CF ₂) ₃SO ₂The mixtures of F, 3 milliliters of tetraethylene glycol dimethyl ethers, 30 milliliters of adiponitriles and 1.8 gram potassium fluorides add in 100 milliliters of autoclaves, and add 39 gram HFPOs (HFPO), simultaneously 0 ℃ of stirring.From adding after HFPO begins 5 hours, make reaction mixture sat, when gauge pressure becomes 0MPa, form the layer of two separate.Isolate lower floor, and decompression distillation (boiling point=91 ℃/23 kPas) is to obtain 87.1 gram CF ₃CF (COF) O (CF ₂) ₄SO ₂F (yield: 82.2%).

Be furnished with dropping funel, Liebig cooler and collecting in 200 milliliter of four neck flask of flask, it is anhydrous 1 to add the 11.16 pre-dry potash of gram and 20 milliliters, and the 2-dimethoxy-ethane dropwise slowly adds the above-mentioned CF of 30 grams then ₃CF (COF) O (CF ₂) ₄SO ₂F heats under nitrogen current in 40 ℃ oil bath simultaneously.Warp was stirred in the back continuation that stops to foam 1.5 hours ¹⁹F-NMR analysis confirmation raw material neutralize fully and change into CF ₃CF (CO ₂K) O (CF ₂) ₄SO ₂F.Decompression distillation falls 1 from reactant mixture, the 2-dimethoxy-ethane, and by heating the drying under reduced pressure residues at 140 ℃.When containing CF ₃CF (CO ₂K) O (CF ₂) ₄SO ₂The dried residue decompression (12 kPas) of F is when being heated to 170 ℃, and decarboxylic reaction begins and begin to occur distillate.Further make temperature slowly rise to 185 ℃ at last.The distillation of gained liquid is purified (boiling point: 57 ℃/13.3 kPas) to obtaining 20.6 gram CF ₂=CFO (CF ₂) ₄SO ₂F (yield: 80.6%).

¹⁹F-NMR δ (CFCl ₃Base): 43.8ppm (1F) ,-87.0ppm (2F) ,-110.0ppm (2F) ,-116.9ppm (1F) ,-122.2ppm (2F) ,-124.4ppm (1F) ,-127.0ppm (2F) ,-138.4ppm (1F).

Reference example 3

CF ₂=CFOCF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₂F's is synthetic

With 122 gram I (CF ₂) ₆The mixture of I, 450 milliliters of acetone and 50 ml waters adds to be furnished with in 2 liters of three-neck flasks of reflux column and blender, is placed in the ice bath then and slowly adds 48 gram Na ₂S ₂O ₄, stirred 2 hours at 25 ℃ then.Reactant mixture ¹⁹F-NMR the analysis showed that the I (CF that has generated 68 moles of % ₂) ₆SO ₂The NaO of Na and 6 moles of % ₂S (CF ₂) ₆SO ₂Na.From above-mentioned reactant mixture, distill acetone and I (CF ₂) ₄Behind the I, residue is added among 300 milliliters of HFC43-100mee, filter then and remove solid material.Decompression distillation is fallen HFC43-10mee to reclaim 31.6 gram I (CF from reactant mixture ₂) ₆I.On the other hand, this solid material is added in 500 ml waters, use ethyl acetate extraction then 3 times.Decompression concentrates ethyl acetate solution to obtain solid, warp ¹⁹F-NMR analyzes and confirms that it is I (CF ₂) ₆SO ₂Na.

With above-mentioned I (CF ₂) ₄SO ₂Na transfers in 1 liter of three-neck flask being furnished with gas blow pipe and further adds 300 ml waters.This flask is placed ice bath, and in liquid, be blown into chlorine to form the layer of two separation.Isolate lower floor, obtain 75.1 gram I (CF ₂) ₆SO ₂Cl (yield: 95.2%).

With the 175.1 gram I (CF that as above obtain ₂) ₆SO ₂Cl adds in 500 ml flasks of being furnished with reflux column with 24.8 gram KF and 150 milliliters of acetonitriles, stirs 2 hours at 50 ℃ then.After reaction was finished, it was two-layer to be divided into to add entry in reactant mixture.Isolate lower floor, obtain 66.8 grams and contain I (CF ₂) ₆SO ₂The liquid of F (yield: 91.9%).

The 129 gram I (CF that as above obtaining ₂) ₆SO ₂Add 269 grams, 60% oleum among the F, then under atmospheric pressure 60 ℃ and 80 ℃ of heating 8.5 hours then, with the two separate that obtains reactant mixture layer, and conversion ratio is 100%.Isolate the upper strata, restrain liquid to obtain 89 with concentrated sulfuric acid washing.This liquid warp ¹⁹F-NMR analyzes to confirm it is FOC (CF ₂) ₅SO ₂F (yield: 93%).

¹⁹F-NMR?44.3ppm(1F)、22.5ppm(1F)、-109.7ppm(2F)、-120.0ppm(2F)、-121.8ppm(2F)、-122.5ppm(2F)、-124.1ppm(2F)。

With 79 gram FOC (CF ₂) ₅SO ₂The mixtures of F, 3.5 milliliters of tetraethylene glycol dimethyl ethers, 35 milliliters of adiponitriles and 1.45 gram potassium fluorides add in 100 milliliters of autoclaves, and add 41.4 gram HFPO, simultaneously 0 ℃ of stirring.This moment, conversion ratio was 64%, therefore added 3.5 milliliters of tetraethylene glycol dimethyl ethers again, added 24.2 gram HFPO with 3.5 hours then, simultaneously 0 ℃ of stirring.The reaction after, discharge excessive HFPO and with the inclusion fractionation to isolate lower floor.Thus obtained conversion ratio is 96%.The distillation of gained liquid is restrained CF to obtain 91.6 ₃CF (COF) O (CF ₂) ₆SO ₂F (yield: 81%).

In being furnished with 200 milliliters of three-neck flasks of dropping funel, it is anhydrous 1 to add the 31.9 pre-dry potash of gram and 1000 milliliters, and the 2-dimethoxy-ethane dropwise slowly adds the above-mentioned CF of 120 grams then under nitrogen current ₃CF (COF) O (CF ₂) ₆SO ₂F.

At room temperature continuous stirring 1 hour and further 50 ℃ stir 1 hour after, warp ¹⁹F-NMR analysis confirmation raw material neutralize fully and change into CF ₃CF (CO ₂K) O (CF ₂) ₆SO ₂F.After the filtering reaction liquid, decompression distillation falls 1 from filter liquor, the 2-dimethoxy-ethane, and, restrain CF to obtain 122.2 by at 100 ℃ of heating drying under reduced pressure residues ₃CF (CO ₂K) O (CF ₂) ₆SO ₂F (yield: 96%).

With 82 gram CF ₃CF (CO ₂K) O (CF ₂) ₆SO ₂The F adding is furnished with in 200 milliliters of three-neck flasks of distillation column, and then 180 ℃ to 200 ℃ decompressions (22 to 1.0 kPas) heating 5.25 hours, decarboxylic reaction began and obtained 63.3 to restrain distillates this moment.Thus obtained distillate is further distilled purification to obtain 51.2 gram CF ₂=CFO (CF ₂) ₆SO ₂F (yield: 76%).

¹⁹F-NMR：43.8ppm(1F)、-86.9ppm(2F)、-110.0ppm(2F)、-117.1ppm(1F)、-121.9ppm(2F)、-123.4ppm(2F)、-124.0ppm(2F)、-124.7ppm(1F)、-127.3ppm(2F)、-138.4ppm(1F)。

Embodiment 1

In 200 milliliters of stainless steel autoclaves, add 75 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F and 75 gram HFC43-10mee (CF ₃CHFCHFCF ₂CF ₃).This autoclave is fully purged with nitrogen, change tetrafluoroethene (TFE) then into.Add 0.3 gram (CF ₃CF ₂CF ₂COO) ₂5% solution (it is stored in the refrigerator) in HFC43-10mee is as polymerization initiator, and with TFE autoclave is forced into 0.33MPa.If suitable, add TFE again to keep the pressure of 0.33MPa, simultaneously 35 ℃ of stirrings.0.15 gram (CF reinjects midway ₃CF ₂CF ₂COO) ₂5% solution in HFC43-10mee.After 4.5 hours,, in polyblend, add methyl alcohol and filtration then with the autoclave venting.With the solid material of HFC 43-10mee/ methanol mixed solution (volume ratio=2/1) washing separation, and the dry 7.83 gram white solids that obtain.

In the IR of this solid spectrum, observe SO ₂The peak that the F group produces, it shows that this solid contains SO ₂The F group.Warp ¹⁹F-NMR spectrum confirms that also this solid is to contain CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂The copolymer of F monomeric unit and TFE monomeric unit.

When the D4002 melt index (MI) verifier that uses Dynisco Inc.of USA to make was measured under the condition in 270 ℃, 2.16 kilograms load and 2.09 millimeters apertures, the melt flow rate (MFR) of this polymer (MFR) was 6.46 grams/10 minutes.

Is 50 micron molded membrane 270 ℃ of compactings to obtain thickness with this copolymer.

Above-mentioned film is soaked 1 hour to carry out saponification in the solution of KOH/ methyl-sulfoxide/water (weight ratio=30: 15: 55) of 90 ℃.Subsequently, wash this film with water, soaked 1 hour in 90 ℃ 4N sulfuric acid, wash with water and drying again, obtaining equivalent (EW) is the film (A-film) of 829 gram/equivalents.

The proton conductivity of A-film in 23 ℃ of water is 0.12S/cm.Use 1 * 6 centimetre of membrane sample, in deionized water, measure proton conductivity at 23 ℃ by the 6-sonde method.By the proton conductivity in similar approach measurement the following examples and the Comparative Examples.

The water content of A-film (%) is 26%, and it is following acquisition: the A-film was soaked 30 minutes in 80 ℃ of hot water, measure and wipe surface water A-film weight afterwards rapidly, and it is compared the weight of increase divided by dry polymer weight with dry polymer weight.

Use A﹠amp; DInc., the dynamic viscoelastic measuring equipment " RHEOVIBLONDDV-01-FP " that Japan makes, with 30 millimeters that downcut from the A-film * 3 millimeters rectangle samples, in the temperature dependency of under the condition of the temperature range of room temperature to 300 ℃ and 35Hz frequency, measuring the dynamic viscoelastic of A-film.The maximum loss factor (Tg) that this measurement result is determined is 145 ℃.In measuring process, this film is in the rapid reduction of 193 ℃ of modulus that demonstrate flexibility, thereby causes fracture.

Use Shimadzu Corp., the Shimadzu thermogravimeter TGA-50 that Japan makes in argon gas and air atmosphere and the TGA that under 10 ℃/minute heating rate, carries out the A-film measure.The flow velocity of argon gas and air 50 ml/min of respectively doing for oneself.Reduce at oxygen concentration and not to be higher than 1, begin the measurement in argon atmospher during 000ppm.Use measurement result to obtain temperature-figure-of-merit curve, based on this curve, the initial temperature of thermal decomposition is defined as thermal decomposition and begins before and the crosspoint of the positive tangent of curve afterwards.What record thus is respectively 393 ℃ and 362 ℃ at argon gas and aerial thermal decomposition initial temperature.

(measurement of hydration)

According to the method for describing in the JP-A-57-25331 specification above-mentioned A-film is weighed after 16 hours 110 ℃ of dryings, it was soaked in boiling water 30 minutes, in room temperature water, soaked 5 minutes then according to the method for describing among the open WO 2004/062019 in the world.This film is weighed after wiping surface water rapidly.Obtain water absorption (is 52 weight % for the A-film) by weight gain, by the molal quantity of this water absorption calculating whenever the water of amount sulfonic acid group correspondence, it multiply by the EW value subsequently and obtains hydration.The hydration of A-film is 19,900, and the product of hydration and EW is 16.5 * 10 ⁶Change in size between the dry and wet state is 53%, and it is expressed as the area under the wet condition and the incremental raio (hot water resistance test) of the area under the dried state.

Membrane sample and water are placed the pressure vessel of being furnished with the inner glass cup, and in oil bath, heated 3 hours with 160 ℃.After with this container cooling, film is taken out, dry then, it does not show weight change.

(puncture test in 80 ℃ of water)

By clamping with SUS ring, with in advance in 80 ℃ of water 1 hour film of swelling fix, and place 80 ℃ water-bath, the eleven punch 11 of going forward side by side.Under the condition of 0.5 millimeter pin radius of curvature and 2 mm/second puncture speed, use KATO TECH Corp., the KES-G5 Handy Press testing equipment that Japan makes is measured the intensity that pierces through of film, and after changing into 50 microns wet-film thickness, piercing through intensity is 190gf.

(measurement of low-angle X-ray scattering)

Be immersed at film under the state of pure water, use Rigaku Corp., the low-angle X-ray scattering of the nano level small angle scattering device measuring film that has CFC that Japan makes.Penetrate the X-ray from direction with the film Surface Vertical.The scattering strength that is obtained by observed spectrum is than (I ²/ I ¹) be 9.3, (I wherein ¹) and (I ²) be respectively the intensity under 2 θ of 3 ° and 0.3 °.

Embodiment 2

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 50 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 100 gram HFC43-10 mee and 0.4 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee, and be forced into 0.225MPa with TFE.Ground similar to Example 1, (twice 0.2 gram (CF reinject midway to carry out polymerization 6.8 hours at 35 ℃ ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee) to obtain 10.46 gram white solids.The MFR of polymer is 14.5 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, with acquisition-SO ₃H type film (B-film), it has the ion exchange capacity of 860 gram/equivalents.The Tg of the proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and film is respectively 0.11S/cm, 22% and 150 ℃.

With among the embodiment 1 similarly, the TGA that uses this sulfonic acid polymer to carry out shows, is respectively 395 ℃ and 364 ℃ at argon gas and airborne pyrolysis initial temperature.

With the water absorption of the similar B-film that records among the embodiment 1 be 48 weight %.The hydration that is obtained by above-mentioned water absorption is 19,800, and the product between hydration and the EW is 17.0 * 10 ⁶Change in size between the dry and wet state is 46%.

When measuring low-angle X-ray scattering among the embodiment 1 similarly, scattering strength compares I ²/ I ¹Be 37.

Embodiment 3

In the autoclave identical, add 50 gram CF with embodiment 1 ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 100 gram HFC43-10mee and 0.36 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee, and be forced into 0.325MPa with TFE.(polymerization initiator does not reinject) restrains white solids to obtain 13.52 to carry out polymerization 2.9 hours at 35 ℃.The MFR of polymer is 0.11 gram/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, and thus obtained-SO ₃The ion exchange capacity of H type film (C-film) is 1,080 gram/equivalent.The Tg of the proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and film is respectively 0.068S/cm, 10% and 155 ℃.

With among the embodiment 1 similarly, the TGA that uses this sulfonic acid polymer to carry out shows, is respectively 390 ℃ and 367 ℃ at argon gas and airborne pyrolysis initial temperature.

With the water absorption of the similar C-film that records among the embodiment 1 be 25 weight %.The hydration that is obtained by above-mentioned water absorption is 16,200, and the product between hydration and the EW is 17.5 * 10 ⁶Change in size between the dry and wet state is 27%.

Embodiment 4

In 200 milliliters of stainless steel autoclaves, add 12.75 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F and 39 gram HFC43-10mee.This autoclave fully with behind the nitrogen purging, is added 0.6 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee is as polymerization initiator, and with tetrafluoroethene (TFE) autoclave is forced into 0.3MPa.If suitable, add TFE again to keep the pressure of 0.3MPa, simultaneously 23 ℃ of stirrings.After 1.5 hours,, in polyblend, add methyl alcohol and filtration then with the autoclave venting.With solid material and the drying that HFC 43-10mee separates with methanol wash, obtain 2.42 gram white solids.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, and thus obtained-SO ₃The ion exchange capacity of H type film (D-film) is 1,300 gram/equivalent.Proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and the Tg of film are respectively 0.044S/cm, 7% and 156 ℃.

With the water absorption of the similar D-film that records among the embodiment 1 be 16 weight %.The hydration that is obtained by above-mentioned water absorption is 15,000, and the product between hydration and the EW is 19.5 * 10 ⁶Change in size between the dry and wet state is 19%.

Embodiment 5

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 75 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 75 gram HFC43-10 mee and 0.27 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee, and be forced into 0.33MPa with TFE.Ground similar to Example 1, (twice 0.14 gram (CF reinject midway to carry out polymerization 6.8 hours at 35 ℃ ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee) to obtain 9.19 gram white solids.The MFR of polymer is 9.0 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, and thus obtained-SO ₃The ion exchange capacity of H type film (E-film) is 780 gram/equivalents.The Tg of the proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and film is respectively 0.14S/cm, 47% and 145 ℃.

With the water absorption of the similar E-film that records among the embodiment 1 be 62 weight %.The hydration that is obtained by above-mentioned water absorption is 21,000, and the product between hydration and the EW is 16.4 * 10 ⁶Change in size between the dry and wet state is 49%.

Embodiment 6

In 200 milliliters of stainless steel autoclaves, add 30 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₂F and 30 gram HFC43-10mee.This autoclave fully with behind the nitrogen purging, is added 1.0 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee is as polymerization initiator.Autoclave is purged with tetrafluoroethene (TFE), and further be forced into 0.2MPa with TFE.If suitable, add TFE again to keep the pressure of 0.2MPa, simultaneously 25 ℃ of stirrings.After 6 hours,, in polyblend, add methyl alcohol and filtration then with the autoclave venting.With the solid material of HFC 43-10mee washing separation, and the dry 7.11 gram white solids that obtain.

In the IR of this solid spectrum, observe SO ₂The peak that the F group produces, it shows that this solid contains SO ₂The F group.Warp also ¹⁹F-NMR spectrum confirms that this solid is to contain CF ₂=CFOCF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₂The copolymer of F monomeric unit and TFE monomeric unit.The MFR of this polymer is 9.5 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, and thus obtained-SO ₃The ion exchange capacity of H type film (F-film) is 870 gram/equivalents.The Tg of the proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and film is respectively 0.12S/cm, 31% and 142 ℃.

With among the embodiment 1 similarly, the TGA that uses this sulfonic acid polymer to carry out shows, is respectively 385 ℃ and 373 ℃ at argon gas and airborne pyrolysis initial temperature.

With the water absorption of the similar F-film that records among the embodiment 1 be 51 weight %.The hydration that is obtained by above-mentioned water absorption is 21,400, and the product between hydration and the EW is 18.6 * 10 ⁶Change in size between the dry and wet state is 53%.

Embodiment 7

Each film (A, B, C, E and F-film) that obtains from embodiment 1 to 3 and 5 to 6 downcuts the fragment of 3 centimetres of 3 cm x (0.1 gram), and place the SUS sampling pipe of 5 mm dias, 5 centimeter length, and its entrance and exit is linked to each other with PTFE tube with stainless steel tube respectively.Whole sampling pipe is placed in 200 ℃ the baking oven, and adds air with the speed of 20 ml/min through stainless steel tube.Make air by this pipeline bubbler of filling 80 ℃ of water midway, thus with air wetting.The PTFE tube of outlet is imported 8 milliliters of rare NaOH aqueous solution (6 * 10 ^-3N), and continuously each hour collected a catabolite in 8 hours.

By the measurement of the chromatography of ions, concentration 4 hour after the constant of each hour fluoride ion in collecting liquid, by the measurement data after 4 hours calculate and per 8 hours consequent fluoride ion amounts as follows:

A-film: 0.080 weight % of fluorine total amount in the original polymer

B-film: 0.057 weight % of fluorine total amount in the original polymer

C-film: 0.055 weight % of fluorine total amount in the original polymer

E-film: 0.075 weight % of fluorine total amount in the original polymer

F-film: 0.083 weight % of fluorine total amount in the original polymer

Comparative Examples 1:

To by extruding the film that the copolymer (k/l=5) shown in the following formula (14) forms (thickness=45 micron) at 270 ℃

Carry out with embodiment 1 in similarly saponification and acid treatment, with obtain ion exchange capacity be 950 gram/equivalents-SO ₃H type film (thickness=50 micron).The Tg of the proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and film (P-film) is respectively 0.09S/cm, 23% and 123 ℃.

With among the embodiment 1 similarly, the TGA that uses this sulfonic acid polymer to carry out shows, is respectively 316 ℃ and 314 ℃ at argon gas and airborne pyrolysis initial temperature.

To the fragment of 3 centimetres of 3 cm x of downcutting from this film carry out with embodiment 4 similar resolution test.The concentration constant of similar each that records hour fluoride ion in collecting liquid 4 to 6ppm.The fluoride ion amount that formed thus in per 8 hours that is got by this measurement data calculating is 0.54 weight % of fluorine total amount in the original polymer, and it is than the high one-level of the result among the embodiment 7.

Comparative Examples 2

To by extruding the film that the copolymer (k/l=4.6) shown in the following formula (15) forms (thickness=45 micron) at 270 ℃

Carry out with embodiment 1 in similarly saponification and acid treatment, with obtain ion exchange capacity be 740 gram/equivalents-SO ₃H type film (thickness=50 micron).The Tg of the proton conductivity in 23 ℃ of water, the water content in 80 ℃ of hot water and film (Q-film) is respectively 0.13S/cm, 36% and 148 ℃.

With among the embodiment 1 similarly, the TGA that uses this sulfonic acid polymer to carry out shows, is respectively 314 ℃ and 319 ℃ at argon gas and airborne pyrolysis initial temperature.

To the fragment of 3 centimetres of 3 cm x of downcutting from this film carry out with embodiment 4 similar resolution test.The concentration constant of similar each that records hour fluoride ion in collecting liquid 4 to 6ppm.The fluoride ion amount that formed thus in per 8 hours that is got by this measurement data calculating is 0.47 weight % of fluorine total amount in the original polymer, and it is than the high one-level of the result among the embodiment 7.

Comparative Examples 3

(ion exchange capacity is 1 to Nafion (registered trade mark of DuPont Co.) 117 films on the use market, 100 gram/equivalents, DuPont Co. make and with the film of the corresponding fluorinated sulfonic polymer of general formula (1) of n=1 and m=2) carry out TGA similar to Example 1ly, show at argon gas and airborne thermal decomposition initial temperature to be respectively 317 ℃ and 312 ℃.

Embodiment 8

Suppose that reaction is shown below:

By setting (A): (CF ₂) ₂CFOCF ₂CF ₂SO ₃H, (B): (CF ₂) ₂CFOCF ₂CF ₂CF ₂SO ₃H, (C): (CF ₂) ₂CFOCF ₂CF ₂CF ₂CF ₂SO ₃H and (D): (CF ₂) ₂CFOCF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₃Reaction between each computation model of H and the OH group is carried out density function and is calculated.

In calculating, use Accelrys Corp., the DMo13 of USA as computation model, use DNP as basic function, use PW91 type gradient calibration potential energy as the relevant potential energy of electron exchange.

(A): (CF ₂) ₂CFOCF ₂CF ₂SO ₃H, (B): (CF ₂) ₂CFOCF ₂CF ₂CF ₂SO ₃H, (C): (CF ₂) ₂CFOCF ₂CF ₂CF ₂CF ₂SO ₃H and (D):

(CF ₂) ₂CFOCF ₂CF ₂CF ₂CF ₂CF ₂CF ₂SO ₃The activation energy (based on a unit sulfonic acid group) of the speed of determining in the oxidative pyrolysis process of H reaction is respectively 36.51 kilocalories/equivalent, and 38.99 kilocalories/equivalent, 43.79 kilocalories/equivalent and 54.17 kilocalories/equivalent.

The polymer that uses in polymer that uses among the polymer that uses among the embodiment 1 to 5, the embodiment 6 and the Comparative Examples 2 corresponds respectively to computation model (C), (D) and (A).In other words, the difference trend of the heat resistanceheat resistant-oxidizability shown in the contrast between aforementioned calculation result and embodiment 1 to 7 and the Comparative Examples 2 conforms to.

Embodiment 9 (quickening the OCV test)

At first, anode side gas diffusion electrode and cathode side gas-diffusion electrode are fixed on rightabout, between them, sandwich the polyelectrolyte membranes (A-film and F-film) that obtains in embodiment 1 and 6, and install in the evaluation and test battery.With the 5 weight % solution coat DE NORA NORTH AMERICACo.s of the copolymer (EW=910 gram/equivalent) shown in the following formula (16) in water-ethanol (weight ratio=1: 1), the gas-diffusion electrode that USA makes, ELAT  (carries=0.4 milligram/square centimeter of Pt amount, hereinafter identical), in air, be dried to solid then at 140 ℃.The amount of polymers of load is 0.8 milligram/square centimeter.

Be fixed to evaluating apparatus (TOYO Corp. will evaluating and testing battery, the fuel cell evaluating system 890CL that Japan makes) in and after the heating, hydrogen and air make this system remain on OCV (open circuit voltage) state respectively with the velocity flow anode and the cathode side of 200 cc/min.Before being fed to battery, the water-bubbling method that is used for humidify gas is with hydrogen and air wetting.

Under not pressurizeing the condition of (atmospheric pressure), 100 ℃ battery temperatures, 50 ℃ gas humidification temperature and anode and cathode side do not carry out this test.

Use GTR TEC Corp., whether the flow model gas permeation analyzer GTR-100FA that Japan makes has produced pin hole from hydrogen permeability of measurement of every about 10 hours of this on-test thereby detect in polymer electrode membrane.When the pressure that will evaluate and test the galvanic anode side with hydrogen remains on 0.15MPa, will with the velocity flow of 10 cc/min to the argon gas of cathode side as carrier gas in battery because crossover leakage and add gas chromatograph G2800, to determine the infiltration capacity of hydrogen from the hydrogen of anode side cathode side infiltration.Calculate the permeability L (cubic centimetre centimetre/square centimeter/second/handkerchief) of hydrogen by following formula:

L＝(X×B×T)/(P×A×D)

Wherein, x (cubic centimetre) is the infiltration capacity of hydrogen; B (=1.100) is a correction coefficient; T (centimetre) be the thickness of polymer dielectric film; P (handkerchief) is a hydrogen partial pressure; A (square centimeter) is that the hydrogen impermeable surface of polymer dielectric film is long-pending; And D (second) is a Measuring Time.

During before hydrogen permeability reaches OCV test 10 times, stop test.

As the result of above-mentioned evaluation and test, A-film and F-film all show excellent durability, almost do not have hydrogen leakage in 200 hours test period.

Comparative Examples 4

To by extruding the film that the copolymer (k/l=5) shown in the following formula (17) forms (thickness=45 micron) at 270 ℃

Carry out with embodiment 1 in similarly saponification and acid treatment, with obtain ion exchange capacity be 1,000 gram/equivalent-SO ₃H type film (thickness=50 micron).This film is named as the R-film.

To by extruding the film that the copolymer (k/l=5) shown in the following formula (18) forms (thickness=45 micron) at 270 ℃

Carry out with embodiment 1 in similarly saponification and acid treatment, with obtain ion exchange capacity be 830 gram/equivalents-SO ₃H type film (thickness=50 micron).This film is named as the S-film.

With the film (P-film and Q-film) that obtains in Comparative Examples 1 and 2 and above-mentioned R-film and S-film, quicken the OCV test similar to Example 9ly.For P-film and Q-film, after 20 hours on-tests, hydrogen permeate improves suddenly.For R-film and S-film, hydrogen leakage improves suddenly after on-test 30 and 50 hours respectively.In other words, be 1 corresponding P-film and the R-film deterioration in 20 to 30 hours of general formula (1) with n, and to n be 0 and m be 2 Q-film, also be deterioration in 20 hours, and n be 0 and m to be that 3 S-film can bear long-time slightly, but also deterioration in 50 hours.

Embodiment 10

In 200 milliliters of stainless steel autoclaves being furnished with the inner glass cup, add by what repeat that the method identical with embodiment 1 obtain and 5.0 restrain (dry weight)-SO ₃H type film (EW=820 ,-SO ₂And heated while stirring 4 hours the MFR=3.8 of F type film) and 95 gram water/ethanol (1/1 by weight), at 180 ℃.After being cooled to room temperature, find when opening container that all solids disappears and becomes homogeneous solution.With this solution or dispersion liquid is cultivated in Petri dish and 60 ℃ of dryings 1 hour, then 80 ℃ dry 1 hour again, be 50 microns casting film 200 ℃ of annealing 1 hour to form thickness then.

The water absorption that is similar to this casting film that embodiment 1 records is 48 weight %.The hydration that is obtained by above-mentioned water absorption is 17,900, and the product of hydration and EW is 14.7 * 10 ⁶Change in size between the dry and wet state is 32%.That is to say in 1 hour casting film of 200 ℃ of annealing and embodiment 1, almost do not have what difference between the film of compacting.

Embodiment 11

Under different dryings and annealing conditions, make casting film by solution that makes among the embodiment 10 or dispersion liquid.At first, by 90 ℃ of dryings 10 minutes, then 200 ℃ of annealing 10 minutes, preparation thickness is 30 microns casting film.The water absorption of this film is 49 weight %.The hydration that is obtained by above-mentioned water absorption is 18,300, and the product of hydration and EW is 15.0 * 10 ⁶Change in size between the dry and wet state is 33%.Secondly, by 60 ℃ of dryings 1 hour and 80 ℃ dry 1 hour again, then 170 ℃ of annealing 1 hour, make the casting film of another 50 micron thickness.The water absorption of this film is 65 weight %.The hydration that is obtained by above-mentioned water absorption is 24,300, and the product of hydration and EW is 19.9 * 10 ⁶Change in size between the dry and wet state is 47%.That is to say anneal almost do not have what difference between 10 minutes 200 ℃ of annealing 1 hour with at 200 ℃, the hydration when 170 ℃ of annealing is higher.

Embodiment 12

The films and 47.5 that obtain among adding 2.5 gram (dry weight) embodiment 6 in being furnished with 200 milliliters of stainless steel autoclaves of inner glass cup restrain water/ethanol (1/1 by weight) and heated while stirring 4 hours at 180 ℃.After being cooled to room temperature, find when opening container that all solids disappears and becomes homogeneous solution.With this solution or dispersion liquid is cultivated in Petri dish and 60 ℃ of dryings 1 hour, then 80 ℃ dry 1 hour again, be 50 microns casting film 200 ℃ of annealing 1 hour to form thickness then.

The water absorption that is similar to this casting film that embodiment 1 records is 51 weight %.The hydration that is obtained by above-mentioned water absorption is 21,400, and the product of hydration and EW is 18.6 * 10 ⁶Change in size between the dry and wet state is 40%.

Embodiment 13

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 80 gram HFC43-10mee and 1.0 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee, and be forced into 0.22MPa with TFE.Ground similar to Example 1 carries out polyase 13 hour to obtain 5.8 gram white solids at 35 ℃.The MFR of polymer is 86.3 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 815 gram/equivalents.

With the water absorption of similar this film that records among the embodiment 1 be 60 weight %.The hydration that is obtained by above-mentioned water absorption is 22,200, and the product of hydration and EW is 18.1 * 10 ⁶Change in size between the dry and wet state is 55%.

When measuring by the anti-molten test in 160 ℃ of hot water, this film weight has reduced by 9% after test similar to Example 1ly.Carry out the puncture test of this film in 80 ℃ of water, when changing into the wet film basis of 50 micron thickness, it shows the intensity that pierces through of 92gf similar to Example 1ly.

When measuring low-angle X-ray scattering among the embodiment 1 similarly, it shows 49 scattering strength and compares I ²/ I ¹

Embodiment 14

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 80 gram HFC43-10mee and 0.8 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee, and be forced into 0.22MPa with TFE.Ground similar to Example 1 carries out polymerization 5.3 hours to obtain 13.3 gram white solids at 25 ℃.The MFR of polymer is 0.03 gram/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 1045 gram/equivalents.This film has 144 ℃ Tg, and in measuring process in the rapid reduction of 243 ℃ of modulus that demonstrate flexibility, this causes fracture.

With the water absorption of similar this film that records among the embodiment 1 be 25 weight %.The hydration that is obtained by above-mentioned water absorption is 15,000, and the product of hydration and EW is 15.7 * 10 ⁶Change in size between the dry and wet state is 28%.Carry out the puncture test of this film in 80 ℃ of water, when changing into the wet film basis of 50 micron thickness, it shows the intensity that pierces through of 308 gf similar to Example 1ly.

When measuring low-angle X-ray scattering among the embodiment 1 similarly, it shows 38 scattering strength and compares I ²/ I ¹

Embodiment 15

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 80 gram HFC43-10mee and 1.0 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee, and be forced into 0.30MPa with TFE.Ground similar to Example 1 carries out polymerization 2.25 hours to obtain 12.5 gram white solids at 35 ℃.The MFR of polymer is 1.6 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 997 gram/equivalents.This film have 147 ℃ Tg and in measuring process in the rapid reduction of 249 ℃ of modulus that demonstrate flexibility, this causes fracture.

With the water absorption of similar this film that records among the embodiment 1 be 32 weight %.The hydration that is obtained by above-mentioned water absorption is 17,800, and the product of hydration and EW is 17.7 * 10 ⁶Change in size between the dry and wet state is 36%.

Embodiment 16 (evaluation and test of the battery that acts as a fuel)

The following durability evaluation and test that is used for the polyeletrolyte of fuel cell.Preparation electrode catalyst layer as described below.1.00 grams are carried Pt carbon (TANAKA Precious Metals Corp., the TEC10E40E that Japan makes, Pt=36.4 weight %) adds in the 3.31 gram polymer solutions, this solution is thickened to 11 weight % by 5 weight % solution of copolymer (EW=910 gram/equivalent) shown in the formula (16) that is dissolved in water-ethanol (weight ratio=1: 1), add 3.24 gram ethanol then, fully mix to obtain electrode ink with homogenizer then.By silk screen print method electrode ink is applied on the PTFE plate.Use two kinds of coating weights: a kind of is that the Pt of load and the polymer of load all are 0.15 milligram/square centimeter, and another kind is that the Pt of load and the polymer of load all are 0.30 milligram/square centimeter.With at room temperature dry 1 hour of PTFE plate and 120 ℃ air drying 1 hour, obtain the electrode catalyst layer that thickness is about 10 microns thus.The coating weight of the Pt of working load and the polymer of load all be 0.15 milligram/square centimeter electrode as anode catalyst layer, the coating weight of the polymer of the Pt of working load and load all is that 0.30 milligram/square centimeter electrode is as cathode catalyst layer simultaneously.

Thus obtained anode catalyst layer and cathode catalyst layer are fixed on rightabout, between them, sandwich polymer dielectric film.By hot pressing under the end force of 160 ℃ and 0.1MPa, anode catalyst layer and cathode catalyst layer are transferred on the polymer dielectric film, MEA is made in assembling then.

All stick carbon cloth (USA makes for ELAT: registered trade mark B-1, DE NORA NORTH AMERICA) on the two sides of this MEA (outer surface of anode catalyst layer and cathode catalyst layer) as gas diffusion layers and install in the evaluation and test battery.Be fixed to evaluating apparatus (TOYOCorp. will evaluating and testing battery, the fuel cell evaluating system 890CL that Japan makes) in and be heated to after 80 ℃, respectively the antianode side is with the speed of 260 cc/min and target side speed supply of hydrogen and the air with 800 cc/min, and antianode side and cathode side all are forced into 0.20 MPa (absolute pressure).Before being fed to each battery, the water-bubbling method that is used for humidify gas with hydrogen and air respectively at 90 ℃ and 80 ℃ of humidifications.Under these conditions, measure current-voltage curve to check initial characteristic.

After checking initial characteristic, under 100 ℃ battery temperature, carry out endurance test.Two kinds of gases are all at 60 ℃ of humidifications.Supply the hydrogen of 74 cc/min flow velocitys and in down pressurization of 0.30MPa (absolute pressure), the target side is supplied the air of 102 cc/min flow velocitys and, generated electricity with the current density of 0.3 peace/square centimeter down under the condition of pressurization at 0.15 MPa (absolute pressure) simultaneously in the antianode side.Have one minute in the middle of per 10 minutes, opening circuit, to make electric current be 0 to detect OCV (open circuit voltage).

When in the endurance test process, on polymer dielectric film, having produced pin hole, the phenomenon of so-called crossover leakage has taken place exactly, this moment, a large amount of hydrogen leakage arrived cathode side.The concentration of measuring hydrogen in the waste gas of cathode side with microGC (Holland makes for CP4900, Varian Inc.) is to check the degree of this crossover leakage.When measured value obviously raises, stop this test.

Performance by the casting film that is used for fuel cell of preparation among the above-mentioned evaluating method evaluation and test embodiment 10.The result shows below good initial characteristic---the current density of 1.20 peace/square centimeters and the voltage of 0.6V under 80 ℃ battery temperature.Endurance test shows the durability that is not shorter than 500 hours excellence under 100 ℃ battery temperature.

Embodiment 17

Evaluate and test the performance of the film that is used for fuel cell of embodiment 1 preparation similar to Example 16ly.The result shows below good initial characteristic---the current density of 1.20 peace/square centimeters and the voltage of 0.6V under 80 ℃ battery temperature.Endurance test shows the durability that is not shorter than 500 hours excellence under 100 ℃ battery temperature.

Embodiment 18

Evaluate and test the performance of the film that is used for fuel cell of embodiment 12 preparations similar to Example 16ly.The result shows below good initial characteristic---the current density of 1.20 peace/square centimeters and the voltage of 0.6V under 80 ℃ battery temperature.Endurance test shows the durability that is not shorter than 500 hours excellence under 100 ℃ battery temperature.

Comparative Examples 5

In being furnished with 200 milliliters of stainless steel autoclaves of inner glass cup, add the films that obtain in 5.0 gram (dry weight) Comparative Examples 2 and 95 gram water/ethanol (1/1, by weight), and heated while stirring 4 hours at 180 ℃.After being cooled to room temperature, find when opening container that all solids disappears and becomes homogeneous solution.With this solution or dispersion liquid is cultivated in Petri dish and 60 ℃ of dryings 1 hour, then 80 ℃ dry 1 hour again, be 50 microns casting film 200 ℃ of annealing 1 hour to form thickness then.

Evaluate and test the thus obtained performance that is used for the casting film of fuel cell similar to Example 16ly.The result shows below good initial characteristic---the current density of 1.20 peace/square centimeters and the voltage of 0.6V under 80 ℃ battery temperature.On the other hand, after operation 280 hours, endurance test demonstrates the rapid rising of crossover leakage under 100 ℃ battery temperature, thereby causes test to stop.As above observed, although initial characteristic is good, can not obtain sufficient durability.

Embodiment 19

Solution or dispersion liquid coating DE NORA NORTHAMERICA with preparation among the embodiment 10, the gas-diffusion electrode ELAT  that USA makes (carrying=0.4 milligram/square centimeter of Pt amount), make the polymer load capacity to be 0.8 milligram/square centimeter, then 140 ℃ of dryings 1 hour, in air, became solid again in dry 30 minutes then, to obtain to be used for the gas-diffusion electrode of electrode evaluation and test with 200 ℃.

In the acceleration OCV test of carrying out similar to Example 9 of film (P-film) that in use Comparative Examples 1, obtains and above-mentioned gas diffusion electrode, move just sharply rising of hydrogen leakage amount after 60 hours.

Comparative Examples 6

Quicken the OCV test with the gas-diffusion electrode of preparation similar to Example 19, different solution that is to use preparation in the Comparative Examples 5 or dispersion liquid replace the solution or the dispersion liquid of preparation among the embodiment 10.The hydrogen leakage amount sharply rises after 20 hours in operation.

Embodiment 20

Carry out the evaluation and test test of fuel cell, the different 5 weight % solution of copolymer (EW=910 gram/equivalent) shown in the formula (16) that the solution that obtains among the embodiment 10 or dispersion liquid replace being dissolved in water-ethanol (weight ratio=1: 1) that are to use are to prepare electrode ink similar to Example 16ly.The result shows below good initial characteristic---the current density of 1.20 peace/square centimeters and the voltage of 0.6V under 80 ℃ battery temperature.Endurance test shows the durability that is not shorter than 500 hours excellence under 100 ℃ battery temperature.

Embodiment 21

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 80 gram HFC43-10mee, 3.1 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee and 0.05 restrains methyl alcohol, and is forced into 0.30MPa with TFE.Ground similar to Example 1 carries out polymerization 1.5 hours to obtain 8.0 gram white solids at 35 ℃.The MFR of polymer is 72 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 965 gram/equivalents.This film have 145 ℃ Tg and in measuring process in the rapid reduction of 234 ℃ of modulus that demonstrate flexibility, this causes fracture.

With the water absorption of similar this film that records among the embodiment 1 be 41 weight %.The hydration that is obtained by above-mentioned water absorption is 21,200, and the product of hydration and EW is 20.5 * 10 ⁶Change in size between the dry and wet state is 38%.In the hot water resistance test at 160 ℃ similar to Example 1, the weight of this film has reduced by 4% after the test.Show the intensity that pierces through that changes into 50 microns wet coating thicknesses of 132gf with the puncture test of similar this film that in 80 ℃ of water, carries out among the embodiment 1.

Comparative Examples 7

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 80 gram HFC43-10mee, 3.1 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee and 0.08 restrains methyl alcohol, and is forced into 0.3MPa with TFE.Ground similar to Example 1 carries out polymerization 1.6 hours to obtain 9.5 gram white solids at 35 ℃.The MFR of polymer is 600 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 1,035 gram/equivalent.This film have 145 ℃ Tg and in measuring process in the rapid reduction of 178 ℃ of modulus that demonstrate flexibility, this causes fracture.That is to say, compare that the fracture temperature is much lower with embodiment 13.

With the water absorption of similar this film that records among the embodiment 1 be 54 weight %.The hydration that is obtained by above-mentioned water absorption is 32,200, and the product of hydration and EW is 33.3 * 10 ⁶Change in size between the dry and wet state is 59%.

In the hot water resistance test at 160 ℃ similar to Example 1, the weight of this film has reduced by 32% in the process of the test.Show the intensity that pierces through that changes into 50 microns wet coating thicknesses of 44gf with the puncture test of similar this film that in 80 ℃ of water, carries out among the embodiment 1.

When measuring low-angle X-ray scattering among the embodiment 1 similarly, it shows 164 scattering strength and compares I ²/ I ¹

Comparative Examples 8

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂5% (the CF of F, 80 gram HFC43-10mee, 5.32 gram HFC 43-10mee ₃CF ₂CF ₂COO) ₂Solution, and be forced into 0.23MPa with TFE.Ground similar to Example 1 carries out polymerization 1.5 hours to obtain 8.5 gram white solids at 35 ℃.The MFR of polymer is 720 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 843 gram/equivalents.This film have 142 ℃ Tg and in measuring process in the rapid reduction of 163 ℃ of modulus that demonstrate flexibility, this causes fracture.

With the water absorption of similar this film that records among the embodiment 1 be 84 weight %.The hydration that is obtained by above-mentioned water absorption is 33,200, and the product of hydration and EW is 27.8 * 10 ⁶Change in size between the dry and wet state is 90%.

In the hot water resistance test at 160 ℃ similar to Example 1, film is serious damage in process of the test, therefore can't measure its weight.Show the intensity that pierces through that changes into 50 microns wet coating thicknesses of 48gf with the puncture test of similar this film that in 80 ℃ of water, carries out among the embodiment 1.

When measuring low-angle X-ray scattering among the embodiment 1 similarly, it shows 131 scattering strength and compares I ²/ I ¹

Embodiment 9

In the autoclave identical with embodiment 1, ground similar to Example 1 adds 40 gram CF ₂=CFOCF ₂CF ₂CF ₂CF ₂SO ₂F, 80 gram HFC43-10mee, 3.1 gram (CF ₃CF ₂CF ₂COO) ₂5% solution in HFC 43-10mee and 0.06 restrains methyl alcohol, and is forced into 0.30MPa with TFE.Ground similar to Example 1 carries out polymerization 1.5 hours to obtain 9.4 gram white solids at 35 ℃.The MFR of polymer is 204 grams/10 minutes.

With among the embodiment 1 similarly, this polymer is suppressed film forming, saponification and acid treatment, thus obtained-SO ₃The ion exchange capacity of H type film is 986 gram/equivalents.This film have 144 ℃ Tg and in measuring process in the rapid reduction of 189 ℃ of modulus that demonstrate flexibility, this causes fracture.

With the water absorption of similar this film that records among the embodiment 1 be 43.5 weight %.The hydration that is obtained by above-mentioned water absorption is 23,500, and the product of hydration and EW is 23.2 * 10 ⁶Change in size between the dry and wet state is 40%.In the hot water resistance test at 160 ℃ similar to Example 1, the weight of this film has reduced by 12% in the process of the test.

Embodiment 22

Adding dimethylacetylamide (hereinafter being called DMAc) in solution that embodiment 10 obtains or dispersion liquid (No. 1 liquid), refluxed 1 hour at 120 ℃, then at the solution (No. 2 liquid) of evaporator for decompression and concentration with preparation polymer/DMAc=1.5/98.5 (weight ratio).On the other hand, in autoclave, to gather [2,2 '-(metaphenylene)-5,5 '-biphenyl and imidazoles] (Sigma Aldrich Japan Corp. makes, hereinafter be called PBI) be dissolved in DMAc at 200 ℃, and further consist of the solution (No. 3 liquid) of PBI/DMAc=1/99 (weight %) with preparation with the DMAc dilution.

Subsequently, in No. 2 liquid of 10 grams, add No. 3 liquid of 1.63 grams, mix, add No. 1 liquid of 9.7 grams then, stir simultaneously, concentrate to obtain potting syrup 80 ℃ of decompressions.Polymer and the PBI concentration in potting syrup is respectively 5.5 weight % and 0.14 weight %.

This potting syrup cultivated in Petri dish and 60 ℃ of dryings 1 hour, then 80 ℃ dry 1 hour again, be 50 microns casting film 200 ℃ of annealing 1 hour to form thickness then.

To the fragment of 3 centimetres of 3 cm x of downcutting from this film carry out with embodiment 4 similar resolution test.After operation 4 hours, similar each that records hour is the concentration of fluoride constant in collecting liquid.By this data computation 8 hours in the amount of the fluoride ion that so forms be 0.038 weight % of original polymer fluorine total amount, compare with embodiment 7, adding PBI makes this value reduce half.

Embodiment 1,2,3,6,13,14,15 and 21 and Comparative Examples 7,8 and 9 in the MFR that obtains and the relation generalization between the hydration at Fig. 2.

By with embodiment 1 and 15 and the films that obtain of Comparative Examples 7 and 8 be immersed in the low-angle X-alpha spectrum of measuring in the water and be summarised among Fig. 3.

Industrial applicibility

The present invention is based on following discovery: the fluorine with specific side-chain structure and particular range molecular weight Change sulfonic acid polymer can as have excellent chemical stability (non-oxidizability, heat endurance), The material of change in size between high-fire resistance, high proton conductance and high mechanical properties and little dry and wet state Material. The present invention can be used for having excellent durability and is particularly suitable for polymer in high-temperature area work The membrane electrode assembly that electrolyte fuel battery is used is characterized in that using the fluorinated sulfonic polymer as film At least a with catalyst binder, with and the associated components material.

The accompanying drawing summary

Fig. 1 has shown the aerial TGA data of the fluorinated sulfonic polymer in embodiment 1 and the Comparative Examples 2.

Fig. 2 has shown the MFR value of the fluorinated sulfonic polymer shown in the general formula (6) and the relation between the hydration.

Fig. 3 has shown by the film that will contain the fluorinated sulfonic polymer shown in the general formula (6) the low-angle X-alpha spectrum of measuring under water.The content of figure A, B, C and D is represented the spectrum of the film of embodiment 1, Comparative Examples 8, embodiment 15 and Comparative Examples 7 respectively.

Claims

2. according to the membrane electrode assembly of claim 1, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has the ion exchange capacity of 600 to 1,300 gram/equivalents.

3. according to the membrane electrode assembly of claim 1 and 2, it is characterized in that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) has the glass transition temperature that is not less than 130 ℃.

4. according to each membrane electrode assembly of claim 1 to 3, it is characterized in that measuring by TGA, when temperature in air rose with 10 ℃/minute, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) had the thermal decomposition initial temperature that is not less than 330 ℃ and is not higher than 450 ℃.

5. according to each membrane electrode assembly of claim 1 to 4, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when the polymer of film shape continuously with 80 ℃ of water saturated air when contacting 8 hours for 200 ℃, the amount of the fluorine ion of generation is no more than 0.3 weight % of fluorine total amount in the original fluorinated sulfonic polymer.

6. according to each membrane electrode assembly of claim 1 to 5, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), based on sulfonic acid group, the activation energy that uses the density function method to calculate reaction rate-determining step in the thermal oxidation decomposable process that obtains is not less than 40 kilocalories/equivalent and is not higher than 80 kilocalories/equivalent.

7. according to each membrane electrode assembly of claim 1 to 6, it is characterized in that described fluorinated sulfonic polymer contains monomeric unit and the tetrafluoroethylene units shown in the general formula (3) at least.

8. according to each membrane electrode assembly of claim 1 to 7, the monomeric unit shown in its formula of (3) is the monomeric unit shown in the following general formula (4):

Wherein p is 4 to 8 integer.

9. according to the membrane electrode assembly of claim 8, wherein in general formula (4), p is 4 or 6.

10. according to each membrane electrode assembly of claim 1 to 9, wherein use ionic conductivity in 23 ℃ water to be not less than the fluorinated sulfonic polymer of 0.06S/cm.

11., wherein use ionic conductivity in 23 ℃ water to be not less than the fluorinated sulfonic polymer of 0.1S/cm according to each membrane electrode assembly of claim 1 to 9.

12., it is characterized in that it is that the monomeric unit of 4 general formula (4) and having is not higher than 100 scattering strength than (I that the fluorinated sulfonic polymer that uses contains p according to each membrane electrode assembly of claim 1 to 11 ²/ I ¹), I wherein ¹Be the scattering strength under 3 ° 2 θ when measuring polymer under water with small angle x-ray scattering (SAXS), and I ²It is the scattering strength under 0.3 ° 2 θ.

13. contain the film that is used for polymer electrolyte fuel cells of fluorinated sulfonic polymer, this fluorinated sulfonic polymer contains the monomeric unit shown in the following general formula (3):

14. be used for the film of polymer electrolyte fuel cells, it contains the fluorinated sulfonic polymer of the claim 13 that is not less than 60 weight %.

15. be used for the film of polymer electrolyte fuel cells, it is characterized in that containing the fluorinated sulfonic polymer of the claim 13 that is not less than 60 weight %, and further contain be not less than 0.1 weight % and be lower than 40 weight % at least a and be selected from the polymer that contains aryl, contain the polymer of basic group and the material of reinforcement material.

16. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 15, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has 2 * 10 ⁶To 23 * 10 ⁶Ion exchange capacity and the product of hydration.

17. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 16, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has and is not less than 2,000 and be lower than 22,000 hydration.

18. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 17, the fluorinated sulfonic polymer that wherein contains monomeric unit shown in the general formula (3) has the ion exchange capacity of 600 to 1,300 gram/equivalents.

19., it is characterized in that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) has the glass transition temperature that is not less than 130 ℃ according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 18.

20. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 19, it is characterized in that measuring by TGA, when temperature in air rose with 10 ℃/minute, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) had the thermal decomposition initial temperature that is not less than 330 ℃ and is not higher than 450 ℃.

21. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 20, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when the polymer of film shape continuously with 80 ℃ of water saturated air when contacting 8 hours for 200 ℃, the amount of the fluorine ion of generation is no more than 0.3 weight % of fluorine total amount in the original fluorinated sulfonic polymer.

22. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 21, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), based on sulfonic acid group, the activation energy that uses the density function method to calculate reaction rate-determining step in the thermal oxidation decomposable process that obtains is not less than 40 kilocalories/equivalent and is not higher than 80 kilocalories/equivalent.

23., it is characterized in that described fluorinated sulfonic polymer contains monomeric unit and the tetrafluoroethylene units shown in the general formula (3) at least according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 22.

24. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 23, the monomeric unit shown in its formula of (3) is the monomeric unit shown in the following general formula (4):

Wherein p is 4 to 8 integer.

25. according to the film that is used for polymer electrolyte fuel cells of claim 24, wherein in general formula (4), p is 4 or 6.

26., it is characterized in that the ionic conductivity in 23 ℃ water is not less than 0.06S/cm according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 25.

27., it is characterized in that the ionic conductivity in 23 ℃ water is not less than 0.1S/cm according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 25.

28. according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 27, it is characterized in that the fluorinated sulfonic polymer that uses contains the monomeric unit that p is 4 general formula (4), and have and be not higher than 100 scattering strength than (I ²/ I ¹), I wherein ¹Be the scattering strength under 3 ° 2 θ when measuring polymer under water with small angle x-ray scattering (SAXS), and I ²It is the scattering strength under 0.3 ° 2 θ.

29. be used for the membrane electrode assembly of polymer electrolyte fuel cells, it is characterized in that using according to each the film that is used for polymer electrolyte fuel cells of claim 13 to 28.

30. a fluorinated sulfonic polymer, it contains the monomeric unit that p is 6 general formula (4).

32. according to the fluorinated sulfonic polymer solution or the dispersion liquid of claim 31, wherein in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), ion exchange capacity is 600 to 1,300 gram/equivalents.

33., it is characterized in that the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) has the glass transition temperature that is not less than 130 ℃ according to the fluorinated sulfonic polymer solution or the dispersion liquid of claim 31 or 32.

34. according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 33, it is characterized in that measuring by TGA, when temperature in air rose with 10 ℃/minute, the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3) had the thermal decomposition initial temperature that is not less than 330 ℃ and is not higher than 450 ℃.

35. according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 34, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), when the polymer of film shape continuously with 80 ℃ of water saturated air when contacting 8 hours for 200 ℃, the fluorine ion amount of generation is no more than 0.3 weight % of fluorine total amount in the original fluorinated sulfonic polymer.

36. according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 35, it is characterized in that in the fluorinated sulfonic polymer that contains monomeric unit shown in the general formula (3), based on sulfonic acid group, the activation energy that uses the density function method to calculate reaction rate-determining step in the thermal oxidation decomposable process that obtains is not less than 40 kilocalories/equivalent and is not higher than 80 kilocalories/equivalent.

37., it is characterized in that the fluorinated sulfonic polymer contains monomeric unit and the tetrafluoroethylene units shown in the general formula (3) at least according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 36.

38. according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 37, the monomeric unit shown in its formula of (3) is the monomeric unit shown in the following general formula (4):

Wherein p is 4 to 8 integer.

39. according to the fluorinated sulfonic polymer solution or the dispersion liquid of claim 38, wherein in general formula (4), p is 4 or 6.

40., it is characterized in that the ionic conductivity of described fluorinated sulfonic polymer in 23 ℃ water is not less than 0.06S/cm according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 39.

41., it is characterized in that the ionic conductivity of described fluorinated sulfonic polymer in 23 ℃ water is not less than 0.1S/cm according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 40.

42. a method of making the fluorinated sulfonic polymer film is characterized in that using according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 41 forming film by cast.

43., it is characterized in that after forming film, being not less than under the temperature of glass transition temperature and carry out annealing in process by cast according to the method for the manufacturing fluorinated sulfonic polymer film of claim 42.

44. make the method contain the electrolytical gas-diffusion electrode of solid polymerization, it is characterized in that according to each fluorinated sulfonic polymer solution or dispersion liquid and catalyst mix of claim 31 to 41, be coated in then in the substrate and dry.

45. make the method contain the electrolytical gas-diffusion electrode of solid polymerization, it is characterized in that making according to each fluorinated sulfonic polymer solution or dispersion liquid of claim 31 to 41 and immerse and do not contain the electrolytical gas-diffusion electrode of solid polymerization, dry then.

46. the method for an operation of fuel cells is characterized in that using each the fuel cell of membrane electrode assembly of claim 1 to 12 and claim 29 to move being not less than under 80 ℃ the temperature.